Natural Thermal and Magnetic Entanglement in 1D Heisenberg Model

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Liang Guo Stephen L.Hodson Timothy S.FisherXianfan Xu1e-mail:xxu@ School of Mechanical Engineering and Birck Nanotechnology Center,Purdue University,West Lafayette,IN47907Heat Transfer AcrossMetal-Dielectric Interfaces During Ultrafast-Laser Heating Heat transfer across metal-dielectric interfaces involves transport of electrons and pho-nons accomplished either by coupling between phonons in metal and dielectric or by cou-pling between electrons in metal and phonons in dielectric.In this work,we investigate heat transfer across metal-dielectric interfaces during ultrafast-laser heating of thin metalfilms coated on dielectric substrates.By employing ultrafast-laser heating that cre-ates strong thermal nonequilibrium between electrons and phonons in metal,it is possible to isolate the effect of the direct electron–phonon coupling across the interface and thus facilitate its study.Transient thermo-reflectance measurements using femtosecond laser pulses are performed on Au–Si samples while the simulation results based on a two-temperature model are compared with the measured data.A contact resistance between electrons in Au and phonons in Si represents the coupling strength of the direct electron–phonon interactions at the interface.Our results reveal that this contact resist-ance can be sufficiently small to indicate strong direct coupling between electrons in metal and phonons in dielectric.[DOI:10.1115/1.4005255]Keywords:interface thermal resistance,ultrafast laser,thermo-reflectance,two-temper-ature model,electron–phonon coupling1IntroductionInterface heat transfer is one of the major concerns in the design of microscale and nanoscale devices.In metal,electrons,and pho-nons are both energy carriers while in dielectric phonons are the main energy carrier.Therefore,for metal-dielectric composite structures,heat can transfer across the interface by coupling between phonons in metal and dielectric or by coupling between electrons in metal and phonons in dielectric through electron-interface scattering.Phonon–phonon coupling has been simulated mainly by the acoustic mismatch model and the diffuse mismatch model[1].As for electron–phonon coupling,there are different viewpoints.Some studies have assumed that electron–phonon coupling across a metal-dielectric interface is negligible and heat transfer occurs as electron–phonon coupling within metal and then phonon–phonon coupling across the interface[2].Electron–phonon coupling between metal(Cr,Ti,Al,Ni,and Pt)and SiO2 has exhibited negligible apparent thermal resistance using a parallel-strip technique[3].On the other hand,comparison between simulations and transient thermal reflectance(TTR) measurements for Au-dielectric interfaces reveals that energy could be lost to the substrate by electron-interface scattering dur-ing ultrafast-laser heating,and this effect depends on electron temperature and substrate thermal properties[4–6].In this study,we employ TTR techniques to investigate inter-face heat transfer for thin goldfilms of varying thicknesses on sili-con substrates.(Here,we consider silicon as a dielectric since heat is carried by phonons in silicon.)Similar work has been reported [5].In our model,we consider two temperatures in metal and also the temperature in the dielectric substrate.This allows us to inves-tigate the effect of both the coupling between electrons in metal and phonons in the dielectric substrate,and the coupling between phonons in metal and phonons in the dielectric substrate,and allows us to isolate the effect of the electron–phonon coupling across the interface that can be determined from the TTR mea-surement.Experimentally,we employ pulse stretching to mini-mize the effect of nonequilibrium among the electrons.As a result,the experimental data can be well-explained using the com-putational model.The thermal resistance between electrons in Au and phonons in Si,which quantifies the direct electron–phonon coupling strength,is calculated from the measured data.The results reveal that in the thermal nonequilibrium state,this electron–phonon coupling at the interface is strong enough to dominate the overall interface heat transfer.2TTR MeasurementAu–Si samples of varying Au thicknesses were prepared by thermal evaporation at a pressure of the order of10À7Torr.The thicknesses of the goldfilms are39,46,60,77,and250nm,meas-ured using an atomic force microscope.The pump-and-probe technique is used in a collinear scheme to measure the thermo-reflectance signal.The laser pulses are generated by a Spectra Physics Ti:Sapphire amplified femtosecond system with a central wavelength of800nm and a repetition rate of5kHz.The wave-length of the pump beam is then converted to400nm with a sec-ond harmonic crystal.The pump pulse has a pulse width(full width at half maximum-FWHM)of390fs measured by the sum-frequency cross-correlation method and is focused onto the sam-ple with a spot radius of20.3l m.The probe beam has a central wavelength of800nm and a pulse width of205fs measured by autocorrelation and is focused with a spot radius of16.9l m.This pump pulse width is intentionally stretched from the original pulse width of50fs to minimize the influence of thermal nonequili-brium among electrons since the electron thermalization time in Au can be of the order of100fs[7].This thermalization time is pump wavelength and pumpfluence dependent,and can be of the order of10fs if higher laserfluence is used[8,9].Our experiments did show the importance of pulse stretching.Figure1shows the TTR measurement results for the sample of thickness77nm with different pumpfluences before and after stretching the pulse.The plots show the normalized relative reflectance change(ÀD R/R)1Corresponding author.Contributed by the Heat Transfer Division of ASME for publication in the J OURNAL OF H EAT T RANSFER.Manuscript received May18,2011;final manuscript received September30,2011;published online February13,2012.Assoc.Editor: Robert D.Tzou.with the delay time between the pump and the probe pulses to show the contrast in cooling rates.With a shorter pulse (Fig.1(a )),a steep initial drop is seen in the signal,which is attributed to the behavior of nonequilibrium among electrons.Since the TTM to be used for simulation assumes a well-defined tempera-ture for electrons,i.e.,the electrons in gold have reached thermal equilibrium (not necessarily a uniform temperature),the model cannot predict the fast initial drop in the signals in Fig.1(a ).As will be shown later,the signals obtained by stretching the pulse can be predicted well using the TTM.3Two-Temperature Model for Thermal Reflectance MeasurementsUltrafast-laser heating induces thermal nonequilibrium between electrons and phonons in metal,which can be described by the TTM [10–13].We note that the heterogeneous interface consid-ered here involves three primary temperature variables (two in the metal and one in the dielectric).The “two-temperature”model is applied to the metal side.For investigating electron–phonon and phonon–phonon coupling at the interface,two thermal resistances are defined:R es (its reciprocal)indicates the coupling strength between electrons in metal and phonons in dielectric,while R ps indicates the coupling strength between phonons in metal and phonons in dielectric.(Large thermal resistance corresponds to weak coupling.)The resulting governing equations,initial,and interface conditions areC e @T e @t ¼k e @2T e@x2ÀG ðT e ÀT p ÞþS (1a )C p @T p @t ¼k p @2T p @x 2þG ðT e ÀT p Þ(1b )C s @T s @t ¼k s @2T s@x(1c )T e ðt ¼0Þ¼T p ðt ¼0Þ¼T s ðt ¼0Þ¼T 0(2)Àk e@T e @xx ¼L ¼T e ÀT s R es x ¼L(3a )Àk p @T px ¼L ¼T p ÀT s ps x ¼L(3b )Àk s@T sx ¼L ¼T e ÀT s es x ¼L þT p ÀT s ps x ¼L(3c )The subscripts e ,p ,and s denote electrons in metal,phonons in metal,and phonons in the dielectric substrate,respectively.C is the volumetric heat capacity,k is the thermal conductivity,G is the electron–phonon coupling factor governing the rate of energy transfer from electrons to phonons in metal,and L is the thickness of the metal layer.At the front surface of the metal layer insula-tion boundary condition is used due to the much larger heat flux caused by laser heating relative to the heat loss to air.At the rear surface of the substrate,since the thickness of the substrate used is large enough (1l m)so that there is no temperature rise during the time period of consideration,the insulation boundary condition is also applied.Thermal properties of phonons in both metal and dielectric are taken as temperature-independent due to the weak temperature dependence.The thermal conductivity of phonons in metal is much smaller than that of the electrons and is taken in this work as 0.001times the bulk thermal conductivity of gold (311W/(mK)).The volumetric heat capacity of the metal phonon is taken as that of the bulk gold.C e is taken as proportional to T e [14]with the proportion coefficient being 70J/(m 3K 2)[15],and k e is calculated by the model and the data used in Ref.[13]which is valid from the room temperature to the Fermi temperature (6.39Â104K in Au,[14]).G can be obtained using the model derived in Ref.[16].In this work,the value of G at the room tem-perature is taken as 4.6Â1016W/(m 3K)[17],and its dependence on electron and phonon temperatures follows [16].The laser heat-ing source term S is represented by the model used in [13]asS ¼0:94ð1ÀR ÞJ t p ðd þd b Þ1Àexp ÀL d þd bexp Àx d þd b À2:77t t p2"#(4)which assumes all the absorbed laser energy is deposited in the metal layer.J is the fluence of the pump laser,R is the surface re-flectance to the pump,t p is the pulse width (FWHM),d is the opti-cal penetration depth,and d b is the electron ballistic length (around 100nm in Au,[18]).R es and R ps are treated as free pa-rameters for fitting the experimental data.The wavelength of the probe laser in the experiment is centered at 800nm.For this wavelength,the incident photon energy is below the interband transition threshold in Au,which is around 2.47eV [18],and the Drude model can be used to relate the tem-peratures of electrons and phonons to the dielectric function and then the index of refraction,which is expressed as [19]e ¼e 1Àx 2px ðx þi x s Þ(5)x is the frequency of the probe laser and x p is the plasma fre-quency (1.37Â1016rad/s in Au evaluated using the data in Ref.[14]).x s is the electron collisional frequency,the inverse of the electron relaxation time.The temperature dependence ofelectricalFig.1TTR measurement results for the Au–Si sample of Authickness 77nm with different fluences.(a )Results before pulse stretching;(b )results after pulse stretching.resistivity indicates that x s is approximately proportional to pho-non temperature at high temperature [14]and from the Fermi liq-uid theory,its variation with electron temperature is quadratic (T e 2)[20].Therefore,x s is related to T e and T p approximately asx s ¼A ee T 2e þB ep T p(6)A ee is estimated from the low-temperature measurement [21]andB ep is usually estimated from the thermal or electrical resistivity near the room temperature [14].In this work,A ee is taken as the lit-erature value 1.2Â107s À1K À2[6]while e 1and B ep are evaluated by fitting the room-temperature value of the complex dielectric con-stant at 800nm wavelength provided in Ref.[22],which are found to be 9.7and 3.6Â1011s À1K À1,respectively.The complex index of refraction n 0þin 00is the square root of the dielectric ing Eqs.(5)and (6),n 0and n 00are evaluated as 0.16and 4.90,respectively,which agree with the empirical values [23].The re-flectance is then calculated from n 0and n 00by the method of transfer matrix [24],which considers multiple reflections in thin films.4Results and DiscussionThe results of TTR measurements with a pump fluence of 147J/m 2are plotted in Fig.2.The fast decrease of the reflectance indicates that energy transfer between electrons and phonons in metal,followed by a relatively slow decrease after several ps which indicates electrons and phonons have reached thermal equi-librium.The initial cooling rates are smaller for samples with thicknesses less than the electron ballistic length since the electron temperature is almost uniform across the thin film,and coupling with phonons within the metal film and the dielectric substrate is the only cooling mechanism.For a thicker sample of thickness 250nm,the initial decrease is much faster due to thermal diffu-sion in the gold film caused by a gradient of the electron tempera-ture in the film.We investigate the effect of R es and R ps using the thermo-reflectance signal.Two values of R ps ,1Â10À10m 2K/W and 1Â10À7m 2K/W,are used,each with a parameterized range of values for R es .Figure 3shows the calculated results for the sample with a 39nm-thick gold film.Little difference can be seen between Figs.3(a )and 3(b )while different cooling rates are obtained with varying R es in either plot,indicating that the cooling rate is not sensitive to the coupling strength between phonons in metal and dielectric.Note that an interface resistance of 1Â10À10m 2K/W is lower than any reported value,indicating a very high coupling strength between the phonons in metal and dielectric.Conversely,the results vary greatly with the coupling strength between electrons in metal and phonons in dielectric at the interface.This is because the lattice (phonon)temperature rise in metal is much smaller than the elec-tron temperature that the interface coupling between phonons in metal and dielectric does not influence the surface temperature,which directly determines the measured reflectance.On the other hand,the temperature rise of electrons is much higher,and conse-quently,the cooling rate is sensitive to R es .The relatively high sensitivity of R es to that of R ps demonstrates that the former can be isolated for the study of the coupling between electrons in metal and phonons in dielectric.We now use the measured TTR data to estimate R es ,the thermal resistance between electrons in metal and phonons in dielectric.R es is adjusted by the least square method to fit the simulation results with the measured data,and the results are shown in Fig.4.We note that it is impossible to fit the measured results using insu-lation interface condition (i.e.,no coupling or extremely large thermal resistance between electrons in metal and phonons in the dielectric substrate),which will significantly underestimate the cooling rate.For thin samples,we find that the value of R es is of the order of 10À10to 10À9m 2K/W.This value is below the ther-mal resistances of representative solid–solid interfaces measured in thermal equilibrium [25].This indicates that the direct coupling between electrons in metal and phonons in dielectric is strong.It is also noted that the resistance values increases with the thickness of the gold film,indicating a decrease in the coupling strength between electrons in metal and the dielectric substrate.This could be due to the lower electron temperature obtained in thicker films,and a decrease of the coupling strength with a decrease in the electron temperature [5].For the sample of thickness 250nm,R es has little effect on the simulation result since the interface is too far from the absorbing surface to influence the surface tempera-ture,and therefore it is not presented here.The agreement between the fitted results and the measured data is generally good.The small discrepancy between the measured and the fitted results can result from inaccuracy in computingtheFig.2TTR measurement results on Au–Si samples of varying AuthicknessesFig.3Simulation results with varying R es for the Au–Si sample of Au thickness 39nm.(a )R ps 51310210m 2K/W;(b )R ps 5131027m 2K/W.absorption or the temperature.Figure 1(b)shows the normalized TTR measurement results on the sample of thickness 77nm with three laser fluences.It is seen that small variations in the shape of the TTR signals can be caused by different laser fluences and thus the maximum temperature reached in the film.Absorption in metal,multiple reflections between the metal surface and the Au–Si inter-face,and possible deviations of the properties of thin films from those of bulk can all contribute to uncertainties in the temperature simulation;therefore affecting the calculated reflectance.With the values of R es shown in Fig.4,the calculation shows that the highest electron temperature,which is at the surface of 39nm–thick gold film,is about 6700K.The highest temperature of electrons is roughly inversely proportional to the thickness of the films for the four thinner films.The highest temperature of elec-trons is much less than the Fermi temperature and thus ensures the validity of the linear dependence of C e on T e [14].The highest temperature for the lattice in metal is about 780K,also in the 39nm-thick gold film.This large temperature difference between electrons and lattice indicates that the interface heat transfer is dominated by the coupling between electrons in metal and the phonons in the dielectric substrate.As shown in Fig.4,the meas-ured R es is very low,of the order of 10À10to 10À9m 2K/W.Even if R ps ,which is not determined in this study,is also that low (note that 10À10to 10À9m 2K/W is lower than any reported values),because of the large difference in temperatures between electrons and the phonons in metal,the interface heat transfer rate (Eqs.(3a )–(3c ))due to the coupling between electrons in metal and the substrate is much larger than that due to the coupling between phonons in metal and the substrate.5ConclusionsIn conclusion,TTR measurements using femtosecond laser pulses are performed on Au–Si samples and the results are analyzed using the TTM model.It is shown that due to the strong nonequilibrium between electrons and phonons during ultrafast-laser heating,it is possible to isolate the effect of the direct electron–phonon coupling across the interface,allowing investiga-tion of its ing stretched femtosecond pulses is shown to be able to minimize the nonequilibrium effect among electrons,and is thus more suitable for this study.The TTR measurement data can be well-represented using the TTM parison between the TTR data and the TTM results indicates that the direct coupling due to electron-interface scattering dominates the interface heat transfer during ultrafast-laser heating of thin films.AcknowledgmentThis paper is based upon work supported by the Defense Advanced Research Projects Agency and SPAWAR Systems Cen-ter,Pacific under Contract No.N66001-09-C-2013.The authors also thank C.Liebig,Y.Wang,and W.Wu for helpful discussions.NomenclatureA ee ¼coefficient in Eq.(6),s À1K À2B ep ¼coefficient in Eq.(6),s À1K À1C ¼volumetric heat capacity,J/(m 3K)G ¼electron–phonon coupling factor,W/(m 3K)i ¼unit of the imaginary number J ¼fluence of the pump,J/m 2k ¼thermal conductivity,W/(mK)L ¼metal film thickness,mn 0¼real part of the complex index of refractionn 00¼imaginary part of the complex index of refraction R ¼interface thermal resistance,m 2K/W;reflectance S ¼laser source term,W/m3Fig.4Comparison between the measurement and the simulation results for Au–Si samples of different Au thicknesses.The open circle represents the meas-ured data and the solid line represents the simulation results.(a )39nm fitted by R es 55310210m 2K/W;(b )46nm fitted by R es 56310210m 2K/W;(c )60nm fitted by R es 51.231029m 2K/W;and (d )77nm fitted by R es 51.831029m 2K/W.T¼temperature,Kt¼time,st p¼pulse width of the pump(FWHM),sx¼spatial coordinate,me¼complex dielectric constante1¼constant in the Drude modeld¼radiation penetration depth,md b¼electron ballistic depth,mx¼angular frequency of the probe,rad/sx p¼plasma frequency,rad/sx s¼electron collisional frequency,rad/sSubscripts0¼initial statee¼electron in metales¼electron in metal and phonon in dielectricp¼phonon in metalps¼phonon in metal and phonon in dielectrics¼phonon in 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伊朗法尔斯地区第三系砂岩的古地磁

伊朗法尔斯地区第三系砂岩的古地磁

a,
Dominique
Frizon de Lamotte b
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' , C h a r l e s A u b o u r g a,
Jamshid Hassanzadeh
" Universitg de Cergy-Pontoise, Dept. des Sciences de la Terre (CNRS, URAI759), F95011, Cergy-Pontoise Cedex, France I~Institute of Geophysics, Tehran UniversiO, PO. Box 14155-6466, Tehran, lran
Keywords: fold-thrust belt; magnetic fabric; sandstone; weak deformation; Arc of Fars; Zagros (Iran)
1. I n t r o d u c t i o n In sedimentary rocks undergoing horizontal shortening, the initial sedimentary fabric is progressively erased and replaced by a tectonic one (Ramsay and Huber, 1983). The analysis of these initial stages of deformation during which the inherited sedimentary fabric and the tectonic fabric interact, is generally not well documented due to the subtlety of the ini-

里德堡原子微波电场测量

里德堡原子微波电场测量

doi:10.11823/j.issn.1674-5795.2021.01.01里德堡原子微波电场测量白金海,胡栋,贡昊,王宇(航空工业北京长城计量测试技术研究所,北京100095)摘要:里德堡原子是处于高激发态的原子,其主量子数大、寿命高,具有极化率高、电偶极矩大等特点,对外电场十分敏感。

基于热蒸气室中里德堡原子的量子干涉原理(电磁感应透明和Autler-Towns分裂效应)的微波电场精密测量不仅具有远高于传统偶极天线的灵敏度,且具有自校准、对外电场干扰少、测量频率范围大等优点,是下一代电场测量标准。

本文综述了里德堡原子的微波电场测量研究,详细介绍了其基本原理和当前研究进展,并讨论了未来发展方向。

关键词:量子精密测量;里德堡原子;微波电场;电磁感应透明中图分类号:TB97文献标识码:A文章编号:1674-5795(2021)01-0001-09Rydberg Atoms Based Microwave Electric Field SensingBAIJinhai,HU Dong,GONG Hao$WANG Yu(Changcheng Institute of Metrology&Measurement,Beijing100095,China)Abstract:Rydberg atoms are the atoms in highly excited states with lar-e principaO quantum numbers n,and long lifetimes.The lar-e Ryd-ber-atom polarizabilitu and strong dipole transitions between enereetically nearby states are highly sensitive to electris fielOs.The new developed scheme for microwave electric field precision measurement is based on quantum interference effects(electromaaneticclly induced transparency and Autler-Townes splitting)in Rydbere atoms contained in a dielectric vapoe cell.The mininium measured strengths of microwave electric fieies of the new scheme are far below the standard values obtained by traditional antenna methods.And it has several advantages,such as self-calibra­tion,non-perturbation to the measured field,a broadband measurement frequency range,etc,is the next-generation electric field standard.In this review,we describe work on the new method for measuring microwave electric field based on Rydberg atoms.We introducc the basic theory and experimental techniques of the new method,and discuss the future development direction.Key words:quantum precision measurement;Rydberg atoms;microwave electric fielO;electromagnetically induced transparency0引言原子是一种典型的量子体系,具有可复现、性能稳定、能级精确等优点。

压电材料的研究新进展

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压电材料发展的类型主要有单晶、多晶、微晶玻璃、有机高分子、复合材料等。

20世纪80年代以来,随着压电陶瓷材料从二元系向三元、多元系的开发研究高潮的结束,压电材料的研究一度进展缓慢。

随着科学技术快速发展,应用需求牵引下的开发探索给予了压电材料研究的新动力,加上科技工作者在基础性研究和生产工艺改进上的不懈努力,近十几年来,新型的压电材料不断涌现出,并呈现出无铅化、高性能化、薄膜化的态势,使得压电材料研究的面貌焕然一新,带动相应的应用器件研究也日趋活跃。

本文就近些年来国内外压电材料技术研究中所呈现出的新趋势和最新进展进行介绍,并对今后研究的努力发展方向进行展望,并提出一些建议。

2 压电材料研究的新趋势2.1 无铅化随着环境保护和社会可持续发展的要求,发展环境协调性材料及技术已是公认的大势所趋。

为了防止环境污染,国内外科研人员对无铅压电材料开展了大量的研究工作并取得了令人鼓舞的进展[2]。

太赫兹波段超材料的制作、设计及应用

太赫兹波段超材料的制作、设计及应用

第6卷 第3期2013年6月  中国光学 Chinese Optics Vol.6 No.3June 2013 收稿日期:2013⁃02⁃17;修订日期:2013⁃04⁃15 基金项目:国家自然科学基金资助项目(No.10834015;No.61077082);陕西省科技新星资助项目(No.2012KJXX⁃27);陕西省光电技术与功能材料省部共建国家重点实验室培育基地基金资助项目(No.ZS12018)文章编号 1674⁃2915(2013)03⁃0283⁃14太赫兹波段超材料的制作、设计及应用潘学聪1,姚泽瀚2,徐新龙1,2∗,汪 力1(1.中国科学院物理研究所北京凝聚态物理国家实验室,北京100190;2.西北大学光子学与光子技术研究所光电技术与功能材料国家重点实验室培育基地,陕西西安710069)摘要:本文从制作方法、结构设计和材料选择几方面综述了超材料在太赫兹波段的电磁响应特性和潜在应用。

首先,介绍了获得不同维度、具有特异电磁响应以及结构可调超材料的各种微加工制作方法,进而分析和讨论了超材料的电磁响应特性。

文中指出,结构设计可以控制超材料的电磁响应特性,如各向异性、双各向异性、偏振调制、多频响应、宽带响应、不对称透射、旋光性和超吸收等。

超材料的电磁响应依赖于周围微环境的介电性质,因而可用于制作对环境敏感的传感器件。

此外,电光、磁光、相变、温度敏感等功能材料的引入可以获得光场、电场、磁场、温度等主动控制的太赫兹功能器件。

最后,简单介绍了超材料在太赫兹波段进一步发展所面临的机遇和挑战。

关 键 词:超材料;太赫兹技术;结构设计;调制;偏振中图分类号:O441;TB34 文献标识码:A doi:10.3788/CO.20130603.0283Fabrication ,design and application of THz metamaterialsPAN Xue⁃cong 1,YAO Ze⁃han 2,XU Xin⁃long 1,2∗,WANG Li 1(1.Beijing National Laboratory for Condensed Matter Physics ,Institute of Physics ,Chinese Academy of Sciences ,Beijing 100190,China ;2.State Key Laboratory Incubation Base of Photoelectric Technology and Functional Materials ,Institute of Photonics &Photon⁃Technology ,Northwest University ,Xi′an 710069,China )∗Corresponding author ,E⁃mail :xlxuphy@ Abstract :In this paper,the electromagnetic responses and potential applications of THz metamaterials are re⁃viewed through the focus on fabrication,unit structure design,and material selection,respectively.It de⁃scribes different kinds of fabrication technologies for obtaining metamaterials with special electromagnetic re⁃sponses such as magnetic resonance and reconfigurable tunability,which is helpful for further understanding of electromagnetic resonances in metamaterials.The paper analyzes the electromagnetic response characteristics in detail and points out that the unit structure design can be used to obtain desired electromagnetic characteris⁃tics,such as anisotropy,bianisotropy,polarization modulation,multiband response,broadband response,asymmetric transmission,optical activity,and perfect absorption,etc .The dependence of electromagnetic re⁃sponses upon surrounding dielectrics can be used not only to control resonant frequency by a proper substrateselection,but also for sensing applications.Furthermore,the introduction of functional materials with control⁃lable dielectric properties by external optical field,electrical field,magnetic field and temperature has the po⁃tential to achieve tunable metamaterials,which is highly desirable for THz functional devices.Finally,the op⁃portunities and challenges for further developments of THz metamaterials are briefly introduced.Key words:metamaterials;THz technology;structure design;modulation;polarization1 引 言 通过对自然材料的裁剪、加工和设计,从而实现对电子、光子以及其他一些元激发准粒子的人为调控,一直是光电科学研究的重点。

advanced optical materials分区

advanced optical materials分区

Advanced Optical MaterialsIntroductionAdvanced optical materials are a class of materials that possess unique optical properties and are engineered to enhance light-matter interactions. These materials have revolutionized various fields such as photonics, optoelectronics, and nanotechnology. In this article, we will explore the different types of advanced optical materials, their applications, and the future prospects of this exciting field.Types of Advanced Optical MaterialsPhotonic CrystalsPhotonic crystals are periodic structures that can manipulate the propagation of light. They consist of a periodic arrangement ofdielectric or metallic components with alternating refractive indices. These structures can control the flow of light by creating energy bandgaps, which prohibit certain wavelengths from propagating through the material. Photonic crystals find applications in optical communication, sensing, and solar cells.MetamaterialsMetamaterials are artificially engineered materials that exhibit properties not found in nature. They are composed of subwavelength-sized building blocks arranged in a periodic or random manner. Metamaterials can manipulate electromagnetic waves by achieving negative refractive index, perfect absorption, and cloaking effects. These unique properties have led to applications in invisibility cloaks, super lenses, and efficient light harvesting.Plasmonic MaterialsPlasmonic materials exploit the interaction between light and free electrons at metal-dielectric interfaces to confine light at nanoscale dimensions. This confinement results in enhanced electromagnetic fields known as surface plasmon resonances. Plasmonic materials have diverse applications such as biosensing, photothermal therapy, and enhanced solar cells.Quantum DotsQuantum dots are nanoscale semiconductor crystals with unique optical properties due to quantum confinement effects. Their size-tunable bandgap enables them to emit different colors of light depending ontheir size. Quantum dots find applications in display technologies (e.g., QLED TVs), biological imaging, and photovoltaics.Organic Optoelectronic MaterialsOrganic optoelectronic materials are based on organic compounds that exhibit electrical conductivity and optical properties. These materials are lightweight, flexible, and can be processed at low cost. They find applications in organic light-emitting diodes (OLEDs), organic photovoltaics (OPVs), and organic field-effect transistors (OFETs).Applications of Advanced Optical MaterialsInformation TechnologyAdvanced optical materials play a crucial role in information technology. Photonic crystals enable the miniaturization of optical devices, leading to faster and more efficient data transmission. Metamaterials offer possibilities for creating ultra-compact photonic integrated circuits. Plasmonic materials enable the development of high-density data storage devices.Energy HarvestingAdvanced optical materials have revolutionized energy harvesting technologies. Quantum dots and organic optoelectronic materials are used in next-generation solar cells to enhance light absorption and efficiency. Plasmonic nanoparticles can concentrate light in solar cells, increasing their power output. These advancements contribute to the development of sustainable energy sources.Sensing and ImagingThe unique optical properties of advanced optical materials make them ideal for sensing and imaging applications. Quantum dots are used as fluorescent probes in biological imaging due to their bright emissionand excellent photostability. Metamaterial-based sensors offer high sensitivity for detecting minute changes in refractive index ormolecular interactions.Biomedical ApplicationsAdvanced optical materials have significant implications in biomedical research and healthcare. Plasmonic nanomaterials enable targeted drug delivery, photothermal therapy, and bioimaging with high spatial resolution. Organic optoelectronic materials find applications in wearable biosensors, smart bandages, and flexible medical devices.Future ProspectsThe field of advanced optical materials is rapidly evolving with continuous advancements being made in material synthesis, characterization techniques, and device fabrication processes. Thefuture prospects of this field are promising, with potential breakthroughs in areas such as:1.Quantum Optics: Integration of advanced optical materials withquantum technologies could lead to the development of quantumcomputers, secure communication networks, and ultra-precisesensors.2.Flexible and Wearable Electronics: Organic optoelectronicmaterials offer the potential for flexible and wearable electronic devices, such as flexible displays, electronic textiles, andimplantable medical devices.3.Optical Computing: Photonic crystals and metamaterials may pavethe way for all-optical computing, where photons replace electrons for faster and more energy-efficient data processing.4.Enhanced Optoelectronic Devices: Continued research on advancedoptical materials will lead to improved performance and efficiency of optoelectronic devices such as solar cells, LEDs, lasers, andphotodetectors.In conclusion, advanced optical materials have opened up newpossibilities in various fields by enabling unprecedented control over light-matter interactions. The ongoing research and development in this field promise exciting advancements in information technology, energy harvesting, sensing and imaging, as well as biomedical applications. The future looks bright for advanced optical materials as they continue to revolutionize technology and shape our world.。

泰山医学院材料导论题库

泰山医学院材料导论题库

泰山医学院《材料导论》试题库1、The nucleus of an atom containsA ProtonsB ElectronsC NeutronsD All of the abovev E Both A and C2、What type(s) of electron subshell(s) does an L shell contain?A a p f sB s and fv C s and p3、What is the maximum number of electrons that an M shell may contain?v A.18B.32C.84、Match the electron structure below with the element type it represents.1s22s22p63s23p63d104s1A. Inert gasB. HalogenC. Alkali metalD. Alkaline earth metalv E. Transition metal5、What is the predominant type of bonding for titanium (Ti)?A. IonicB. HydrogenC. CovalentD. van der Waalsv E. Metallic6、Of those elements in the list situated below the periodic table, select the one that is one electron short of having its outer shell of electrons completely filled.v A. IB. NC. SD. SrE. Ar7、Which of the following materials may form crystalline solids?A. PolymersB. MetalsC. Ceramicsv D. All of the above8、Which of the following are the most common coordination numbers for ceramic materials?A. 2B. 3 and 6C. 4 and 12v D. 4,6 and 89、Which crystal system(s) listed below has (have) the following relationship for the unit cell edge lengths?a =b ≠cA. CubicB. HexagonalC. TriclinicD. MonoclinicE. RhombohedralF. OrthorhombicG. Tetragonalv H. Both C and E10、Which crystal system(s) listed below has (have) the following interaxial angle relationship? α= β = γ = 90°v A. CubicB. HexagonalC. TriclinicD. MonoclinicE. RhombohedralF. OrthorhombicG. Both A and D11、把a、b、c、d四块金属片浸入稀硫酸中,用导线两两相连组成原电池。

Effect of alloying elements on the microstructure and mechanical properties of nanostructured

Effect of alloying elements on the microstructure and mechanical properties of nanostructured

LetterEffect of alloying elements on the microstructure and mechanical properties of nanostructured ferritic steels produced by spark plasmasinteringSomayeh Pasebani,Indrajit Charit ⇑Department of Chemical and Materials Engineering,University of Idaho,Moscow,ID 83844,USAa r t i c l e i n f o Article history:Received 23November 2013Received in revised form 23January 2014Accepted 29January 2014Available online 15February 2014Keywords:NanostructuresMechanical alloying Powder metallurgyTransmission electron microscopy High temperature alloya b s t r a c tSeveral Fe–14Cr based alloys with varying compositions were processed using a combined route of mechanical alloying and spark plasma sintering.Microstructural characteristics of the consolidated alloys were examined via transmission electron microscopy and atom probe tomography,and mechanical prop-erties evaluated using microhardness nthanum oxide (0.5wt.%)was added to Fe–14Cr leading to improvement in microstructural stability and mechanical properties mainly due to a high number den-sity of La–Cr–O-enriched nanoclusters.The combined addition of La,Ti (1wt.%)and Mo (0.3wt.%)to the Fe–14Cr base composition further enhanced the microstructural stability and mechanical properties.Nanoclusters enriched in Cr–Ti–La–O with a number density of 1.4Â1024m À3were found in this alloy with a bimodal grain size distribution.After adding Y 2O 3(0.3wt.%)along with Ti and Mo to the Fe–14Cr matrix,a high number density (1.5Â1024m À3)of Cr–Ti–Y–O-enriched NCs was also detected.For-mation mechanism of these nanoclusters can be explained through the concentrations and diffusion rates of the initial oxide species formed during the milling process and initial stages of sintering as well as the thermodynamic nucleation barrier and their enthalpy of formation.Ó2014Elsevier B.V.All rights reserved.1.IntroductionNanostructured ferritic steels (NFSs),a subcategory of oxide dis-persion strengthened (ODS)steels,have outstanding high temper-ature strength,creep strength [1,2]and excellent radiation damage resistance [3].These enhanced properties of NFSs have been attrib-uted to the high number density of Y–Ti–O-enriched nanoclusters (NCs)with diameter of 1–2nm [4].The Y–Ti–O-enriched NCs have been found to be stable under irradiation and effective in trapping helium [5].These NCs are formed due to the mechanical alloying (MA)of Fe–Cr–Ti powder with Y 2O 3during high energy ball milling followed by hot consolidation route such as hot isostatic pressing (HIP)or hot extrusion [6–8].Alinger et al.[4]have investigated the effect of alloying elements on the formation mechanism of NCs in NFSs processed by hot isostatic pressing (HIP)and reported both Ti and high milling energy were necessary for the formation of ler and Parish [9]suggested that the excellent creep properties in yttria-bearing NFSs result from the pinning of thegrain boundaries by a combined effect of solute segregation and precipitation.Although HIP and hot extrusion are commonly used to consoli-date the NFSs,anisotropic properties and processing costs are con-sidered challenging issues.Recently,spark plasma sintering (SPS)has been utilized to sinter the powder at a higher heating rate,low-er temperature and shorter dwell time.This can be done by apply-ing a uniaxial pressure and direct current pulses simultaneously to a powder sample contained in a graphite die [10].Except for a few studies on consolidation of simple systems such as Fe–9Cr–0.3/0.6Y 2O 3[11]and Fe–14Cr–0.3Y 2O 3[10],the SPS process has not been extensively utilized to consolidate the NFSs with complex compositions.Recently,the role of Ti and Y 2O 3in processing of Fe–16Cr–3Al–1Ti–0.5Y 2O 3(wt.%)via MA and SPS was investigated by Allahar et al.[12].A bimodal grain size distribution in conjunc-tion with Y–Ti–O-enriched NCs were obtained [12,13].In this study,Fe–14Cr (wt.%)was designed as the base or matrix alloy,and then Ti,La 2O 3and Mo were sequentially added to the ferritic matrix and ball milled.This approach allowed us to study the effect of individual and combined addition of solutes on the formation of NCs along with other microstructural evolutions.Furthermore,SPS instead of other traditional consolidation methods was used to consolidate the NFS powder.The mixture/10.1016/j.jallcom.2014.01.2430925-8388/Ó2014Elsevier B.V.All rights reserved.⇑Corresponding author.Tel.:+12088855964;fax:+12088857462.E-mail address:icharit@ (I.Charit).of Fe–Cr–Ti–Mo powder with Y2O3was also processed and characterized in a similar manner for comparison with the rest of the developed alloys.2.ExperimentalThe chemical compositions of all the developed alloys along with their identi-fying names in this study are given in Table1.High energy ball milling was per-formed in a SPEX8000M shaker mill for10h using Ar atmosphere with the milling media as steel balls of8mm in diameter and a ball to powder ratio(BPR) of10:1.A Dr.Sinter Lab SPS-515S was used to consolidate the as-milled powder at different temperatures(850,950and1050°C)for7min using the pulse pattern 12–2ms,a heating rate of100°C/min and a pressure of80MPa.The SPSed samples were in the form of disks with8mm in height and12mm in diameter.The density of the sintered specimens was measured by Archimedes’method. Vickers microhardness tests were performed using a Leco LM100microhardness tester operated at a load of1000g–f(9.8N).A Fischione Model110Twin-Jet Elec-tropolisher containing a mixture of CH3OH–HNO3(80:20by vol.%)as the electrolyte and operated at aboutÀ40°C was used to prepare specimens for transmission elec-tron microscopy(TEM).A FEI Tecnai TF30–FEG STEM operating at300kV was used. The energy dispersive spectroscopy(EDS)attached with the STEM was used to roughly examine the chemical composition of the particles.A Quanta3D FEG instrument with a Ga-ion source focused ion beam(FIB)was used to prepare spec-imens for atom probe tomography(APT)studies on14L,14LMT and14YMT sam-ples.The APT analysis was carried out using a CAMECA LEAP4000X HR instrument operating in the voltage mode at50–60K and20%of the standing volt-age pulse fraction.The atom maps were reconstructed using CAMECA IVAS3.6soft-ware and the maximum separation algorithm to estimate the size and chemical composition of NCs.This was applied to APT datasets each containing20–30million ions for each specimen.Lower evaporationfield of the nanoparticles and trajectory aberrations caused estimation of higher Fe atoms in the nanoclusters.Although the contribution of Fe atoms from the matrix was examined here,the matrix-correction was not addressed in this study.3.Results and discussionThe TEM brightfield micrographs for the various alloys SPSed at 950°C for7min are illustrated in Fig.1a–d.The microstructure of 14Cr alloy shown in Fig.1a revealed a complex microstructure with submicron subgrain-like structures,relatively high density of dislocations and low number density of oxide nanoparticles. The nanoparticles were larger(25–65nm)than the other SPSed al-loys and found to have chemical compositions close to Cr2O3and FeCr2O4as analyzed by energy dispersive spectroscopy.The microstructure of the consolidated14L alloy is shown in Fig.1b.The microstructure consisted of more ultrafine grains (<1l m but>100nm),a few nanograins with sharp boundaries and a higher number of nanoparticles mainly in the grain interiors. The number density of nanoparticles was higher than that of14Cr alloy shown in Fig.1a but lower than14LMT(Fig.1c)and14YMT (Fig.1d).In14L alloy,the nanoparticles with2–11nm in diameter were found inside the grains(hard to be observed at magnification given in Fig.1b and micrographs taken at higher magnifications was used for this purpose)whereas the nanoparticles with 50–80nm in diameter were located at the grain boundary regions. The particles on the boundaries are likely to be mainly Cr2O3and LaCrO3,but the chemical analysis of those smallest particles could not be done precisely due to the significant influence of the ferritic matrix.Fig.1c shows the microstructure of the SPSed14LMT alloy, consisting of both ultrafine grains(as defined previously)and nanograins(6100nm).The nanoparticles present in the micro-structure were complex oxides of Fe,Cr and Ti.The nanoparticles with faceted morphology and smaller than10nm in diameter were enriched in La and Ti.No evidence of stoichiometric La2TiO5or La2Ti2O7particles was observed based on the EDS and diffraction data.A similar type of microstructure was revealed in the SPSed 14YMT alloy as shown in Fig.1d.The particle size distribution histograms of the14Cr,14L, 14LMT and14YMT alloys are plotted in Fig.2a–d,respectively. Approximately1000particles were sampled from each alloy to de-velop the histograms.The average particle size decreased in order of14Cr,14L,14LMT and14YMT.The highest fraction of the particle size as shown in the histograms of14Cr,14L,14LMT and14YMT was found to be associated with25±5nm(18±2.5%),10±5nm (28±3%),5±1nm(40±6%)and5±1nm(46±5%)in diameter, respectively.The number density of nanoparticles smaller than 5±1nm was higher in14YMT than14LMT alloy.The3-D APT maps for14L alloy revealed a number density (%3Â1022mÀ3)of CrO–La–O-enriched NCs.The average Guinier radius of these NCs was1.9±0.6nm.The average composition of the NCs in14L was estimated by using the maximum separation algorithm to be Fe–17.87±3.4Cr–32.61±3.2O–8.21±1.1La(at.%).A higher number density(%1.4Â1024mÀ3)and smaller NCs with average Guinier radius of 1.43±0.20nm were observed in the APT maps for14LMT alloy as shown in Fig.3a.The NCs were Cr–Ti–La–O-enriched with the average composition of Fe–10.9±2.8Cr–30.9±3.1O–17.3±2.5Ti–8.2±2.2La(at.%).According to the LEAP measurements,the chemical composition of NCs dif-fered considerably from stoichiometric oxides.A large amount of Fe and Cr was detected inside the NCs,and La/Ti and La/O ratios were not consistent with La2TiO5or La2Ti2O7as expected based on thermodynamic calculations,rather the ratios were sub-stoichi-ometric.The3-D APT maps for14YMT alloy were similar to14YMT alloy as shown in Fig.3b.The NCs with an average radius of 1.24±0.2nm and a number density of1.5Â1024mÀ3were Cr–Ti–Y–O-enriched.The chemical composition of NCs was estimated close to Fe–8.52±3.1Cr–37.39±4.5O–24.52±3.1Ti–10.95±3.1Y (at.%).The matrix-corrected compositions are currently being ana-lyzed and will be reported in a full-length publication in near future.The relative density of various alloys sintered at850–1050°C is shown in Fig.4a.Generally,a higher density was obtained in the specimens sintered at higher temperatures.At850and950°C, the density of unmilled14Cr specimen(97.2%and97.5%)was higher than the milled/SPSed14Cr(92.8%and95.5%)because the unmilled powder particles were less hard(due to absence of strain hardening)and plastically deformed to a higher degree than the milled powder leading to a higher density.Adding0.5and 0.7wt.%of La2O3and0.3wt.%Y2O3to the14Cr matrix significantly decreased the density of the specimen,especially at850and 950°C;however,adding Ti to14L and14Y improved the density to some extent.The microhardness data of various alloys processed at different temperatures are shown in Fig.4b.In general,microhardness in-creased with increasing SPS temperatures up to950°C and then decreased.Both Y and La increased the hardness due to the disper-sion hardening effect.The hardness increased at the higher content of La due to the greater effect of dispersion hardening.Adding Ti separately to the14Cr matrix improved the hardness due to theTable1The alloy compositions and processing conditions(milled for10h and SPSed at850-1050°C for7min).Alloy ID Elements(wt.%)Cr Ti La2O3Y2O3Mo Fe14Cr-unmilled140000Bal.14Cr140000Bal.14T141000Bal.14L1400.500Bal.14Y14000.30Bal.14LM1400.500.3Bal.14LT1410.500Bal.14LMT(0.3)1410.300.3Bal.14LMT1410.500.3Bal.14LMT(0.7)1410.700.3Bal.14YMT14100.30.3Bal.S.Pasebani,I.Charit/Journal of Alloys and Compounds599(2014)206–211207dispersion hardening but only at lower temperature(850°C).The coarsening of Ti-enriched particles at above850°C plausibly decreased the hardness.However,at950°C,higher hardness (457HV)was achieved by a combined addition of La and Ti toFig.2.Particle size frequency histogram for(a)14Cr,(b)14L,(c)14LMT and(d)14YMT alloys. Fig.1.TEM brightfield micrographs for various alloys(a)14Cr,(b)14L,(c)14LMT and(d)14YMT.the14Cr matrix to produce14LT.Further addition of Mo to14LT improved the hardness through solid solution strengthening in 14LMT(495HV).High dislocation density and no well-defined grain boundaries were characteristics of14Cr alloy as shown in Fig.1a.The presence of a low number density and larger oxide particles(FeCr2O4and Cr2O3)at the boundaries could not create an effective pinning effect during sintering.As a result,some of these particles became confined within the grain interiors.The coarse grains had the capacity to produce and store high density of dislocations that subsequently resulted in the strain hardening effect.The hardening mechanism in14Cr alloy can thus be attributed to greater disloca-tion activities and resulting strain hardening effect.The grain boundary or precipitation hardening cannot be the dominant mechanism because of larger particles,greater inter-particle spac-ing and weakened Zener drag effect at the temperature of sinter-ing.Such strain hardening capability in nanocrystalline Fe consolidated via SPS was reported by other researchers,too [14,15].Interestingly,the high hardness in Fe–14Cr alloy consoli-dated via SPS at1100°C for4min by Auger et al.[10]wasFig.3.Three-dimensional atom maps showing NCs for(a)14LMT–91Â34Â30nm3and(b)14YMT–93Â30Â30nm3.Fig.4.(a)The relative density and(b)microhardness values for different SPSed alloys processed at different SPS temperatures for a dwell time of7min.attributed to the formation of martensitic laths caused by higher carbon content diffusing from the die,possible Cr segregation and rapid cooling during SPS.It is noteworthy to mention that no martensite lath was observed in the consolidated14Cr alloy in the present study.The level of solutes in the bcc matrix could be much greater than the equilibrium level,associated with a large number of vacancies created during milling.Our recent study[16]has shown that high energy ball milling has a complex role in initiating nucle-ation of La–Ti–O-enriched NCs in14LMT alloy powder,with a mean radius of%1nm,a number density of3.7Â10À24mÀ3and a composition of Fe–12.11Cr–9.07Ti–4.05La(at.%).The initiation of NCs during ball milling of NFSs has also been investigated by other researchers[8,17,18].According to Williams et al.[8],due to a low equilibrium solubility of O in the matrix,the precipitation of nanoparticles is driven by an oxidation reaction,subsequently resulting in reduction of the free energy.As the SPS proceeds,the number density of NCs would decrease and larger grain boundary oxides would form with the grain structure developing simulta-neously during the sintering process[8].Formation of larger grain boundary oxides as shown in Fig.1a could have been preceded by segregation of O and Cr to grain boundaries leading to a decrease in the level of the solutes in the ferritic matrix.The initial oxides forming in a chromium-rich matrix can be Cr2O3as suggested by Williams et al.[8].However,formation of LaCrO3in14L alloy (shown in Fig.1b)was associated with a higher reduction in the free energy according to the enthalpy of formation of various oxi-des given in Table2.The presence of nanoparticles caused grain boundary pinning and subsequently stabilized the nanocrystalline grains.The high density of defects(dislocations and vacancies)in a supersaturated solid solution,such as14LMT and14YMT alloys, could dramatically increase the driving force for accelerated sub-grain formation during the initial stage of sintering.At the initial stage,the vacancies created during the milling are annihilated [8,17].Meanwhile,the temperature is not high enough to produce a significant number of thermal vacancies;subsequently,any nucleation of new NCs will be prevented.As the SPS proceeds with no nucleation of new NCs,the high concentrations of extra solutes in the matrix are thermodynamically and kinetically required to precipitate out to form larger oxide particles.The larger solute-enriched oxide particles can be formed more favorably on the grain boundaries due to the higher boundary diffusivity.On the other hand,it should be considered that there is a dynamic plastic deformation occurring within the powder particles during SPS. The interaction of larger particles and dislocations introduced by dynamic hot deformation can explain the coarsening in some grains;because larger particles could not effectively pin the dislo-cations and the grain boundary migration could be facilitated fol-lowing the orientation with lower efficiency of Zener drag mechanism[19].Once the extra solutes present in the matrix pre-cipitated out,the microstructure will remain very stable because of the grain boundary pinning by triple-junctions of the grain bound-aries themselves[20],along with the high density of NCs and other ultrafine oxide particles[8].Further coarsening of the grains will be prevented even for longer dwell times at950°C.Therefore,a bi-modal grain size distribution emerged.The hardening of14LMT and14YMT alloys were attributed to a combined effect of solid solution strengthening,Hall-Petch strengthening and precipitation hardening.Based on the APT studies of the as-milled powder[16]and for-mation mechanism of the oxide particles suggested by Williams et al.[8]it could be speculated that in14LMT and14YMT alloys, Cr–O species formfirst and then absorb Ti and La/Y.This is associ-ated with a change in the interfacial energy of Cr–O species even though it is not thermodynamically the most favorable oxide.It has been established that the driving force for the oxide precipi-tates to form is the low solubility limit of oxygen in the ferritic ma-trix.The change in free energy due to oxidation reaction and nucleation of oxide nanoparticles is the leading mechanism[8].The majority of the oxygen required to generate the oxide nano-particles may be provided from the surface oxide during milling process.Furthermore,higher concentrations of Cr led to greater nucleation of Cr–O by influencing the kinetics of oxide formation. Concentrations and diffusivities of the oxide species along with the energy barrier for nucleation will control the nucleation of oxide nanoparticles.After the Cr–O formed during sintering,the Ti–O and Y/La-enriched clusters could form.The sub-stoichiome-tric NCs in14LMT and14YMT alloys were not due to insufficient level of O in the matrix[8].Formation of stoichiometric Y2Ti2O7 and Y2TiO5requires very high temperatures[8],which were outside the scope of this study.4.ConclusionThe SPSed Fe–14Cr alloy was found to have a higher hardness at room temperature due to the strain hardening effect.The stability of its microstructure at high temperatures was improved by addi-tion of La forming the Cr–La–O-enriched NCs.Adding La and Ti to Fe–14Cr matrix significantly improved the mechanical behavior and microstructural stability further due to the high number density of Cr–Ti–La–O-enriched NCs in14LMT alloy.It is demon-strated that the potential capability of La in developing new NFSs is promising but further investigations on their thermal and irradiation stability will still be required.AcknowledgementThis work was supported partly by the Laboratory Directed Research and Development Program of Idaho National Laboratory (INL),and by the Advanced Test Reactor National Scientific User Facility(ATR NSUF),Contract DE-AC07-05ID14517.The authors gratefully acknowledge the assistance of the staff members at the Microscopy and Characterization Suite(MaCS)facility at the Center for Advanced Energy Studies(CAES).References[1]M.J.Alinger,G.R.Odette,G.E.Lucas,J.Nucl.Mater.307–311(2002)484.[2]R.L.Klueh,J.P.Shingledecker,R.W.Swindeman,D.T.Hoelzer,J.Nucl.Mater.341(2005)103.[3]M.J.Alinger,G.R.Odette,D.T.Hoelzer,J.Nucl.Mater.329–333(2004)382.[4]M.J.Alinger,G.R.Odette,D.T.Hoelzer,Acta Mater.57(2009)392.Table2The standard enthalpies of formation of various oxide compounds at25°C[8,21,22].Element CompositionÀD H f(kJ molÀ1(oxide))Cr Cr2O31131CrO2583Fe Fe3O41118Fe2O3822Ti TiO543TiO2944Ti2O31522Ti3O52475Y Y2O31907YCrO31493Y2Ti2O73874La La2O31794La2Ti2O73855LaCrO31536210S.Pasebani,I.Charit/Journal of Alloys and Compounds599(2014)206–211[5]G.R.Odette,M.L.Alinger,B.D.Wirth,Annu.Rev.Mater.Res.38(2008)471.[6]ai,T.Okuda,M.Fujiwara,T.Kobayashi,S.Mizuta,H.Nakashima,J.Nucl.Sci.Technol.39(2002)872.[7]ai,M.Fujiwara,J.Nucl.Mater.307–311(2002)749.[8]C.A.Williams,P.Unifantowicz,N.Baluc,G.D.Smith,E.A.Marquis,Acta Mater.61(2013)2219.[9]ler,C.M.Parish,Mater.Sci.Technol.27(2011)729.[10]M.A.Auger,V.De Castro,T.Leguey,A.Muñoz,Pareja,R,J.Nucl.Mater.436(2013)68.[11]C.Heintze,M.Hernández-Mayoral, A.Ulbricht, F.Bergner, A.Shariq,T.Weissgärber,H.Frielinghaus,J.Nucl.Mater.428(2012)139.[12]K.N.Allahar,J.Burns,B.Jaques,Y.Q.Wu,I.Charit,J.I.Cole,D.P.Butt,J.Nucl.Mater.443(2013)256.[13]Y.Q.Wu,K.N.Allahar,J.Burns,B.Jaques,I.Charit,D.P.Butt,J.I.Cole,Cryst.Res.Technol.(2013)1,/10.1002/crat.201300173.[14]K.Oh-Ishi,H.W.Zhang Hw,T.Ohkubo,K.Hono,Mater.Sci.Eng.A456(2007)20.[15]B.Srinivasarao,K.Ohishi,T.Ohkubo,K.Hono,Acta Mater.57(2009)3277.[16]S.Pasebani,I.Charit,Y.Q.Wu, D.P.Butt,J.I.Cole,Acta Mater.61(2013)5605.[17]M.L.Brocq,F.Legendre,M.H.Mathon,A.Mascaro,S.Poissonnet,B.Radiguet,P.Pareige,M.Loyer,O.Leseigneur,Acta Mater.60(2012)7150.[18]M.Brocq,B.Radiguet,S.Poissonnet,F.Cuvilly,P.Pareige,F.Legendre,J.Nucl.Mater.409(2011)80.[19]H.K.D.H.Bhadeshia,Mater.Sci.Eng.A223(1997)64.[20]H.K.D.H.Bhadeshia,Mater.Sci.Technol.16(2000)1404.[21]W.Gale,T.Totemeier,Smithells Metals Reference Book,Amsterdam,Holland,2004.[22]T.J.Kallarackel,S.Gupta,P.Singh,J.Am.Ceram.Soc.(2013)1,http:///10.1111/jace.12435.S.Pasebani,I.Charit/Journal of Alloys and Compounds599(2014)206–211211。

热变性

热变性

Direct measurement of the melting temperature of supported DNA by electrochemical methodRita Meunier-Prest*,Suzanne Raveau,Eric Finot 1,Guillaume Legay 1,Mustapha Cherkaoui-Malki 2and Norbert Latruffe 2Laboratoire de SyntheÁse et d'Electrosynthe Áse Organome Âtalliques,UMR CNRS 5188,Universite Âde Bourgogne,6Bd.Gabriel,21000Dijon,France,1Laboratoire de Physique,UMR CNRS 5027,F-21011Dijon,France and 2Laboratoire de Biologie MoleÂculaire et Cellulaire,GDR CNRS 2583,Universite Âde Bourgogne,F-21000Dijon,FranceReceived July 18,2003;Revised September 29,2003;Accepted October 7,2003ABSTRACTThe development of biosensors based on DNA hybridization requires a more precise knowledge of the thermodynamics of the hybridization at a solid interface.In particular,the selectivity of hybridiza-tion can be affected by a lot of parameters such as the single-strand (ss)DNA density,the pH,the ionic strength or the temperature.The melting tempera-ture,T m ,is in part a function of the ionic strength and of the temperature and therefore provides a useful variable in the control of the selectivity and sensitivity of a DNA chip.The electrochemical tech-nique has been used to determine the T m values when the probe is tethered by a DNA self-assembled monolayer (SAM).We have built a special thin layer cell,which allows the recording of the cyclic voltam-mogram under controlled temperature conditions.T m has been determined by recording the thermo-gram (current versus temperature)of a redox indica-tor on a double-stranded hybrid (dsDNA)modi®ed electrode and comparison with the corresponding ssDNA response.T m of supported DNA varies linearly with the ionic strength.The stability of the SAMs has been considered and comparison between T m in solution and on a solid support has been discussed.INTRODUCTIONThe knowledge of the melting temperature,T m ,is of technological interest to understand the hybridization mech-anism involved in a DNA chip.T m is generally used as a parameter to adjust the properties of the cell in a DNA chip.The number of bases of DNA is modi®ed so that T m is maintained constant for each cell.The T m value used is that measured in liquid medium.T m in solution is well determined by spectroscopy and many empirical formulas were developed to account for both the ionic strength and the mole fraction ofG-C base pairs (1,2).More precise T m values can be obtained through on-line T m calculators (/)(3).However,the environment of oligomers can differ between a solid interface and the bulk solution due to difference between ionic strengths.The change in surface charge density induced by the hybridization is expected to in¯uence the T m value.There is rather scarce information on T m when DNA strands are immobilized on to a surface.The dif®culty is to measure the true surface temperature of the substrate and therefore ®nd the more appropriate method to heat the DNA support.The nature of the substrate onto which the DNA is immobilized is generally governed by the choice of the signal transduction.For example,in classical tests involving ¯uorescent or radiolabeled arrays,DNA probes are attached mostly to silica or glass surfaces (4±7)whereas piezoelectric,surface plasmon resonance or electrochemical detection involve nucleic acids immobilized on gold elec-trodes (4,8,9).For DNA on silica,the `supported'T m values have been determined by using ¯uorescence (10)and impedance meas-urements (11).The thermodynamic stability of immobilized double-stranded (ds)DNA is different from that of dsDNA in bulk solution and depends on the DNA density,namely the nearest-neighbor interactions (10).Concerning the DNA attached to gold via an alkanethiol anchor,T m has been measured by two-color surface plasmon resonance spectroscopy (12).As the substrate is deposited on a prism,the immobilized DNA is heated indirectly by means of the solution.These three techniques give T m values close to those in solution,varying by <10°C.Nevertheless,some key issues are still unclear:the thermal stability of SAMs is of crucial importance in the determination of T m ;aliphatic alkanethiols have been reported to thermally desorb (13±16).The desorption temperature ranges from 37°C to >100°C depend-ing on the aliphatic chain length and on the surface state.We propose a new approach that can provide an alternative and easy way to both measure the T m of supported DNA ®lm and verify the stability of the immobilization.The electro-chemistry has the advantage of combining the analytical power of electrochemical methods with the speci®city of the biological recognition process.The present work aims to*To whom correspondence should be addressed.Tel/Fax:+33380396086;Email:rita.meunier-prest@u-bourgogne.frNucleic Acids Research,2003,Vol.31,No.23e150DOI:10.1093/nar/gng150at Istanbul University Central Library on December 14, 2010 Downloaded frominvestigate the capability of the electrochemical methods to determine the T m of supported DNA.We have adapted the electrochemical cell for heating the substrate within0.1°C accuracy and measuring the electrical signal of a redox indicator.Different redox indicators have been tested to select the best candidates for thermal studies.The high packing density of the DNA monolayer is controlled using permeabil-ity experiments.In such experiments,the stability of self-assembled monolayer(SAM)versus the applied potential is very important.SAMs have been shown to be stable to potentials between approximately+0.8and±1.4V versus saturated calomel electrode(SCE)depending on the type of thiol derivative and on the properties of the metallic surface(17±22).Within these limits,thiol SAMs do retain structural order and high packing density especially in aqueous medium. Therefore,the indicators used in this study are electroactive within this potential window.Discussion focuses on the comparison between T m in solution and on the electrochemical probe to correlate the T m with the ionic strength.MATERIALS AND METHODSMaterialsMethylene blue(MB)(Aldrich),potassium ferricyanide (Aldrich)and hexaammineruthenium(III)chloride(Aldrich) were used as received at a concentration of5Q10±5,10±4and 10±4M,respectively.HPSFâpuri®ed5¢-TTT TTT TTT TTT TTT-(CH2)6-SH-3¢and underivatized complement were purchased from MWG Biotech(Evry,France).Mercaptohexyloligonucleotides were stored frozen to prevent oxidation of the thiol. HybridizationMercapto-and underivatized oligonucleotides(0.1mM)were hybridized in5mM phosphate/50mM NaCl by heating to 90°C for10min followed by slow cooling to room tempera-ture.In all experiments,hybridization is performed before the immobilization on to the gold electrode. Derivatization of gold electrodesAu(III)surfaces were prepared by thermal evaporation at a pressure of10±6Pa(0.1nm/s)of a thick gold layer(175nm)on to glass plated with4nm of chromium.Freshly evaporated gold electrodes were then modi®ed by incubation in0.1mM solutions of derivatized DNA duplexes in5mM phosphate/ 50mM NaCl(pH7.4)for18±48h at ambient temperature. Modi®ed electrodes were rinsed in phosphate buffer prior to use.The DNA density was previously quanti®ed by 32P-radiolabeling(23).We obtained a surface coverage of 8Q1011strands/cm2.ElectrochemistryAll the electrochemical experiments were carried out in a deoxygenated buffer made of5mM phosphate/x mM NaCl (x=35,50,100,200)Millipore water(pH7.4).The electrochemical instrumentation used for these experiments includes an EG&G283potentiostat connected to a PC.Data collection and analysis were performed using a Princeton Applied Research Software Model270.The DNA modi®ed electrodes were used as working electrodes.Potentials were measured relative to the Ag|AgCl|NaCl xmM reference elec-trode and then recalculated with respect to the SCE.The electrochemical techniques used are cyclic voltammetry and square-wave voltammetry.We have shown previously(23) that the electrochemical response and in particular the signal-to-noise ratio is greatly improved by using square-wave voltammetry.Square-wave voltammetry(24)is a dynamic method in which a train of pulses is applied at a stationary electrode.A rather large amplitude symmetrical square-wave perturbation is applied,each cycle of the square-wave coinciding with one cycle of an underlying staircase (Fig.1A).The waveform is characterized by D E S,the step height of the staircase,E SW,the half-peak-to-peak amplitude of the square-wave and t,the period of the square-wave excitation.The time parameters may be described alterna-tively by the frequency,f=t±1,or the pulse width,t p=t/2.The pulse width is the characteristic time of the experiment. Current is sampled over sampling interval t s.The current sampled on the forward-going or®rst half-cycle is referred to as the forward current(i f).The reverse current(i r)corresponds to the second half-cycle.Generally the net peak current (D i=i f±i r)is used because it is greater than i f since i r for a reversible system is opposite in sign to i f near the peak.W1/2is de®ned as the net peak half-height width.After optimization of the different parameters,the best results have been obtained with f=100Hz,D E S=1mV and E SW=50mV.All the square-wave voltammograms have been carried out under these conditions.Measurement cellA special cell was developed to control the temperature of the DNA modi®ed electrode(Fig.1B),as described previously (23).The main characteristic of the cell is its small internal volume(3Q1.5Q9mm)thereby permitting us to handle only a few microliters of solution using a microsyringe.Inlets and outlets of liquid of110m m in diameter are located in the cell base.The tightness of the cell is ensured by pressing all elements using four screws.All solutions passing through the cell are deoxygenated prior to experiments.Due to the small size of the cell,deoxygenation is not necessary during experiments.The electrode support constitutes the upper part of the cell.Located in the lower part,the auxiliary electrode is a platinum disk of2mm in diameter and the reference is a thermodynamic Ag|AgCl|NaCl xmM electrode, which relies on chloride concentration in the¯ow stream.The temperature is controlled within0.1°C accuracy from20up to 80°C using a Peltier heating plate in contact with the electrode support.To ensure a good equilibrium in temperature, electrochemical measurements are performed10min after the increase in temperature.RESULTS AND DISCUSSIONSurface controlThe negative anion Fe(CN)64±was chosen since it does not bind to the DNA,a poly-anionic molecule,due to repulsive effects(25)and is electro-inactive even at over-potentials as high as+1V.Fe(CN)64±becomes particularly interesting toe150Nucleic Acids Research,2003,Vol.31,No.23P AGE2OF8at Istanbul University Central Library on December 14, Downloaded fromestimate the DNA coverage on the electrode.Therefore,when the electrode is covered with a densely built-up monolayer,the cyclic voltammogram presents a lack of signal.Alternatively,when the gold electrode is partially uncovered,Fe(CN)64±is oxidized on the gold surface leading to a characteristic electrochemical response of ferrocyanide at 0.18V whose intensity is proportional to the amount of desorbed DNA.Cyclic voltammetry of Fe(CN)64±is used then as a routine method to guarantee a good derivatization of the probe.Choice of the redox indicatorFigure 2shows the square-wave voltammograms of three redox species at a DNA modi®ed electrode:ferrocyanide Fe(CN)64±,hexaammineruthenium(III)Ru(NH 3)63+and MB.The second redox indicator,Ru(NH 3)63+,is a groove binding agent (26).Its reduction proceeds through the facilitated diffusion of the ruthenium complex along the grooves of the DNA helix (25).Recording the electrochemical response of Ru(NH 3)63+as a function of temperature does not yield measurable differences.This may be due to the binding modeof Ru(NH 3)63+,which remains rather far from the stacked bases responsible for the electron transfer.The best results have been obtained with MB.The intensity of the square-wave voltammogram is 12t-fold higher than that of Ru(NH 3)63+.MB behaves as an adsorbed molecule:in cyclic voltammetry,the peak current varies like v and the shape of the peak corresponds to a strong adsorbed system (27).MB intercalates into the DNA base stack and therefore participates in electron transfer mediated by the stacked bases.This is the reason why MB has been chosen as the electrochemical intercalator in the following.At ambient temperature,the peak intensity is nearly the same whether the DNA is hybridized or not.The DNA duplex helices are tightly packed on the gold surface necessitating that MB binds at sites close to the DNA/solvent interface.In contrast,diffusion of MB into the single strand (ssDNA)monolayer becomes facilitated (28,29).This phenomenon counterbalances the rapid electron transfer observed with hybridized DNA (30,31)and therefore provides approximately the same signal inten-sity for both modi®ed electrodes.It is worth noting that the electrochemical study of Ozsoz et al .(28,29),which presents a diminution of the peak height after hybridization,involves DNA strands lying on the surface of the electrode,therefore ET through the p -stacks of the double helical DNA does not occur;in dsDNA,the bases are less accessible than in the ssDNA so the signal of dsDNA is reduced.In our case,the DNA strands form a densely packed monolayer upright oriented with respect to the gold electrode,favorable to ET.The monolayer thickness has been estimated by AFM between 4and 6nm for a 15mer oligonucleotide.This corresponds to upright or slightly bent strands.The same observations,obtained by ellipsometry measurements,have also been reported by Kelley and Barton (32).Desorption phenomenaFigure 3shows the variation of the maximum net peak current of MB in square-wave voltammetry as a function of the electrode temperature varying between 20up to 80°C bystepsFigure 2.Square-wave voltammetry of:(black line)10±4M Fe(CN)64±;(red line)10±4M Ru(NH 3)63+and (blue line)5Q 10±5M MB at a gold electrode modi®ed with 5¢-TTT TTT TTT TTT TTT-(CH 2)6-SH-3¢hybridized to its complement in 5mM phosphate/50mM NaCl.Voltammograms were obtained with f =100Hz,D E S =1mV and E SW =50mV.Figure 1.(A )Potential time waveform for square-wave voltammetry and de®nition of the different parameters:E sw is the square-wave amplitude,D E s the staircase step height,t p =t /2the pulse width.(B )The cell design.P AGE 3OF 8Nucleic Acids Research,2003,Vol.31,No.23e150at Istanbul University Central Library on December 14, 2010 Downloaded fromof 0.5°C.When the temperature increases,the signal of MB with both ssDNA and dsDNA grows until a temperature of 28.5°C for ssDNA and 32°C for dsDNA,then falls down until a value of D i/W 1/2=1.8m A.mV ±1.Such a bell-shaped curve has been observed with alkanethiol SAMs and imputed to dynamic movements of the SAMs (13,33).Molecular dynamic simulations predict that at a low temperature the chains are orientationally ordered.When increasing the temperature,chain-disordering processes occur passing from a crystalline-like to a melted state.Partial desorption and surface migration of thiolates have also been observed.The experiment has been repeated with other 15mer DNA duplexes containing guanine bases.The thermograms present the same aspect,namely a maximum of the curve coupled with a limiting value D i/W 1/2=1.8m A.mV ±1at temperatures >70°C.The maximum intensity 20%higher with a 15mer DNA containing seven guanines indicates a greater af®nity of MB to guanine and cytosine bases (34,35).The current decrease does not depend on the DNA sequence reaching the same limiting value at high temperatures (T >70°C).Lets ®nd the possible origin explaining such a current decrease.It is well known that in square-wave voltammetry,moderately slow quasi-reversible redox reactions give responses larger than much fasterreversible reactions (36±38).It has been shown theoretically (36)that in the quasi-reversible region,the contributions of the forward and reverse currents to the net current are approxi-mately equal near the maximum net peak height,then the net peak splits into two.Experimentally,when the net intensity decreases,a split has never been observed and both contribu-tions of the forward and reverse currents remain of the same order.Moreover,the forward and reverse peaks were found to be symmetrical even at high temperatures.These results suggest that the increase in the reaction rate induced by the temperature increase cannot explain the current fall.Alternatively,some authors have suggested that a thermal desorption of alkanethiols SAMs can occur (14±16).This can be considered as the ultimate stage of the SAMs dynamic movements'process.The electrochemical response of MB on a bare gold electrode has been recorded as a function of the temperature (Fig.3).MB presents the characteristics of an adsorbed system;in particular,the cyclic voltammogram has a shape corresponding to an electrochemical reaction occurring on the electrode surface and the current is proportional to the scan rate (27,39,40).The low current value at the initial temperature reveals a smaller amount of MB adsorbed on the bare electrode compared with the DNA modi®ed electrode.From 20to 35°C the net peak decreases due to the apparition of a pre-peak (39,41)close to the other peak on the forward current.This induces a broadening of the net peak and a decrease of its height.When increasing the temperature,the two peaks merge.The current of MB at the gold electrode increases as expected for an activated process (42)until D i/W 1/2=1.8m A.mV ±1is reached at T =70°C,which matches with the minimum of the DNA modi®ed electrode signal at high temperature.Moreover,cyclic voltammograms have been carried out with Fe(CN)64±on a gold electrode tethered with 5¢-TTT TTT TTT TTT TTT-(CH 2)6-SH-3¢hybridized with its complementary strand.A study in function of the temperature shows a lack of electrochemical signal until 60°C (Fig.4A and B).Then,the electrochemical response of Fe(CN)64±merges progressively with increasing the tempera-ture and reaches nearly the same intensity as that observed on a bare gold electrode at T =80°C (Fig.4A).Note that Fe(CN)64±is not oxidized on a well covered electrode due to repulsion of the DNA.The electrochemical signal at high temperatures reveals a partial destruction of the DNA monolayer and a strip of the gold surface where oxidation of Fe(CN)64±can occur.The thermal desorption of thiol SAMs has already been reported for aliphatic alkanethiol SAMs (13±16).Let us de®ne by T 1/2the temperature corresponding to desorption of half of the monolayer.Figure 4C represents the variation of T 1/2with the logarithm of the salt concentration.The thermal desorption of the SAMs is dramatically emphasized by an increase of the ionic strength.The sensibility of DNA SAMs to temperatures is of great importance in the practical use of such DNA probes.In particular,it has been shown that hybridization of an ssDNA immobilized by a thiol anchor has to be realized under mild temperature conditions and at rather low ionic strength.T m determination and effect of ionic strengthWe have reported in Figure 5B the literature `supported'T m values (solid lines)and compared them to the corresponding T m in solution (dotted lines).For the 25mer DNA (12)aFigure 3.Variation of the ratio of the square-wave peak current on the half-height width (D i/W 1/2)as a function of the temperature for 5Q 10±5M MB in 5mM phosphate/35mM NaCl (black solid circle)at a bare gold electrode and at a gold electrode modi®ed with:(red open circle)the single strand 5¢-TTT TTT TTT TTT TTT-(CH 2)6-SH-3¢and (blue open circle)the duplex 5¢-TTT TTT TTT TTT TTT-(CH 2)6-SH-3¢hybridized to its complement.(Blue solid line)Fitted curve obtained by calculation of a 6order polynomial regression on the whole experimental curve after elimination of the points that form the bulge.e150Nucleic Acids Research,2003,Vol.31,No.23P AGE 4OF 8at Istanbul University Central Library on December 14, 2010 Downloaded fromdecrease of ~10°C between the DNA in solution and the supported DNA has been observed.Different results have been obtained for the dA20:dT20duplex:the solution T m values calculated with an empirical formula (/)(3)are of the same order as those for DNA on silica (10).In that case,the slope d T m /dlog(c NaCl )is little different.An easy way to determine the T m is to compare the electrochemical responses given by both an electrode tethered with an ssDNA,i.e.5¢-TTT TTT TTT TTT TTT-(CH 2)6-SH-3¢and a second electrode tethered with the corresponding hybridized strands (dsDNA).The signal obtained for both ssDNA and dsDNA increases with increasing temperature up to 28.5°C for ssDNA and 32°C for dsDNA (Fig.3).Contrary to the rise of the current that is regular for the ssDNA,the one obtained with the dsDNA presents a bulge at 24°C (for a salt concentration of c NaCl =35mM).A ®ne procedure has been developed to determine precisely the temperature related to the peak maxima.The ®tted curve has been obtained by calculating a high order polynomial ®t on the whole experimental curve after elimin-ation of the experimental points that form the bulge.For example,the curve corresponding to dsDNA with a salt concentration of c NaCl =35mM (blue circles in Fig.3)can be ®tted by a polynomial equation of order 6or more (blue solid line in Fig.3).Figure 5A shows the difference between the experimental measurements and the `regular'®t (blue solid line in Fig.3).As the temperature approaches T m ,the progressive separation of the two strands of the helicalDNAFigure 4.(A )Cyclic voltammetry of 10±4M Fe(CN)64±in 5mM phosphate/50mM NaCl (black dotted line)at a bare gold electrode at T =80°C and at a gold electrode modi®ed with 5¢-TTT TTT TTT TTT TTT-(CH 2)6-SH-3¢hybridized to its complement at different temperatures:(red solid line)T =21°C;(green solid line)T =60°C and (blue solid line)T =80°C.(B )Peak current height of 10±4M Fe(CN)64±in 5mM phosphate/50mM NaCl as a function of the temperature (same DNA as A).(C )Variation of the half desorption temperature (T 1/2)with the logarithm of the ionic strength (log c NaCl )for the 15mer duplex 5¢-TTT TTT TTT TTT TTT-(CH 2)6-SH-3¢hybridized to its complement and tethered on a gold electrode.P AGE 5OF 8Nucleic Acids Research,2003,Vol.31,No.23e150at Istanbul University Central Library on December 14, 2010 Downloaded fromfacilitates the diffusion of MB into the DNA monolayer,leading to an increase in the electrochemical response.Then,the complement strand is completely dehybridized and the signal falls down.To make sure that this temperature can be attributed to T m ,which is known to vary as a function of ionic strength,the experiment has been repeated at different salt concentrations (35mM `c NaCl `200mM)and theelectrochemical thermograms (current versus temperature)have been drawn.For ssDNA a regular curve is obtained while for dsDNA a bulge is observed.The same procedure as described previously has been performed and the results presented in Figure 5.When increasing the ionic strength,T m is shifted towards higher temperatures,indicating stabilization by greater Na +concentrations.To compare our results with those in solution,we have determined the T m of the DNA±MB complex in solution by UV spectroscopy.The equivalent oligonucleotide concentration has been calculated as follows:the electrode area is 0.15Q 0.9=0.135cm 2on which the DNA density is 8Q 1011strands/cm 2.This corresponds to 1.79Q 10±13mol in a cell volume of 4.05Q 10±5l,i.e.a concentration of 4Q 10±9M.The absorbance for l =260nm has been reported as a function of the temperature carefully measured with a thermocouple plunged into the solution.This melting curve has been repeated with different ionic strengths.The straight line obtained is presented in Figure 5B (blue dotted line).The T m of the DNA±MB complex in solution is lowed by 10°C with respect to the DNA without MB in solution.MB intercalates between the bases and therefore provides a deformation of the DNA,which induces a lower stability of the DNA and facilitates pletely different results have been observed with major groove binding agents (43,44),which contribute to increase the DNA cohesion:it has been shown that DNA is stabilized by iridium or ruthenium complexes and T m increases with nearly 5±10°C (43,44).When the DNA±MB complex is tethered on a support,the stability increases.The `supported'T m varies linearly as a function of log(c NaCl )with approxi-mately the same slope as that obtained in solution but shifted by >12°C compared with the solution.The T m increase observed for supported DNA can be interpreted as an increase of the salt concentration in the monolayer.Moreover,it appears that high packing density facilitates some destabiliza-tion of hybridized immobilized oligonucleotides and therefore diminished the T m (45).Figure 5B regroups our results together with the literature results obtained with a 20base (10)and a 25base tethered DNA (12).The melting temperature rises as the DNA length increases and the slope [d T m /d(log c NaCl )]is of the same order of magnitude whatever the DNA sequence,indicating an identical sensitivity of T m to the ionic strength.In the study of Peterlinz et al.(12),comparison between T m in solution and tethered on the gold electrode shows a decrease of 5°C for immobilized oligonucleotides.These results seem to be under estimated values due to thermal gradients in the SPR apparatus between the modi®ed prism surface and the thermal regulator as noticed by the authors.In our case,the temperature measurement corresponds well to the temperature of the DNA probe because the Peltier element is directly in contact with the electrode.CONCLUSIONSA more precise knowledge of the hybridization occurring at a solid interface is important in the development of DNA chip.Our work provides a comparison between tethered and untethered DNA.We have shown that the melting tempera-ture,T m ,of immobilized DNA can be obtained via the square-wave voltammetric response of MB as a function of the temperature probe.The supported melting temperaturesvaryFigure 5.(A )Current difference obtained by subtraction of the experimental points with the `regular'®t (blue solid line in the inset of Fig.3)as a function of the temperature for 5Q 10±5M MB in 5mM phosphate/x mM NaCl at a gold electrode modi®ed with the duplex 5¢-TTT TTT TTT TTT TTT-(CH 2)6-SH-3¢hybridized to its complement.Magenta open diamond,x =35mM;green open up triangle,x =50mM;blue open circle,x =100mM and red open square,x =200mM.(B )Variation of the T m with the logarithm of the ionic strength (log c NaCl ).Solid lines correspond to DNA tethered on solid support,dotted lines to the corresponding DNA in solution.Experimental results for (blue solid square)the 15mer duplex 5¢-TTT TTT TTT TTT TTT-(CH 2)6-SH-3¢hybridized to its complement and tethered onto a gold electrode in presence of MB,(blue solid circle)the 15mer duplex 5¢-TTT TTT TTT TTT TTT-(CH 2)6-SH-3¢hybridized to its complement in presence of MB in solution and literature results obtained with:(red open up triangle)silica coated with dA20:dT20(10);(green cross)5¢-HS-(CH 2)6-CAC GAC GTT GTA AAA GCA CGG CCA G-3¢hybridized to its complement (12).e150Nucleic Acids Research,2003,Vol.31,No.23P AGE 6OF 8at Istanbul University Central Library on December 14, 2010 Downloaded from。

纳米锰基普鲁士白的制备及电化学储钠性能

纳米锰基普鲁士白的制备及电化学储钠性能

第34 7期2018年7月无机化学学报CHINESE JOURNAL OF INORGANIC CHEMISTRYVol.34 No.71327-1332纳米锰基普鲁士白的制备及电化学储钠性能陈新1徐丽1沈志龙2刘双宇1李慧1王博1谢健!,2姜银珠2刘海镇1盛鹏1赵广耀1全球能源互联网研究院有限公司,先进输电技术国家重点实验室,北京1022117(2浙江大学材料科学与工程学院,杭州3100277摘要:采用高温共沉淀法制备锰基菱方相的普鲁士白正极材料,研究合成温度对产物微结构和电化学性能的影响。

研究发现,随着合成温度的提高,产物的结晶度、颗粒尺寸和嵌钠容量明显提高。

当合成温度为90 "时,产物在M m A j-1下首次充放电容量分别达到142和U A m A lv i-1。

在30和'O m A.g-1分别循环300和600次时,容量仍保持在111和SAm Ah.g-1。

关键词:钠离子电池(正极材料(普鲁士白(电化学性能中图分类号:TB34 文献标识码:A 文章编号!1001-4861(2018)07-1327-06DOI:10.11862/CJIC.2018.177Preparation and Electrochemical Performance of theNanostructure Mn-Based Prussian WhiteCHEN Xin1XU Li1SHEN Zhi-Long2LIU Shuang-Yu1LI Hui1WANG Bo1XIE Jian!,2JIANG Yin-Zhu2LIU Hai-Zhen1SHENG Peng1ZHAO Guang-Yao1(^State Key Laboratory of A dvanced Transmission Technology, Global Energy InterconnectionResearch Institute Co. Ltd” Beijing 102211, China)(^School of M aterials Science and Engineering, Zhejiang University, Hangzhou310027, China) Abstract:Rhombohedral phase Mn-based Prussian white materials were synthesized by high-temperature coprecipitation method and the effect of synthesis temperature on the microstructure and electrochemical performance of the products was investigated. It is found that the crystallinity,particle size and Na-insertion capacity increase obviously with the increasing synthesis temperature. At a synthesis temperature of 90 ",the first charge and discharge capacities of the product reach 142 and 139 mAh'g-1at 15 mA'g-1.After 300 cycles at 30 mA'g-1 and 600 cycles at 50 mA'g-1,the discharge capacities are kept at 111 and 89 mAh'g-1,respectively. Keywords:sodium-ion batteries; cathode materials; Prussian white; electrochemical performance0引言随着能源和的日重,开发清洁、可持续能已成为球的研究[16。

碳包覆的磁性纳米材料萃取酞酸酯

碳包覆的磁性纳米材料萃取酞酸酯

第32卷㊀第12期2013年㊀㊀12月环㊀境㊀化㊀学ENVIRONMENTALCHEMISTRYVol.32,No.12December2013㊀2013年3月27日收稿.㊀∗国家自然科学基金(21207059,21171085);山东省自然科学基金(ZR2010BM027,ZR2011BQ012)资助.㊀∗∗通讯联系人,Tel:13864593698;E⁃mail:lduzsx@126.comDOI:10.7524/j.issn.0254⁃6108.2013.12.003碳包覆的磁性纳米材料萃取酞酸酯∗王颖辉1㊀腾㊀飞2㊀张媛媛3㊀张升晓3∗∗㊀刘军深3㊀吴㊀茜3(1.烟台开发区城市管理环保局,烟台,264006;㊀2.上海通用东岳汽车有限公司,烟台,264006;3.鲁东大学,烟台,264025)摘㊀要㊀利用水热反应制备碳材料包覆的Fe3O4(Fe3O4/C)纳米颗粒,并将这种材料用作固相萃取吸附剂,从环境水样中富集酞酸酯类(PAEs)污染物.由于纳米材料大的比表面积和碳材料强的吸附能力,Fe3O4/C吸附剂拥有较高的萃取效率.从500mL的环境水样中定量萃取PAEs目标物,只需50mg的吸附剂.PAEs在Fe3O4/C表面的吸附可快速达到平衡,并且用少量的乙腈就能将分析物洗脱下来.在优化的固相萃取条件下,几种PAEs的检出限在17 58ng㊃L-1之间.通过水样的加标回收率来评价该方法,其加标回收率在94.6% 106.6%之间,相对标准偏差为2% 8%.关键词㊀酞酸酯,磁性固相萃取,碳材料.酞酸酯类化合物(PAEs)作为增塑剂用于塑料制品的生产,来提高塑料强度和增大可塑性.这类物质会从塑料制品中迁移转化进入环境,从而对环境造成污染.PAEs具有三致(致突㊁致畸㊁致癌)作用,属于环境内分泌干扰物,其中有6种化合物已被美国国家环保局列为 优先监控污染物 [1].目前测定水体PAEs的前处理方法主要有液液萃取[2]㊁固相萃取[3]㊁固相微萃取[4]等方法.李玫瑰等[5]以甲苯为萃取溶剂,采用微滴液相微萃取方法快速分析水溶性食品中的PAEs.王东新[6]以中空纤维膜液相微萃取方法从天然水体中萃取了4种PAEs,并结合气相色谱进行分析.胡庆兰[7]采用自制的固相微萃取涂层,通过顶空固相微萃取与气相色谱法联用测定水中的PAES.固相萃取法以有机溶剂消耗少㊁操作简便等优点被广泛采用.王鑫等[8]采用C18小柱萃取饮用水和自来水中的4种PAEs类污染物,并用气相色谱法测定.陈永山等[9]研究了流速和除水方式等条件对C18固相萃取柱富集PAEs回收率的影响,他们还用罗里硅土净化土壤提取液,测定了土壤中的11种PAEs类污染物[10].纳米材料拥有大的比表面积和短的扩散路径,使其具有很高的萃取效率和较快的吸附速度,近年来被开发研究用作固相萃取吸附剂,从环境或生物样品中富集污染物[11⁃12].然而纳米材料填充的固相萃取小柱具有很大的反压,样品通过小柱需要消耗大量的时间.因此,磁性纳米材料用作固相萃取吸附剂的研究应运而生[13⁃15],张小乐等[16]合成了C18基团修饰的磁性介孔硅胶材料,并利用该材料建立了磁性固相萃取⁃色谱分析方法,测定了环境水样中PAEs污染物的含量.我们以前的研究[17⁃19]表明,在基于磁性纳米颗粒的固相萃取方法中,可将经过修饰的磁性纳米材料分散到样品中进行目标物吸附,达到吸附平衡后,利用磁铁快速将吸附了目标物的磁性材料分离出来,然后将目标物进行洗脱㊁测定,该快速磁分离方法避免了传统固相萃取中耗时的过柱操作,能够节省大量时间.本文制备了一种新型的磁性纳米材料(Fe3O4/C),并以该纳米材料为固相萃取吸附剂从环境水样中富集PAEs污染物.优化了吸附剂用量㊁平衡时间㊁盐度㊁pH㊁解吸附等固相萃取条件,并将这种新型的固相萃取技术与高效液相色谱(HPLC)结合,开发了一种分析环境水体中PAEs的新方法.1㊀实验部分1.1㊀化学试剂和材料㊀㊀酞酸丙酯(DPP)㊁酞酸丁酯(DBP)㊁酞酸环己酯(DCP)和酞酸辛酯(DOP)标准样品从美国Acros2244㊀环㊀㊀境㊀㊀化㊀㊀学32卷Organics公司购得.十八烷基三乙氧基硅烷购买自日本东京化学试剂公司.FeCl3㊃4H2O和FeCl2㊃6H2O从北京化学试剂公司购买.葡萄糖购买自北京红星化学公司.色谱纯的甲醇和乙腈购自美国的ThermoFisher公司.实验用的纯水来自于美国Milli⁃Q纯水系统.1.2㊀Fe3O4和Fe3O4/C纳米材料的制备和表征采用化学共沉淀的方法制备Fe3O4磁性纳米材料.首先将2.0gFeCl2㊃4H2O和5.2gFeCl3㊃6H2O溶解到25mL的预先脱氧的去离子水,再加入0.85mL浓盐酸.将以上溶液逐滴加到250mL1.5mol㊃L-1的NaOH溶液,边加边机械搅拌并通氮气保护.反应完成后,生成的黑色Fe3O4纳米颗粒用200mL去离子水洗2次,再分散到110mL的去离子水中,悬浮液中Fe3O4纳米颗粒的浓度约为20mg㊃mL-1.采用水热法在纳米Fe3O4的表面包覆一层碳材料.将0.4gFe3O4用去离子水冲洗,直至溶液为中性,然后分散到80mL0.5mol㊃L-1的葡萄糖溶液中,将此混合物超声20min后转移到聚四氟乙烯内衬的反应釜中.将反应釜在180ħ加热4h,反应完成后,用磁铁将Fe3O4/C纳米材料分离,再用去离子水和乙醇冲洗几次除去杂质.最后将反应产物分散到70mL的去离子水中得到10mg㊃mL-1的Fe3O4/C.利用透射电镜(TEM,H⁃7500,Hitachi,Japan)观察制得的吸附材料的形貌和粒径,工作电压为80kV.材料的能谱图(EDS)采用S⁃3000N能谱仪(Hitachi,Japan)测定.材料的红外谱图采用KBr压片的方式在NEXUS670傅立叶变换红外光谱仪(NicoletThermo,U.S.)采集.1.3㊀固相萃取的程序将50mg的Fe3O4/C吸附剂分散到500mL水样中,搅拌20s使吸附剂在溶液中均匀分散.将1个Nd⁃Fe⁃B强力磁铁置于容器底部进行磁分离.经过大约10min,溶液变清澈,吸附剂被完全分离到容器底部,将上清液倒掉.在吸附剂中加入2mL乙腈,超声10s后置于磁铁上分离,洗脱液转移到离心管中,取20μL进HPLC系统测定.由于塑料制品可能会释放出PAEs,因此在实验过程中使用玻璃容器.1.4㊀HPLC分析利用美国安捷伦公司的高效液相色谱系统对PAEs进行分离和分析,迪马C18色谱柱(250ˑ4.6mm,粒径5μm),采用梯度淋洗的方法分离,50%的乙腈水溶液和纯乙腈分别为流动相A和B,流速为1mL㊃min-1.梯度淋洗程序如下:前15min内B保持在40%,在10min内B由40%升至100%,保持10min,随后在3min内回到初始状态.PAEs采用紫外检测器测定,波长设在226nm.2㊀结果与讨论2.1㊀吸附剂的表征图1为Fe3O4和Fe3O4/C的透射电镜图片.Fe3O4纳米颗粒为近似球形,粒径分布比较均匀,平均直径大约为10nm.Fe3O4/C纳米颗粒呈现出明显的核壳结构,内层颜色较深的为Fe3O4核,而外层颜色相对较浅的部分是碳层.Fe3O4核使得材料具有磁性,而碳包覆层赋予材料强的吸附能力.图1㊀Fe3O4(a)和Fe3O4/C(b)纳米材料的透射电镜图(放大倍数:200000)Fig.1㊀TEMimagesofFe3O4(a),andFe3O4/C(b)nanoparticle㊀12期王颖辉等:碳包覆的磁性纳米材料萃取酞酸酯2245㊀Fe3O4和Fe3O4/C的能谱图见图2.在Fe3O4纳米颗粒的能谱图中只有一个很小的碳峰,在其表面包覆一层碳材料后,Fe3O4/C的能谱图中出现了一个较大的碳峰,其表面碳元素的摩尔百分含量达到54 4%,而铁元素的摩尔百分含量降低到13.8%,说明碳材料被成功的包覆到了Fe3O4纳米颗粒表面.图2㊀Fe3O4(a)和Fe3O4/C(b)纳米材料的能谱图Fig.2㊀EDSspectraofFe3O4(a)andFe3O4/C(b)nanoparticle利用傅立叶变换红外光谱分析Fe3O4和Fe3O4/C材料的表面基团.由图3可见,Fe3O4和Fe3O4/C的红外谱图上都有1个580cm-1的吸收峰,为Fe3O4的特征吸收峰[20].在Fe3O4/C的谱图上1700cm-1和1616cm-1的峰是C O和C C的振动吸收峰[21],这表明在水热反应的过程中,葡萄糖碳化包覆到了纳米Fe3O4的表面.1000 1300cm-1的峰是C OH的伸缩振动峰和O H弯曲振动峰[22],3100 3700cm-1之间的宽峰是O H伸缩振动峰[23].Fe3O4/C纳米材料的表面上羟基和羧基基团的存在使得该材料具有表面亲水性,能够在水溶液中分散和稳定存在,并且材料的表面亲水性降低了分析物在其表面的不可逆吸附,能够在一定程度上克服碳材料用作固相萃取洗脱困难的缺点.2.2㊀萃取条件的优化2.2.1㊀吸附剂用量的选择为了获得最优的目标物回收率,在0 100mg的范围改变Fe3O4/C吸附材料的加入量进行萃取,其结果列于图4.随Fe3O4/C吸附剂加入量的增加,PAEs的回收率也逐渐增加,当吸附剂用量为40mg时,PAEs的回收率达到最大值,吸附剂的用量继续增加,回收率基本保持平衡,不会再有明显的增加.使用没有修饰的Fe3O4作为固相萃取的吸附剂,即使其用量达到100mg,对PAEs的回收率也不会超过10%.图3㊀Fe3O4和Fe3O4/C纳米材料的红外谱图Fig.3㊀IRspectraofFe3O4andFe3O4/Cnanoparticle图4㊀吸附剂用量对PAEs回收率的影响Fig.4㊀EffectoftheamountofFe3O4/CsorbentontheextractionefficiencyofPAEs㊀㊀结果表明,能够有效吸附PAEs的是Fe3O4/C材料表面的碳层.碳纳米管和有机化合物之间的吸附主要通过疏水作用,π⁃π键㊁氢键作用和静电作用[24],Fe3O4/C纳米颗粒表面也是碳材料,因此其相互2246㊀环㊀㊀境㊀㊀化㊀㊀学32卷作用机理相同.要达到满意的回收率只需要Fe3O4/C吸附剂40mg,可能是因为Fe3O4/C材料拥有大的比表面积和碳材料的强吸附能力.为保证分析物的完全吸附,在水样中加入50mg的Fe3O4/C纳米吸附剂.2.2.2㊀乙腈用量和平衡时间的选择选用乙腈从Fe3O4/C吸附剂上解吸PAEs.为了能够将PAEs充分解吸附,将Fe3O4/C吸附剂在洗脱液中超声20s再分离.由图5(a)可以看出,只需1mL乙腈就可将80%以上的目标物解吸下来,增加乙腈的用量,PAEs的回收率略有增加,但影响不大,本实验选用2mL乙腈作为洗脱剂.传统的碳材料用作固相萃取吸附剂时,常常面临洗脱困难的问题[25].而本研究中Fe3O4/C材料较易洗脱,一方面可能是因为包覆在纳米材料上的薄层碳使得分析物的扩散路径较短,便于洗脱,另一方面可能是因为包覆上的碳材料表面是亲水性,有效避免了分析物在其上发生不可逆吸附.Fe3O4/C是超顺磁性并且拥有大的饱和磁强度,但由于其在水溶液中分散良好且表面羧基使颗粒之间存在静电斥力,因此从纯水中用磁铁分离需要较长时间.为了帮助磁分离,在水溶液中加入2mL1mol㊃L-1的NaCl溶液提供补偿离子.用一个Nd⁃Fe⁃B强力磁铁能在10min将吸附剂完全吸附到容器的底部.通常要达到完全吸附目标物和吸附剂要有充分的接触时间.改变平衡时间考察目标物回收率的变化,由图5(b)可以看出,随着平衡时间由0到120min,PAEs的回收率没有明显变化,说明分析物能在很短的时间内完全吸附到Fe3O4/C材料上.这种快的吸附速率应归功于纳米材料短的扩散路径.磁性分离和快速的吸附,使这种新型固相萃取方法能够避免耗时的过柱操作,具有可操作性和实用性.图5㊀洗脱液乙腈用量(a)和平衡时间(b)对PAEs回收率的影响Fig.5㊀Effectofacetonitrilevolume(a)andstandingtime(b)ontherecoveryofPAEs2.2.3㊀盐度和pH的选择为了考察盐度对PAHs回收率的影响,在溶液中加入NaCl调整盐度.由图6(a)可以看出,在盐度为1 500mmol㊃L-1的范围内,目标物的回收率基本不受影响,表明Fe3O4/C能从高盐度水样中萃取目标物而不受影响.吸附剂表面电荷的类型和密度通常会随溶液pH的改变而变化,因此溶液的pH可能会影响一些分析物在Fe3O4/C纳米材料上的吸附.改变溶液的pH值在3 10范围内考察其对PAHs萃取回收率的影响.由图6(b)可以看出,在设定的pH范围内PAEs的回收率没有明显变化,说明Fe3O4/C纳米材料在此pH范围内比较稳定,不会被破坏,另一方面可能是因为PAEs在设定的条件以中性分子形式存在,材料表面电荷的改变对它们的吸附没有明显的影响.基于Fe3O4/C的磁性固相萃取方法无需严格控制溶液pH,用于环境水样品的分析更加便利和稳定.2.2.4㊀水样体积选择利用Fe3O4/C作吸附剂进行固相萃取,可以将材料分散在溶液中进行吸附,达到吸附平衡后用磁铁将吸附剂分离出来进行洗脱,该方法免去了耗时的过柱操作,因此非常适用于大体积环境水样的分析.如图7所示,利用50mgFe3O4/C吸附剂,当水样的体积由200mL增加到1000mL时,PAHs的回收率没有明显下降,说明Fe3O4/C吸附材料具有大的穿透体积.通过从1000mL水样中萃取目标物并将洗脱液浓缩到2mL,PAEs的富集系数可以达到500倍.㊀㊀12期王颖辉等:碳包覆的磁性纳米材料萃取酞酸酯2247图6㊀盐度(a)和溶液pH值(b)对PAEs回收率的影响Fig.6㊀Effectofsalinity(a)andsolutionpH(b)ontheextractionefficiencyofPAEs图7㊀水样体积对PAEs回收率的影响Fig.7㊀EffectofwatersamplevolumeontherecoveyofPAEs2.3㊀分析方法相关参数固相萃取程序结合HPLC⁃UV检测建立了标准曲线,其线性范围为0.1 20ng㊃mL-1.从500mL纯水样品中萃取目标物并用2mL溶剂洗脱,PAEs的富集系数为250倍.线性范围㊁线性相关系数和检出限等参数列于表1.由表1可以看出,该方法有较高的灵敏度㊁宽的线性范围和良好的精密度,PAEs的线性相关系数R2>0.999.DPP㊁DBP㊁DCP㊁DOP的检出限(信噪比为3)分别为35㊁58㊁17㊁33ng㊃L-1.表1㊀标准曲线的方法参数Table1㊀Analyticalparametersoftheproposedmethod分析物线性范围/(ng㊃mL-1)曲线方程线性相关系数(R2)方法检出限a/(ng㊃L-1)DPP0.1 20y=0.5578x+0.05610.999835DBP0.1 20y=0.5476x+0.06340.999758DCP0.1 20y=0.9865x-0.03270.999717DOP0.1 20y=0.5948x+0.10360.999933㊀㊀a检测限根据信噪比为3确定(S/N=3),x为分析物浓度,y为紫外信号强度.2.4㊀实际水样的测定实际水样选取实验室自来水和校园人工湖的湖水,采用所建立的磁性固相萃取方法测定水样中和加标后的水样中的PAEs,3次平行测定水样和加标水样结果平均值㊁加标水样的回收率平均值及标准偏差列于表2.自来水样中DPP浓度为0.104ng㊃mL-1,其他未检出;湖水中DPP和DBP浓度分别为0 215和0.132ng㊃mL-1,其余未检出.水样中低浓度的PAEs可能来自于塑料管路或者是塑料制品的释放.加标水样中PAEs的平均回收率在94.6% 106.6%之间,相对标准偏差为2% 8%.图8为湖水样品及其加标色谱图,其峰型良好,基质相对比较干净,没有太多杂峰的干扰.2248㊀环㊀㊀境㊀㊀化㊀㊀学32卷表2㊀实际水样中PAEs的浓度及其加标回收结果Table2㊀ConcentrationsofPAEsinrealwatersamplesandrecoveriesofsamplesspikedwithanalytes水样加标/(ng㊃mL-1)测定值a/(ng㊃mL-1)DPPDBPDCPDOP回收率ʃ相对标准偏差/%bDPPDBPDCPDOP0.000.104ndcndnd自来水0.50.6120.5040.5240.533101.6ʃ3101.0ʃ2104.8ʃ6106.6ʃ855.155.104.864.79100.9ʃ2102.0ʃ497.2ʃ495.8ʃ70.000.2150.132ndnd湖水0.50.7450.6530.5230.492106.0ʃ7104.2ʃ6104.6ʃ798.4ʃ454.954.964.734.8494.7ʃ696.6ʃ594.6ʃ796.8ʃ6㊀㊀注:a3次平行测定结果.b3次测定相对标准偏差.cnd未检出.图8㊀湖水样品中PAEs的色谱图.湖水样品(a),湖水加标0.5ng㊃mL-1(b)和5ng㊃mL-1(c)Fig.8㊀HPLC⁃UVchromatogramsoflakewater(a),anditsspikedsampleswith0.5ng㊃mL-1(b)and5ng㊃mL-1(c)ofeachanalyte3㊀结论制备了超顺磁性的Fe3O4/C吸附剂,并用其从大体积环境水样中富集痕量的PAEs污染物.与传统的和文献报道的固相萃取方法比较,该方法具有如下优点:(a)超顺磁性吸附剂可以直接分散到水样中吸附目标物,达到吸附平衡后用磁铁分离洗脱,磁分离方法避免了耗时的过柱操作.(b)Fe3O4/C具有纳米材料大的比表面积和碳材料强的吸附能力,因此从大体积水样中萃取目标物只需要少量吸附剂就能获得满意的结果.(c)目标物的回收率不受溶液盐度和pH值的影响,因此在萃取时不需要对水样进行繁琐的调整.(d)Fe3O4/C吸附剂的制备方法简单,所用试剂价格低廉,无毒.在进行萃取的过程中不会在环境水样中引入有毒有害的物质,环境友好.参㊀考㊀文㊀献[1]㊀王红芬,程晗煜,洪坚平.环境中酞酸酯的污染现状及防治措施[J].环境科学与管理,2010,35(7):33⁃36[2]㊀CaiYQ,CaiYE,ShiYL,etal.Aliquid⁃liquidextractiontechniqueforphthalateesterswithwater⁃solubleorganicsolventsbyaddinginorganicsalts[J].MicrochimicaActa,2007,157:73⁃79[3]㊀王超英,李碧芳,李攻科.固相微萃取/高效液相色谱联用分析水中邻苯二甲酸酯[J].分析测试学报,2005,24(5):35⁃38[4]㊀PeñalverA,PocurllE,BorrullF,etal.Determinationofphthalateestersinwatersamplesbysolid⁃phasemicroextractionandgaschromatographywithmassspectrometricdetection[J].JChromatogrA,2000,872:191⁃201[5]㊀李玫瑰,李元星,毛丽秋.微滴液相微萃取技术用于气相色谱⁃质谱法测定食品中的酞酸酯[J].色谱,2007,25(1):35⁃38[6]㊀王东新.中空纤维液相微萃取⁃气相色谱测定不同天然水体中的酞酸酯类化合物[J].南京师范大学学报(工程技术版),2008,8(3):43⁃46[7]㊀胡庆兰.自制固相微萃取涂层同时测定水中的多环芳烃和酞酸酯[J].吉林大学学报(理学版),2013,51(2):317⁃320[8]㊀王鑫,许小苗,俞晔,等.固相萃取⁃气相色谱法同时测定水中的酞酸酯类环境激素[J].食品工业科技,2008,29(4):287⁃289[9]㊀陈永山,骆永明,章海波,等.固相萃取法处理环境水样中酞酸酯:流速与除水方式的影响[J].环境化学,2010,29(5):954⁃959[10]㊀黄玉娟,陈永山,骆永明,等.气相色谱⁃质谱联用内标法测定土壤中11种酞酸酯[J].环境化学,2013,32(4):658⁃665㊀㊀12期王颖辉等:碳包覆的磁性纳米材料萃取酞酸酯2249[11]㊀CaiYQ,JiangGB,LiuJF,etal.Multiwalledcarbonnanotubesasasolid⁃phaseextractionadsorbentforthedeterminationofbisphenolA,4⁃n⁃Nonylphenol,and4⁃tert⁃Octylphenol[J].AnalChem,2003,75:2517⁃2521[12]㊀WangHY,CampigliaAD.Determinationofpolycyclicaromatichydrocarbonsindrinkingwatersamplesbysolid⁃phasenanoextractionandhigh⁃performanceliquidchromatography[J].AnalChem,2008,80:8202⁃8209[13]㊀ZhaoXL,ShiYL,CaiYQ,etal.Cetyltrimethylammoniumbromide⁃coatedmagneticnanoparticlesforthepreconcentrationofphenoliccompoundsfromenvironmentalwatersamples[J].EnvironSciTechnol,2008,42:1201⁃1206[14]㊀ZhaoXL,ShiYL,WangT,etal.Preparationofsilica⁃magnetitenanoparticlemixedhemimicellesorbentsforextractionofseveraltypicalphenoliccompoundsfromenvironmentalwatersamples[J].JChromatogrA,2008,1188:140⁃147[15]㊀LiJD,ZhaoXL,ShiYL,etal.Mixedhemimicellessolid⁃phaseextractionbasedoncetyltrimethylammoniumbromide⁃coatednano⁃magnetsFe3O4forthedeterminationofchlorophenolsinenvironmentalwatersamplescoupledwithliquidchromatography/spectrophotometrydetection[J].JChromatogrA,2008,1180:24⁃31[16]㊀张小乐,王巍杰,张一江,等.磁性介孔硅胶萃取剂的制备及萃取性能研究[J].环境化学,2012,31(4):422⁃428[17]㊀ZhangSX,NiuHY,CaiYQ,etal.BariumalginatecagedFe3O4@C18magneticnanoparticlesforthepre⁃concentrationofpolycyclicaromatichydrocarbonsandphthalateestersfromenvironmentalwatersamples[J].AnalChimActa,2010,665:167⁃175[18]㊀ZhangSX,NiuHY,HuZJ,etal.PreparationofcarboncoatedFe3O4nanoparticlesandtheirapplicationforsolid⁃phaseextractionofpolycyclicaromatichydrocarbonsfromenvironmentalwatersamples[J].JChromatogrA,2010,1217:4757⁃4764[19]㊀ZhangSX,NiuHY,ZhangYY,etal.Biocompatiblephosphatidylcholinebilayercoatedonmagneticnanoparticlesandtheirapplicationintheextractionofseveralpolycyclicaromatichydrocarbonsfromenvironmentalwaterandmilksamples[J].JChromatogrA,2012,1238:38⁃45[20]㊀BruceIJ,SenT,Surfacemodificationofmagneticnanoparticleswithalkoxysilanesandtheirapplicationinmagneticbioseparations[J].Langmuir,2005,21:7029⁃7035[21]㊀LiY,LengTH,LinHQ,etal.PreparationofFe3O4@ZrO2core⁃shellmicrospheresasaffinityprobesforselectiveenrichmentanddirectdeterminationofphosphopeptidesusingmatrix⁃assistedlaserdesorptionionizationmassspectrometry[J].JProteomeRes,2007,6:4498⁃4510[22]㊀LiY,XuXQ,QiDW,etal.NovelFe3O4@TiO2core⁃shellmicrospheresforselectiveenrichmentofphosphopeptidesinphosphoproteomeanalysis[J].JProteomeRes,2008,7:2526⁃2538[23]㊀LimSF,ZhengYM,ZouSW,etal.CharacterizationofcopperadsorptionontoanalginateencapsulatedmagneticsorbentbyacombinedFT⁃IR,XPS,andmathematicalmodelingstudy[J].EnvironSciTechnol,2008,42:2551⁃2556[24]㊀PanB,XingBS.Adsorptionmechanismsoforganicchemicalsoncarbonnanotubes[J].EnvironSciTechnol,2008.42(24):9005⁃9013[25]㊀HennionMC.Graphitizedcarbonsforsolid⁃phaseextraction[J].JChromatogrA,2000,885:73⁃95Carboncoatedmagneticnanoparticleforsolid⁃phaseextractionofphthalateestersfromwatersamplesWANGYinghui1㊀㊀TENGFei2㊀㊀ZHANGYuanyuan3㊀㊀ZHANGShengxiao3∗㊀㊀LIUJunshen3㊀㊀WUQian3(1.CityManagementBureauofEnvironmentalProtectionofYantaiDevelopmentZone,Yantai,264006,China;2.ShanghaiGeneralMotor(Dongyue)AutoCompany,Yantai,264006,China;㊀3.LudongUniversity,Yantai,264025,China)ABSTRACTCarboncoatedFe3O4nanoparticles(Fe3O4/C)weresynthesizedbyasimplehydrothermalreactionandappliedassolid⁃phaseextraction(SPE)sorbentstoextracttracephthalateesters(PAEs)fromenvironmentalwatersamples.TheFe3O4/Csorbentspossesshighextractionefficiencyduetostrongadsorptionabilityofcarbonmaterialsandlargespecificsurfaceareaofthenanoparticles.Only50mgofsorbentswereneededtoextractPAEsfrom500mLwatersamples.Theadsorptionreachedequilibriumrapidlyandtheanalyteswereelutedwithacetonitrilereadily.SalinityandsolutionpHhadnoobviouseffectontherecoveyofPAHs,whichavoidsfussyadjustmenttowatersamplebeforeextraction.Underoptimizedconditions,thedetectionlimitofPAEswasintherangeof17 58ng㊃L-1.Theaccuracyofthemethodwasevaluatedbytherecoveriesofspikedsamples.Goodrecoveries(94.6% 106.6%)withlowrelativestandarddeviationsfrom2%to8%wereachieved.ThisnewSPEmethodprovidesseveraladvantages,suchashighextractionefficiency,highbreakthroughvolume,convenientextractionprocedure,andshortanalysistime.Keywords:PAEs,magneticsolid⁃phaseextraction,carbonmaterials.。

柴达木盆地咸湖相烃源岩特征——以英西地区下干柴沟组上段为例

柴达木盆地咸湖相烃源岩特征——以英西地区下干柴沟组上段为例

断块油气田FAULT-BLOCK OIL&GAS FIELD第28卷第2期2021年3月doi:10.6056/dkyqt202102007柴达木盆地咸湖相H源岩特征——以英西地区下干柴沟组上段为例舒豫川,胡广,庞谦,胡朝伟,夏青松,谭秀成(西南石油大学地球科学与技术学院,四川成都610500/摘要盐湖环境对油气生成具有重要的地质意义!国内外有诸多含油气盆地发育咸湖相?源岩!自新生代以来,在青藏高原的隆升作用下,柴达木盆地的海拔升高、湖盆逐渐封闭、持续的干寒气候及盐源的充分供应,使得柴达木盆地逐渐变成了一个典型的高原咸化湖盆,其中,下干柴沟组为柴达木盆地西部英西地区的主力?源岩层系!文中通过有机岩石学、有机地球化学及生物标志物地球化学研究,对英西地区下干柴沟组上段进行了?源岩评价,并探讨了其沉积环境及生?母质类型!研究结果表明:英西地区下干柴沟组上段?源岩总有机碳质量分数在0.31%〜1.49%,平均值为0.82%;氯仿沥青“A”质量分数在562.16x10-6~2999.65X10"6,平均值为1619.59x10^o?源岩生?母质为藻类、细菌和高等植物,以低等水生生物为主!有机质类型主要为!型,其次为"型,?源岩成熟度介于低成熟一成熟!英西地区下干柴沟组?源岩综合评价为好的?源岩!生物标志化合物特征表明,下干柴沟组上段?源岩沉积于水体盐度较高、还原性较强的湖相环境之中!关键词?源岩;生物标志化合物;下干柴沟组;英西地区;柴达木盆地中图分类号:TE13513;P618.13文献标志码:ACharacteristics of source rocks of salt lake facies in Qaidam Basin:taking XiaganchaigouFormation in Yingxi region as an exampleSHU Yuchuan?HU Guang,PANG Qian?HU Chaowei,XIA Qingsong?TAN Xiucheng(School of Geoscience and Technology?Southwest Petroleum University?Chengdu61O5OO?China) Abstract:Salt lake environment has important geological significance for oil and gas generation.There are many oil-bearing basins containing salt lake facies source rocks at home and abroad.Since Cenozoic era,with the uplift of the Tibetan Plateau,the Qaidam Basin has gradually become a typical plateau salt lake basin because of the altitude rise,the lake basin gradually closed,the persistent dry and cold climate,and the adequate supply of salt.In the basin,the Xiaganchaigou Formation is the main source rock series in the Yingxi region which located in the western part of Qaidam Basin.Based on study of organic petrology,organic geochemistry and biomarker geochemistry,the source rocks of the Xiaganchaigou Formation in the Yingxi region were evaluated, and their sedimentary environment and the types of hydrocarbon generating parent material were discussed.The results show that the total organic carbon content of source rocks in the Xiaganchaigou Formation in the Yingxi region is0.31%to1.49%,with an average value of0.82%.The value range of chloroform bitumen"A H is562.16X10"6to2,999.65X10"6,with an average of1,619.59x10"6.The source rocks are mainly composed of algae,bacteria and higher plants,mainly low aquatic organisms.The organic matter type is mainly type!,followed by type".The maturity of source rock is between low maturity and prehensive evaluation shows that the source rocks of the Xiaganchaigou Formation in the Yingxi region are good source rocks.The characteristics of biomarkers indicate that the source rocks of Xiaganchaigou Formation are deposited in the lacustrine environment which has high salinity and strong reducibility.Key words:source rocks;biomarker compounds;Xiaganchaigou Formation;Yingxi region;Qaidam Basin近年来,在咸湖相碳酸盐油气地质理论和三维地震攻关技术的助推下,柴达木盆地英西地区古近系盐下油气勘探获得重大突破,多口钻井在下干柴沟组上段盐间和盐下湖相碳酸盐岩中获得了日产超千吨的高产油气流,揭示了柴达木盆地古近系沉积体系所具有收稿日期:2020-07-30"改回日期:2021-01-07o第一作者:舒豫川,1993年生,男,在读硕士研究生,从事沉积岩石学方面的研究工作。

赤藓糖醇相变储热材料研究进展

赤藓糖醇相变储热材料研究进展

化工进展Chemical Industry and Engineering Progress2022年第41卷第8期赤藓糖醇相变储热材料研究进展杨瑜锴,夏永鹏,徐芬,孙立贤,管彦洵,廖鹿敏,李亚莹,周天昊,劳剑浩,王瑜,王颖晶(桂林电子科技大学材料科学与工程学院,广西电子信息材料构效关系重点实验室,广西新能源材料结构与性能协同创新中心,广西桂林541004)摘要:赤藓糖醇具有较高的相变焓、无毒以及优异的热稳定性,作为综合性能较好的中温相变储能材料被广泛研究。

但是,赤藓糖醇在相变过程中存在易泄漏、过冷度大以及导热性能较差的缺点,导致其热能的利用效率不高,极大地限制了其作为储热材料的应用。

本文综述了近年来在解决赤藓糖醇相变储热材料易泄漏、过冷度高和热导率低等问题的研究进展。

赤藓糖醇定型复合相变储热材料的制备方法主要有共混压制法、静电纺丝法、微胶囊法及多孔材料吸附法等,可根据不同制备方法采取相应复合策略以达到对其封装定型、降低过冷度和提高热导率的目的。

最后认为未来对赤藓糖醇复合相变储热材料的研究除了解决其本身存在的热性能问题,还需对其进行功能化,以拓展其应用前景。

关键词:相变储热;赤藓糖醇;封装定型;过冷度;导热性中图分类号:TH3文献标志码:A文章编号:1000-6613(2022)08-4357-10Research progress of erythritol phase change materials for thermalstorageYANG Yukai ,XIA Yongpeng ,XU Fen ,SUN Lixian ,GUAN Yanxun ,LIAO Lumin ,LI Yaying ,ZHOU Tianhao ,LAO Jianhao ,WANG Yu ,WANG Yingjing(School of Material Science and Engineering,Guilin University of Electrical Technology;Guangxi Key Laboratory ofInformation Materials;Guangxi Collaborative Innovation Center of Structure and Property for New Energy and Materials,Guilin 541004,Guangxi China)Abstract:Erythritol,a type of medium temperature phase change material,has attracted considerable attention in thermal storage for its good comprehensive performance such as high enthalpy,non-toxicity and excellent thermal stability.However,its ubiquitous defects,such as easy leakage during its phase transition,severe supercooling and poor thermal conductivity,reduce the efficiency of thermal energy and limit its wide practical application.In this paper,the research progress in solving the problems of easy leakage,high supercooling and low thermal conductivity of erythritol phase change materials is reviewed in recent years.The methods for preparing shape-stabilized erythritol phase-change thermal storage materials mainly include blending pressing,electrospinning,microcapsule and porous material adsorption.Corresponding composite strategies can be implemented according to different preparation综述与专论DOI :10.16085/j.issn.1000-6613.2021-2101收稿日期:2021-10-11;修改稿日期:2021-11-28。

多通道碳阴极活化过一硫酸盐降解水中有机物的性能

多通道碳阴极活化过一硫酸盐降解水中有机物的性能

大连理工大学硕士学位论文摘要活化的过硫酸盐氧化,作为一种新兴的高级氧化技术,是一种矿化难降解有毒污染物的有效方法。

在众多的活化方法中,过硫酸盐通过接受电子完成的电化学活化,具有容易操控和环境友好的特点,被认为是一种有前景的活化技术。

但在电化学活化的过程中,由于静电斥力阻碍了过硫酸盐阴离子和阴极之间的接触,导致过硫酸盐低的分解率和随后低的自由基的产生量,从而使污染物的降解效果变差。

针对此问题,本文使用天然木材衍生的碳化木(CW)制备了具有多通道的流通式阴极(FTC),通过将过一硫酸盐(PMS)阴离子限制在阴极的微通道中,能够显著地强化其与阴极的碰撞与接触,提高电化学活化的效率并增强对污染物的降解。

主要的研究成果如下:(1)通过天然松木的一步碳化制备并组装了具有丰富的介孔,良好的导电性,较高的机械强度,大量有序的微通道以及对PMS有良好的电催化活性的FTC。

以苯酚为目标污染物,探究了不同的反应条件(PMS浓度、电流密度和停留时间)对FTC电活化PMS降解苯酚性能的影响。

结果表明,在苯酚进水浓度为20 mg/L, 进水TOC=18 mg/L,进水PMS浓度为6.51 mM,背景Na2SO4为0.05 M,电流密度为2.75 mA/cm2,进水pH 2.87,停留时间10 min以及常温的条件下,通过FTC电活化PMS,PMS的分解率达到了71.9%。

苯酚和TOC的去除率分别达到了97.9%和39.6%。

EPR实验结果表明,在FTC电活化PMS的过程中,产生了大量的·OH和SO4•-。

同时,自由基淬灭实验也表明,·OH和SO4•-均参与了对苯酚的降解,且·OH对降解的贡献更大。

此外,五次循环实验的结果证明了本研究组装的FTC具有很好的稳定性。

(2)通过封闭CW的微通道,获得了流过式阴极(FBC)。

在相同的优化条件下,详细对比了在FTC中和FBC上的PMS的分解、自由基的产量以及电活化PMS降解三种酚类有机物(苯酚、双酚A和4-氯苯酚)的性能。

热红外高光谱成像仪(ATHIS)对矿物和气体的实验室光谱测量

热红外高光谱成像仪(ATHIS)对矿物和气体的实验室光谱测量

第 39 卷第 6 期2020 年 12 月Vol. 39 No. 6December 2020红外与毫米波学报J. Infrared Millim. Waves文章编号:1001-9014(2020)06-0767-11DOI :10. 11972/j. issn. 1001-9014. 2020. 06.015热红外高光谱成像仪(ATHIS)对矿物和气体的实验室光谱测量李春来匸刘成玉],金健],徐睿],谢佳楠],吕刚-袁立银-柳潇3,徐宏根3**,王建宇心收稿日期:2020- 05- 06 ,修回日期:2020- 10- 14 Received date :2020- 05- 06 , Revised date :2020- 10- 14基金项目:中国科学院青年创新促进会项目(2016218),“十三五”民用航天预研项目(D040104)”Foundation items : Supported by Youth Innovation Promotion Association CAS (2016218), and the National Defense Pre -Research Foundation of China during the 13th Five -Year Plan Period (D040104)作者简介(Biography ):李春来(1982-),男,汉族,湖北当阳人,博士 ,研究员,主要研究方向为高分辨率红外高光谱成像技术、新型计算光谱成 像技术等.E -mail :lichunlai@mail. sitp. ac. cn* 通讯作者(Corresponding author ) : E -mail : honggen_xu@163. com , jywang@mail. sitp. ac. cn(1.中国科学院空间主动光电技术重点实验室,上海200083;2.中国科学院大学杭州高等研究院,浙江杭州310024;3.中国地质调查局武汉地质调查中心,湖北武汉430205)摘要:首先介绍了热红外高光谱成像应用的独特优势,然后论述了机载热红外高光谱成像仪(Airborne Thermal ­Infrared Hyperspectral Imaging System ,ATHIS )灵敏度优化设计方法,结合仪器特点介绍了实验室矿物发射光谱和 气体吸收光谱测量的辐射模型,分析了样本红外光谱与温度分离的数据处理流程。

Porous, Crystalline, Covalent Organic FrameworksS1

Porous, Crystalline, Covalent Organic FrameworksS1

Supporting Information for Crystalline Covalent Organic Frameworks with Hydrazone Linkages Fernando J. Uribe-Romo,†,§ Christian J. Doonan,†,¶ Hiroyasu Furukawa,† Kounosuke Oisaki,†,|| and Omar M. Yaghi*,†,‡†Center for Reticular Chemistry, Center for Global Mentoring, Department of Chemistry and Biochemistry, University of California–Los Angeles, 607 Charles E. Young Dr. East, Los Angeles, California 90095, United States‡Graduate School of EEWS, Korea Advanced Institute of Science and Technology, Daejeon, Korea*Corresponding Author: yaghi@Current addresses: §Cornell University, ¶The University of Adelaide, Australia, ||The University of Tokyo, JapanSection S1 S2 S3 S4 S5 S6 S7 Materials and methods Solid state nuclear magnetic resonance spectroscopy Powder X-ray diffraction, crystal modeling, refinements Thermalgravimetry Low-pressure gas adsorption determinations Scanning electron microscopy FT-IR spectra ReferencesPage S1 S6 S19 S40 S42 S53 S56 S66S1Section S1. Materials and methods All starting materials and solvents, unless otherwise specified, were obtained from Aldrich Chemical Co. and used without further purification. All reactions were performed at ambient laboratory conditions, and no precautions were taken to exclude oxygen or atmospheric moisture unless otherwise specified. A Pyrex glass tube charged with reagents and flash frozen with liquid N2 were evacuated using a Schlenk line by fitting the open end of the tube inside a short length of standard rubber hose that was further affixed to a ground glass tap which could be close to insolate this assembly from dynamic vacuum when the desired internal pressure was reached. Tubes were sealed under the desired static vacuum using an oxygen-propane torch. Elemental microanalyses were performed on a Thermo FlashEA 1112 series CNHS-O analyzer, calibrated with sulfanilamide and using cisteine as external reference. 1,3,5-benzenetricarbaldehyde and 1,3,5-tris(4-formylphenyl)benzene were synthesized according to published procedures [ i ]. Fourier transform Infrared spectra of starting materials, model compounds and synthesized COFs were obtained as KBr pellets using a Shimadzu IRA Affinity-1 spectrometer.Synthesis of 2,5-diethoxy-terephthalohydrazide. 0.5 g (1.97 mmol) of diethyl 2,5-dihydroxy-terephthalate, 2 g of potassium carbonate, 40 mg of potassium iodide were suspended in 40 mL of acetone. 400 ml of ethyl iodide were added to this mixture and heated to reflux with stirring for 48 h. The mixture was hot filtered and the solid residue was rinsed with hotS2acetone to afford a yellow solution, from which the solvent was removed by rotoevaporation. The residue was suspended in water and extracted with 3 × 100 mL of methylene chloride. The organic extracts were mixed, rinsed with brine (3 times) and dried over anhydrous sodium sulfate. The dried solution was rotoevaporated and the obtained solid was recrystallized in methanol. The recrystallized solid was dissolved in 45 mL of ethanol and 6 mL of hydrazine hydrate. The mixture was stirred and heated to reflux for 40 h. After cooling the mixture, white crystals precipitated, which were isolated by filtration and rinsed with water and ethanol. The white solid was dried at 50 ° for 3 hours. Yield: 126 C mg (30%). δH (400 MHz; CDCl3; Me4Si) 1.5 (2H, t, CH3CH2O) 4.3 (3H, q, CH3CH2O) 4.18 (br, NHNH2) 7.85(1H, s, aromatic) 9.19 (br, CONHNH2). δC (400 MHz; CDCl3; Me4Si) 14.83, 65.53, 115.8, 123.9, 150.7, 165.3.Synthesis of COF-42: A Pyrex tube measuring o.d × i.d 10 × 8 mm was charged with benzene-1,3,5-tricarbaldehyde (5 mg, 44 µmol), 2,5-diethoxyterephthalohydrazide (18 mg, 65 µmol), 250 mL of anhydrous dioxane and 750 mL of mesitylene. The was tube immersed in an ultrasonic bath for 15 min; following sonication 100 mL of 6 M aqueous acetic acid were added. The tube was flash frozen at 77 K (liquid N2 bath), evacuated to an internal pressure of 150 mTorr and flame sealed. Upon sealing, the length of the tube was reduced to 18-20 cm. The reaction was heated at 120 ºC for 72 h yielding a pale-yellow solid at the bottom of the tube which was isolated either by filtration or centrifugation and washed with anhydrous dioxane and anhydrous acetone, the resulting powderS3was immersed in anhydrous acetone for 24 h and dried at room temperature and 10-2 mTorr for 12 h to afford a pale-yellow powder. Yield: 18 mg, 78% for C9H9N2O2. Elemental analysis calculated (%): C, 61.46; H, 5.12; N, 15.81. Found (%): C, 54.45; H, 3.35; N, 14.50. FT-IR (cm-1): 3448 (br), 3278 (sh), 2977 (w), 2931 (br), 1658 (vs), 1607 (sh), 1543 (m), 1489(m), 1413 (m), 1388(m), 1303 (w), 1226 (m), 1111 (w), 1086 (w), 1033(w), 948 (w), 894 (w), 780 (m), 674 (w), 648 (w), 688 (w), 439 (br).Synthesis of COF-43: A Pyrex tube measuring o.d × i.d 10 × 8 mm was charged with 1,3,5-tris(4-formylphenyl)benzene (17 mg, 43 µmol), 2,6-diethoxyterephthalohydrazide (18 mg, 65 mmol), 100 mL of anhydrous dioxane and 900 mL of mesitylene. The was tube immersed in an ultrasonic bath for 15 min; following sonication 100 mL of 6 M aqueous acetic acid were added. The tube was flash frozen at 77 K (liquid N2 bath), evacuated to an internal pressure of 150 mTorr and flame sealed. Upon sealing, the length of the tube was reduced to 18-20 cm. The reaction was heated at 120 ºC for 72 h yielding a pale colored solid at the bottom of the tube which was isolated either by filtration or centrifugation and washed with dioxane and acetone, the resulting powder was immersed in anhydrous acetone for 24 h and dried at room temperature and 10-2 mTorr for 12 h to afford a pale-yellow powder. Yield: 27 mg, 82% for C15H13N2O2 based on the hydrazide as limiting reagent. Elemental analysis calculated (%): C, 71.12; H, 5.17; N, 11.06. Found (%): C, 67.24; H, 5.31; N, 10.85. FT-IR (cm-1): 3433 (s, br), 3288 (sh), 3062(w), 2978(w), 2893(w), 2738(w), 1658(vs), 1605(s),S41496 (m), 1412 (m), 1388 (m), 1300(w), 1203(m), 1103(w), 1077(w), 1033 (m), 935(w), 894(w), 825(w), 794(w), 709 (vw), 578(w), 540(w).S5Section S2. Solid-state nuclear magnetic resonance spectroscopy. High-resolution solid-state nuclear magnetic resonance (NMR) spectra were recorded at ambient pressure on a Bruker DSX-300 spectrometer using a standard Bruker magic angle-spinning (MAS) probe with 4 mm (outside diameter) zirconia rotors. The magic angle was adjusted by maximizing the number and amplitudes of the signals of the rotational echoes observed in the79Br MAS FIDsignal from KBr. Cross-polarization with MAS (CP-MAS) used to acquire 13C data at 75.47 MHz. The 1H and13C ninety-degree pulse widths were both 4 ms. TheCP contact time varied from 1 to 10 ms. High power two-pulse phase modulation (TPPM) 1H decoupling was applied during data acquisition. The decoupling frequency corresponded to 72 kHz. The MAS sample-spinning rate was 10 kHz. Recycle delays between scans varied between 3 and 10 s, depending upon the compound as determined by observing no apparent loss in the one scan to the next. The13 13C signal fromC chemical shifts are given relative totetramethylsilane as zero ppm, calibrated using the methylene carbon signal of adamantane assigned to 37.77 ppm as secondary reference. A contact time vs. intensity plot was constructed after measuring spectra with CP contact times at 1, 3, 5, 7 and 10 ms.S6Figure S1.13C CP-MAS spectrum of Triformylbenzene. Small signals below 100 and above 250 ppm correspond to spinning side bands.Signal (ppm) 192.34 136.80 133.71Assignment 1 3 2Comments Carbonyl carbon Aromatic C-H carbon (beta-aldehyde) Aromatic (alpha-aldehyde)S7Figure S2. 13C CP-MAS spectrum of 1,3,5 tris-(4-formyl-phenyl)-benzene.Signal (ppm) 194.38 191.06Assignment 1145.35 142.54 139.97 134.68 127.625 6 2 7 3,4Comments Carbonyl. These two signals correspond to the C=O aldehyde aromatic carbons. Two carbonyl atoms with different shift are observed as effect of having different chemical environments when packed in the solid state [Sii]. Aromatic quaternary C, para-aldehyde. Aromatic quaternary C. Aromatic quaternary C, alpha-aldehyde Aromatic C-H. Aromatic C-H.S8Figure S3. 13C CP-MAS spectrum of 2,4-diethoxyterepthalohydrazide. Signals marked in yellow correspond to spinning side bands.Signal (ppm) 165.36 150.09 122.88 113.58 65.22 16.25Asignment Comment 1 Amide carbon. Aromatic quaternary C-O carbon, alpha-ether, beta3 amide. Aromatic quaternaty carbon, alpha-amide. 2 Aromatic C-H, beta-amide beta-ether. 4 5 Aliphatic methylene carbon. 6 Aliphatic methyl carbon.S9Figure S4. 13C CP-MAS spectrum of N'-benzylidene-benzocarbohydrazide model compound.Signal (ppm) 164.72 150.15 133.72 131.55 129.61 127.58Assignment 6 5 4,7 1, 10 2,9 3,8Comments Amide carbon Imine carbon Aromatic quaternary carbons. Aromatic C-H carbons. Aromatic C-H carbons. Aromatic C-H carbons.S10Figure S5. 13C CP-MAS spectrum of COF-42 with 5 ms contact time.Signal (ppm) 155-162 (broad) 149.37Assignment 4 3Comment Amide carbon. Imine carbon. The imine nature of this signal was unrevealed by measuring spectra varying the cross-polarization contact time (see Figure S9). All the other signals within the 130-160 ppm range correspond to quaternary carbons, which will not have major effect in the intensity when varying cross-polarization time. S11146.5 (shoulder)7133.92 125.80 121.12 113.26 64.38 20.20 15.18 11.782 5 1 6 8 9Aromatic quaternary C-O carbon. Although this signal is in the same chemical shift as the imine carbon, varying the cross polarization contact time, the intensity of this signal does not get affected. Aromatic quaternary carbon. Aromatic quaternary carbon. Aromatic C-H carbon. Aromatic C-H carbon. Methylene carbon. Methyl carbons. These signals correspond to the same CH3 carbon but since this group points towards the pore, it has more degrees of freedom and can interact with different components of the COF, thus having different chemical environments.S12Figure S6. 13C CP-MAS spectrum of COF-42 with 1 ms contact time.S13Figure S7. 13C CP-MAS spectrum of COF-42 with 3 ms contact time.S14Figure S8. 13C CP-MAS spectrum of COF-42 with 7 ms contact time.S15Figure S9. Intensity vs. contact time plot of COF-42. Note the high rise on the intensity of the peak at 149 ppm, sign of a protonated carbon with low motion [Siii], in the same range of the imine carbon observed in the model compound (150 ppm), and with respect to the signals of quaternary carbons with low motion in the range of 125-161 ppm. Signals below 125 ppm are not shown.S16Figure S10. 13C CP-MAS spectrum of COF-43.Signal (ppm) 159.57 (broad) 149.97 148 (shoulder) 140.05 (broad)Assignment 6 7 3 11,12Comment Amide carbon. Imine carbon. Aromatic C-O carbon. This signal is considerably hindered by the imine, as shown for COF-42 Aromatic quaternary carbons.S17132.30 126.72 – 121.15 (broad) 115.07 65.51 21.03 15.098 9,10,13 (5) 4 2 1Aromatic quaternary carbon. Aromatic C-H carbons. Note: signal for quaternary carbon 8 is hindered in the range 120-125ppm. Aromatic C-H carbon. Methylene carbon. Methyl carbons. These signals correspond to the same CH3 carbon but since this group points towards the pore, it has more degrees of freedom and can have different chemical environments inside the COF.S18Section S3. Powder X-ray diffraction Data collection Powder X-ray diffraction data were collected using a Bruker D8-advance θ-2θ diffractometer in reflectance Bragg-Brentano geometry employing Ni filtered CuKα lines focused radiation (1.54059 Å, 1.54439 Å) at 1600 W (40 kV, 40 mA) power and equipped with a Na(Tl) scintillation detector fitted at 0.2 mm radiation entrance slit. Samples were mounted on zero background sample holders by dropping powders from a wide-blade spatula and then leveling the sample with a razor blade. The best counting statistics were achieved by collecting samples using a 0.02º 2θ step scan from 1 – 50º with exposure time of 2 s per step.S19Figure S11. COF-42 as synthesizedS20Figure S12. COF-42 activated.Figure S13. COF-42 compared against 1,3,5-benzenetriscarboxaldehyde.Figure S14. COF-42 compared against 2,5-diethoxy-terepthtalohydrazide.Figure S15. COF-43 as synthesizedFigure S16. COF-43 activated.Figure S17. COF-43 compared against 1,3,5-benzenetriscarboxaldehyde.Figure S18. COF-43 compared against 2,5-diethoxy-terepthtalohydrazide.Crystal structure modeling.The crystal models for COF-40 and COF-41, including cell parameters and atomic positions were generated using Material Studio chemical structure-modeling software [iv] employing the Crystal Building module. Cell parameters were determined as follows: The crystal structure of the molecular specie (E)-N'-benzylidene-benzohydrazide was obtained from the CCDC and used to measure the distance between the centers of the phenyl rings (8.709 Å). This value was used as half the distance between the points of extension (vertices) for the simulated nets. For the expanded version, the molecule (E)-N’-(4-phenyl-)-benzylidene-benzohydrazide was generated in Material Studio by adding a phenyl ring to the initial molecule and measuring the distance of the center of the corresponding phenyl rings. The crystallographic information of the nets (cell parameters, space group, vertex and edges positions) was obtained from the Reticular Chemistry Structure Resource [v] under the symbol gra for staggered trigonal layers (P63/mmc reduced to P63/m to allow asymmetry of the links) and bnn for eclipsed layers (P6/mmm reduced to P6/m to allow asymmetry). Since the unit cell parameters contained in the RCSR correspond to those of the net with unitary edge size, multiplication of a and b cell parameters with measured e from the molecular species will give the cell parameters of the simulated structure. The c cell parameter was kept with a distance of 3.51 Å for the bnn topology and 6.45 Å for gra, similar as observed in other COFs. Vertex position for both nets were replaced with benzene rings and the edge of the nets in the 2-dimensional extension were replaced with the (N'1E,N'4E)-N'1,N'4-dimethylidene-2,5-diethoxy-terephthalohydrazide unit for COF-42 and (N'1E,N'4E)-N'1,N'4-dibenzylidene-2,5-diethoxy-terephthalohydrazide for COF-43. The interlayer edge was left unconnected. The constructed structures were minimized with the Forcite module in Materials Studio using the universal force field (UFF) using charges Q eq from the UFF. [vi] The final optimized structures were used to simulate their powder diffraction patterns in Materials Studio. The Simulated patterns were obtained using the Reflex Powder Diffraction module of Material Studio.Crystallographic information of modeled COFsTable S1. COF-42 bnnSpace group P6/ma = 29.9768 Åc = 4.05 ÅAtom x/a y/b z/cH1 0.33612 0.32403 0.78181H2 0.42474 0.34719 1.22439C3 0.38352 0.67953 0.00000C4 0.37095 0.71716 0.00000C5 0.46151 0.44892 0.00000C6 0.45120 0.48802 0.00000C7 0.46878 0.57675 0.00000C8 0.48730 0.53952 0.00000O9 0.49804 0.62101 0.00000N10 0.41908 0.56296 0.00000N11 0.40520 0.59983 0.00000C12 0.35904 0.58914 0.00000C13 0.59103 0.64612 0.00000O14 0.58395 0.59727 0.00000C15 0.64677 0.68237 0.00000H16 0.65427 0.72135 0.00000H17 0.58795 0.52490 0.00000H18 0.39076 0.52620 0.00000H19 0.26706 0.57759 0.00000H20 0.32947 0.55057 0.00000Table S2COF-42 graSpace group P63/ma = 30.476 Åc = 6.5811 ÅAtom x/a y/b z/cH1 0.86441 1.24332 0.75002 H2 0.76368 1.05657 0.75001 H3 0.94304 1.14220 0.74992 H4 1.00670 1.11882 0.75004 H5 1.06839 1.08994 0.74994 H6 0.62790 1.20166 0.75002 H7 0.74725 1.33177 0.74992 H8 0.83840 1.52284 0.74991 H9 1.02832 1.28998 0.61399 H10 0.94575 1.27080 0.88857 H11 0.68183 1.03058 0.61148 H12 0.61175 1.04961 0.88751 C13 0.05056 0.01195 0.25000 C14 0.03880 0.05050 0.25000 C15 0.33213 0.62025 0.25000 C16 0.37847 0.66496 0.25000 C17 1.25445 0.30151 0.25000 C18 0.76252 0.42571 0.75000 N19 0.76086 0.46685 0.75000 N20 0.80142 0.51609 0.75000 C21 0.78666 0.55386 0.75000 O22 0.74099 0.53803 0.75000 C23 0.82135 0.61016 0.75000 C24 0.87496 0.63493 0.75000 C25 0.90256 0.68822 0.75000 C26 0.87859 0.71780 0.75000 C27 0.79752 0.63971 0.75000 C28 0.82472 0.69251 0.75000 C29 0.91267 0.77456 0.75000 C30 0.92045 0.89702 0.75000 O31 0.95850 0.79178 0.75000 N32 0.89557 0.81057 0.75000 N33 0.93194 0.86169 0.75000 C34 1.00843 1.26747 0.75000 H35 1.01185 1.23287 0.75000 C36 0.67504 1.04704 0.75000 C37 0.61987 1.03373 0.75000 O38 0.70660 1.10092 0.75000 H39 0.59488 0.99192 0.75000 O40 0.79940 0.72052 0.75000Table S3. COF-43 bnn Space group P6/m a = 45.8877 Å c = 3.9784 Å Atom x/a H1 0.57059 H2 0.58046 H3 0.42871 H4 0.41094 H5 0.32594 H6 0.30658 H7 0.37099 H8 0.41508 H9 0.39360 H10 0.56185 C11 0.46527 C12 0.48150 C13 0.45922 C14 0.51709 O15 0.42882 N16 0.47040 N17 0.44711 C18 0.45638 C19 0.36755 C20 0.34451 C21 0.80987 C22 0.73954 C23 0.79865 C24 0.78615 C25 0.76426 C26 0.75172 O27 0.53420 H28 0.60876 C29 0.57010 C30 0.58090y/b 0.63325 0.58451 0.81668 0.75822 0.79429 0.73552 0.85388 0.91078 0.70783 0.53188 0.48203 0.51758 0.53320 0.53580 0.51409 0.56710 0.57855 0.61029 0.69003 0.70192 0.43119 0.38310 0.39671 0.44174 0.37311 0.41831 0.57118 0.64279 0.59017 0.62723z/c 0.22324 0.22588 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000S31Table S4. COF-43 gra Space group P63/m a = 45.3408 Å c = 6.4554 Å Atom x/a H1 0.24698 H2 0.23647 H3 0.66334 H4 0.60482 H5 1.59711 H6 1.53823 H7 1.64703 H8 1.51626 H9 1.57488 H10 1.30275 O11 1.36957 O12 1.29612 H13 1.36293 H14 1.14975 H15 1.09145 H16 1.01892 H17 1.47870 C18 0.79036 N19 0.78097 N20 0.80414 C21 0.79291 O22 0.76250 C23 0.81518 C24 0.85078 C25 0.86829 C26 0.85201 C27 0.79889 C28 0.81640 C29 0.87427 C30 0.87686 O31 0.90469 N32 0.86303 N33 0.88620 C34 0.07268 C35 0.08475 C36 0.11913 C37 0.14288 C38 0.13172 C39 0.09741 C40 0.73502 C41 0.68939y/b 0.32896 0.27034 0.74918 0.70099 1.36036 1.34080 1.37487 1.23821 1.25631 1.19813 1.23767 1.09522 1.13474 1.09494 1.07733 0.95876 0.29558 0.51340 0.53576 0.57052 0.59318 0.58184 0.63109 0.64854 0.68398 0.70321 0.65032 0.68576 0.74111 0.82092 0.75247 0.76377 0.79853 0.02282 -0.00026 0.01065 0.04490 0.06820 0.05748 0.26922 0.28254z/c 0.39676 0.10555 0.39677 0.39455 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000 0.75000S32C42 C43 C44 C45 H46 H47 H48 H49 C50 C51 C52 C53 C54 C55 H56 C57 H58 C59 H600.71187 0.67758 0.72408 0.66646 1.09560 1.13507 1.16230 1.17053 0.03415 0.02413 0.34495 0.36934 0.24694 0.23673 0.27473 0.62089 0.63281 0.64750 0.149660.23472 0.22404 0.29269 0.24737 1.06851 1.12720 1.24389 1.42180 0.01073 0.03518 0.64313 0.67749 0.28643 0.31312 0.29826 0.70665 0.69076 0.74355 0.186910.75000 0.75000 0.75000 0.75000 0.25000 0.25000 0.25000 0.25000 0.25000 0.25000 0.25000 0.25000 0.25000 0.25000 0.25000 0.25000 0.25000 0.25000 0.25000S33Figure S19. COF-42 compared against simulation of the bnn crystal model.S34Figure S20. COF-42 compared against simulation of the gra crystal model.S35Figure S21. COF-43 compared against simulation of the bnn crystal model.S36Figure S22. COF-43 compared against simulation of the gra crystal model.S37Pawley refinement. Extraction of the integrated intensities (Iobs) was conducted with the Powder Refinement routine of the Reflex Module in Material Studio using data from 2θ = 1 – 45º. Backgrounds were first refined applying a 2nd order ChebyschevPolynomial. The profile was calculated starting with the unit cell parameters from the crystal models and the space group P6/m. The integrated intensities (Iobs) were extracted by a full pattern decomposition using a Thomson-Cox-Hasting pseudo Voigt peak profile, followed by refinement of peak asymmetry using Finger et al. asymmetry function (2 parameters). Unit cells and zero-shift were then refined with peak asymmetry. Once this was achieved, the background was refined with 20th-order polynomial. Refinement of unit cell parameters, zero shift, peak asymmetry, crystallite size and strain were used for the final profile. For COF-42, refinements required starting with a cell parameter of c = 10.53 Å equivalent to 3× the observed interlayer distance (dinterlayer = 3.51 Å).Residuals COF-42 a = 28.827(15) Å Rp = 5.23 % COF-43 a = 43.164(12) Å Rp = 1.68 % c = 9.739(12) Å Rwp = 6.62 % c = 3.590(17) Å Rwp = 2.39 %S38Figure S23. COF-42 compared to the simulated bnn structure using c' = 3c.S39Section S4. Thermalgravimetry. Samples were run on a TA Instruments Q-500 series thermal gravimetric analyzer with samples held in a platinum pan under nitrogen atmosphere using a 5 °C min-1 ramp rate. Figure S24. COF-42S40Figure S25. COF-43. As-synthesized.S41Section S5. Low-pressure gas adsorption measurements. Gas adsorption isotherms were measured volumetrically using a Quantachrome Autosorb-1 automated adsorption analyzer. A liquid argon bath (87 K) was used for Ar isotherm, and the Ar was UHP grade (grade 5). Brunauer-Elmett-Teller (BET) and Langmuir models were used to determine the specific surface areas (SBET and SLang, m2 g-1) using adsorption branches in the ranges indicated in the corresponding plots below. BET model was fit in concordance to the consistency criteria of the method in frameworks [vii]. In all isotherm plots, closed circles describe adsorption data points and open circles are used to represent desorption data points.Non-local DFT pore size distribution calculation. The pore size distribution was calculated from Ar adsorption isotherms by the non-local density functional theory (NLDFT) methods using the Ar-zeolite/silica cylindrical pores at 87 K kernel (applicable pore diameters 3.5 Å – 1000 Å) for argon data as implemented in the AUTOSORB data reduction software.S42Figure S26. Argon adsorption isotherm of COF-42 measured at 87 K.S43Figure S27. BET plot of COF-42 from Ar adsorption data.S44Figure S28. Langmuir plot of COF-42 from Ar adsorption data.S45Figure S29. NLDFT fitting of the Ar adsorption isotherm of COF-42.S46Figure S30. Cumulative pore volume vs. pore width (purple) and pore size distribution (black) plots from NLDFT fitting of the Ar adsorption isotherm of COF-42.S47Figure S31. Argon adsorption isotherm of COF-43 measured at 87 K.S48Figure S32. BET plot of COF-43 from Ar adsorption data.S49Figure S33. Langmuir plot of COF-43 from Ar adsorption data.S50。

MATERIALS, DEVICES AND SYSTEMS FOR PIEZOELECTRIC E

MATERIALS, DEVICES AND SYSTEMS FOR PIEZOELECTRIC E

专利名称:MATERIALS, DEVICES AND SYSTEMS FOR PIEZOELECTRIC ENERGY HARVESTING ANDSTORAGE发明人:DAGDEVIREN, Canan,ROGERS, JohnA.,SLEPIAN, Marvin J.申请号:US2015/011245申请日:20150113公开号:WO2015/106282A1公开日:20150716专利内容由知识产权出版社提供专利附图:摘要:Materials and systems that enable high efficiency conversion of mechanicalstress to electrical energy and methods of use thereof are described herein. The materials and systems are preferably used to provide power to medical devices implanted inside or used outside of a patient's body. For medical devices, the materials and systems convert electrical energy from the natural contractile and relaxation motion of a portion of a patient's body, such as the heart, lung and diaphragm, or via motion of body materials or fluids such as air, blood, urine, or stool. The materials and systems are capable of being bent, folded or otherwise stressed without fracturing and include piezoelectric materials on a flexible substrate. The materials and systems are preferably fashioned to be generally conformal with intimate apposition to complex surface topographies.申请人:THE ARIZONA BOARD OF REGENTS ON BEHALF OF THE UNIVERSITY OF ARIZONA,THE BOARD OF TRUSTEES OF THE UNIVERSITY OF ILLINOIS地址:The University of Arizona Tech Transfer Arizona 220 W. Sixth Street 4th Floor Tucson, Arizona 85701 US,352 Henry Administration Building 506 South Wright Street Urbana, Illinois 61801 US国籍:US,US代理人:VORNDRAN, Charles et al.更多信息请下载全文后查看。

energy and environmental materia分区

energy and environmental materia分区

energy and environmental materia分区
Energy and Environmental Materials(能源与环境材料)是一个研究领域,主要关注新型、可持续的能源转换和储存技术,以及环境保护和治理方面的材料研究。

这个领域涉及多种学科,如材料科学、化学、物理学、工程学等。

在能源和环境材料的研究中,科学家们致力于开发高性能、低成本、环保的材料,以应对全球能源危机和环境问题。

能源与环境材料的研究方向主要包括以下几个方面:
1. 新能源材料:如太阳能电池、燃料电池、锂离子电池等。

2. 节能材料:如绝热材料、发光材料、光电显示材料等。

3. 环保材料:如水处理剂、空气净化剂、生物降解材料等。

4. 可持续发展材料:如生物质材料、循环利用材料、低碳水泥等。

5. 能源回收与储存材料:如超级电容器、锂离子电池、钠离子电池等。

6. 纳米材料:如纳米金属、纳米氧化物、纳米复合材料等。

7. 先进陶瓷材料:如高温陶瓷、超导陶瓷、陶瓷纳米纤维等。

在这些方向上,研究人员不断努力创新,为解决能源和环境问题作出贡献。

能源与环境材料的研究成果在国内外受到了广泛关注,相关论文发表在各个顶级学术期刊上。

其中,部分优秀论文来自我国科学家,展示了我国在能源与环境材料领域的研究实力。

总之,能源与环境材料是一个具有重要战略意义的领域,关乎国家能源安全、环境保护和可持续发展。

未来,随着科研技术的不断进步,相信能源与环境材料研究将取得更多突破,为人类创造更美好的未来。

赤铁矿在污染控制方面的晶面效应研究进展

赤铁矿在污染控制方面的晶面效应研究进展

第 43 卷第 3 期2024年 5 月Vol.43 No.3May 2024中南民族大学学报(自然科学版)Journal of South-Central Minzu University(Natural Science Edition)赤铁矿在污染控制方面的晶面效应研究进展张胜男1,李玲一1,胡立鹃2,李俊学1,程微1*(1 中南民族大学资源与环境学院,武汉430074;2 湖北省协诚交通环保有限公司,武汉430050)摘要赤铁矿(α-Fe2O3)是热力学最稳定的氧化铁矿物,广泛存在于土壤和沉积物中,并在元素的生物地球化学循环中发挥重要作用.天然赤铁矿颗粒由于形成条件的差异而具有不同的形貌和暴露晶面.不同原子排列和电子结构的暴露面赋予赤铁矿特定的表面电荷性质和活性位点密度,使其反应性表现出晶面依赖性.综述了产生具有特定晶面的赤铁矿纳米颗粒的合成方法,重点探讨了赤铁矿在还原溶解、吸附、催化和水解反应中的晶面依赖效应以及对污染物去除的作用,还总结了赤铁矿晶面耦合Fe(Ⅱ)对污染控制的最新进展,并对赤铁矿未来的应用和发展进行了展望. 为研究赤铁矿在元素的生物地球化学循环中的影响提供依据,并为污染控制和环境修复奠定理论基础.关键词赤铁矿;纳米晶体;暴露晶面;晶面依赖效应;环境修复中图分类号X506 文献标志码 A 文章编号1672-4321(2024)03-0307-12doi:10.20056/ki.ZNMDZK.20240303Research progress on crystal facet effects of hematite in pollution control ZHANG Shengnan1,LI Lingyi1,HU Lijuan2,LI Junxue1,CHENG Wei1*(1 College of Resources and Environment, South-Central Minzu University, Wuhan 430074, China;2 Hubei Xiecheng Traffic Environmental Protection Co., LTD, Wuhan 430050, China)Abstract Hematite (α-Fe2O3) is the thermodynamically most stable iron oxide mineral, widely distributed in soils and sediments, which plays an important role in the biogeochemistry of elements. Natural hematite particles exhibit different morphologies and exposed crystal facets due to variations in formation conditions. The exposed facets with different atomic arrangements and electronic structures impart specific surface charge properties and active site densities to hematite,resulting in facet-dependent reactivity. An overview of the synthesis methods for hematite nanocrystals with specific crystal facets were provided and the facet-dependent effect in reductive dissolution, adsorption, catalysis, and hydrolysis and its role in pollutant removal were discussed. Additionally, the recent advances in pollution control by coupling Fe (Ⅱ) with hematite facets were summarized,and prospects were made for the future application and development of hematite. It provided a basis for studying the impact of hematite on the biogeochemical cycling of elements, and a theoretical basis for its pollution control and environmental remediation.Keywords hematite; nanocrystals; exposed crystal facets; facet-dependent reactivity; environmental remediation铁(Fe)是地球上最丰富的过渡族金属元素,存在于大量的天然矿物中[1].自然界中常见的铁矿物有赤铁矿(α-Fe2O3)、磁赤铁矿(γ-Fe2O3)、磁铁矿(Fe3O4)、针铁矿(FeOOH)等,其中赤铁矿是热力学最稳定的铁氧化物且在自然界中含量丰富,在环境科学[2]、光催化[3-5]、太阳能[6]、锂离子电池[7]、地球化学[8]、生物技术[9]等领域得到了广泛的研究和应用.赤铁矿(α-Fe2O3)在土壤和沉积物中普遍存在,在元素和环境污染物的归趋和转化过程中发挥重要作用[10],故大量研究在分子水平上揭示了赤铁矿纳米晶体与环境污染物在水土界面上的基本地球化学过程.在矿物形成和随后的溶解过程中,天然收稿日期2023-10-23* 通信作者程微(1988-),女,副教授,博士,研究方向:污染物迁移转化机理和环境修复,E-mail:*******************.cn 基金项目国家自然科学基金资助项目(NSFC22006165);中央高校基本科研业务费专项资金资助项目(CZQ21012)第 43 卷中南民族大学学报(自然科学版)赤铁矿纳米晶体在不同的物理和/或地球化学条件下呈现出不同的形态和尺寸,导致暴露的晶体学表面(如{001}、{110}、{012}等)的比例不同.不同暴露晶面上原子排列方式和电子结构存在巨大差异,这种差异赋予赤铁矿纳米晶体不同的Fe―O键拓扑结构、活性位点密度和表面电荷特性等[11-13],深刻地影响了赤铁矿-水界面的反应性.研究表明赤铁矿纳米晶体的反应活性与暴露晶面有关[6,14],即赤铁矿纳米晶体的反应性具有晶面效应.赤铁矿纳米晶体的晶面效应及环境行为体现在许多方面,如铁还原溶解[15-16],吸附重金属[17-20]、类金属[12,21]和腐殖质物质[22],芬顿降解[23-25],热催化氧化[26-27],水解反应[28-29]等.目前关于赤铁矿晶面效应的综述较少,且前人的研究主要关注纳米晶体不同晶型和暴露晶面的形成机制及影响因素[14]和赤铁矿晶面效应对吸附重金属离子的影响[30],对赤铁矿的晶面效应在其他反应,比如催化与水解反应中的应用未见报道.因此,本文介绍了具有特定晶面的赤铁矿纳米颗粒的合成方法,详细综述了赤铁矿在还原溶解、吸附、催化和水解反应中的晶面效应,总结了赤铁矿晶面耦合Fe(Ⅱ)去除污染物的最新进展,并对赤铁矿相关方面的研究进行了展望.1 赤铁矿的形貌与晶面调控赤铁矿具有六方密堆积结构,其中三分之二的八面体位点被Fe3+占据.每个八面体与同一平面内的三个相邻八面体共边,一个面与相邻平面内的另一个八面体共面[31].这种独特的晶体学结构特征可以导致赤铁矿在自然环境中暴露出{001}、{012}、{113}、{101}、{104}和{110}等不同晶面.赤铁矿晶体的理化性质与其相应的体相结构状态密切相关,可以通过调控其形貌与尺寸来提高特定反应的选择性与活性,因此对赤铁矿晶体的形貌和尺寸进行控制合成的研究非常重要.在过去的几十年里,学者们已成功合成了各种形貌和尺寸的赤铁矿纳米晶体,包括纳米环[图1(a)][32]、纳米纺锤体[图1(b)][33]、纳米棒[图1(c)][34]、纳米管[图1(d)][35]、六边形纳米片[图1(e)][36],纳米圆盘[图1(f)][7],纳米立方体[图1(g)][37],六方双锥[图1(h)][38],多孔微米球[图1(i)][39]等.通过水热法可以高效地获得形貌规整的赤铁矿纳米晶体[40-42],其中合成介质、pH、温度和表面活性剂等因素是影响矿物表面形貌的关键因素.为了控制赤铁矿纳米晶体的尺寸、形貌和结构,需要施加可控的条件,如使用一些有机物或无机物作为吸收剂、还原剂或反应源.在典型的赤铁矿合成过程中,氯化铁或乙酰丙酮铁是最常用的铁源,而醋酸钠、油酸钠、油酸、乙醇等通常被选为反应剂.目前已经开发出了多种有效方法来合成具有不同暴露晶面的赤铁矿纳米晶体[36,38,43-49],表1总结了水热法可控合成不同暴露晶面赤铁矿的方法.CHEN等[36]以氯化铁、乙醇、醋酸钠和水为反应源,制备了优势晶面为{001}的赤铁矿六方纳米片.他们发现乙醇能在{001}晶面上优先吸附,醋酸钠的羧基能与{001}晶面上的铁离子强结合,这些导致了赤铁矿六方纳米片的生长.OUYANG等[38]以乙酰丙酮铁为铁源,氢氧化钠、油酸、乙醇和水为反应剂,获得了具有{001}暴露面的赤铁矿纳米片.其研究表明混合溶剂中水含量的增加可以降低Fe3+的过饱和度,有利于生长形貌规整的赤铁矿纳米片.LIANG等[45]使用氯化铁、氢氧化钠、油酸、乙醇和水得到了平均尺寸为20 nm的赤铁矿纳米立方体,其形状特征符合{012}晶面围成的理想菱面体的几何模型.随后,WANG等[46]使用氯化铁、油酸钠、油酸、乙醇和水同样制备了具有{012}暴露面的赤铁矿纳米立方体.通过煅烧铁氢氧化物的前驱体(如水铁矿和四方纤铁矿)制备出具有{110}暴露晶面的赤铁矿纳米棒,ZHOU等[47]将水铁矿纳米颗粒在300 ℃空气中热脱水1 h制备了赤铁矿纳米棒,WU等[48]使用氯化铁和图1 各种不同形貌的赤铁矿纳米晶体[7,32-39]Fig.1 Various hematite nanocrystals with different morphologies308第 3 期张胜男,等:赤铁矿在污染控制方面的晶面效应研究进展无机盐(如氯化铵、氯化钾和硫酸钠)水热合成了铁尖晶石纳米棒,再将铁尖晶石前驱体在520 ℃下热脱水8 h得到了赤铁矿纳米棒,为{110}暴露晶面赤铁矿纳米晶体的合成提供了一条有效途径.除了常见的{001}、{012}和{110}晶面之外,还有研究可控合成了暴露出不寻常晶面的赤铁矿纳米晶体,如LIN等[49]利用氯化铁、水、氟化钠和氨水获得了优势晶面为{113}的六方双锥赤铁矿纳米晶体.定形貌尺寸或暴露晶面赤铁矿的可控合成为深入理解赤铁矿涉及的地球环境化学基本过程提供了新思路[50-54].如ZENG等[53]通过合成不同尺寸的赤铁矿并研究其对铀酰的吸附,发现随着赤铁矿颗粒尺寸从12 nm增加到125 nm,其对铀酰的吸附容量逐渐降低.MADDEN等[54]发现Cu(Ⅱ)在赤铁矿纳米颗粒表面的吸附量与吸附构型随着赤铁矿纳米颗粒尺寸变化而变化.LIU等[50]揭示了微生物对赤铁矿的还原速率与粒径的关系.这些研究强调了系统研究颗粒尺寸和形貌对界面反应影响的重要性.当前,水热法被广泛应用于赤铁矿不同晶面的制备上,主要通过表面控制试剂,如油酸钠、乙酰丙酮铁等控制晶面的生长方向,从而生长成为以某一个特定晶面为主要暴露面的赤铁矿.但是该方法时间较长且产率较低,还需要探索更简单的方法和工业化的方法来实现对赤铁矿特定暴露晶面的可控合成及工业化应用.2 赤铁矿在还原溶解中的晶面效应赤铁矿纳米晶体的还原溶解过程对污染物的环境行为、生物可利用性和毒性至关重要[14].前期研究表明,赤铁矿纳米晶体的还原溶解性存在显著的晶面依赖性.抗坏血酸、草酸、果糖等还原性的有机酸与铁氧化物形成络合物,可直接将电子转移给铁氧化物,从而还原溶解铁氧化物释放出Fe(Ⅱ).HUANG等[16]系统研究了赤铁矿{001}和{012}晶面与抗坏血酸之间的相互作用,发现抗坏血酸在赤铁矿晶面上的分子构型直接与其还原溶解动力学有关,抗坏血酸在{001}晶面上形成的双齿单核络合物比在{012}晶面上形成的单齿单核配合物更利于赤铁矿的还原溶解过程.另外,HU等[15]发现醌类物质的电子穿梭作用能够促进赤铁矿{001}和{100}晶面的生物还原,且{001}晶面的还原程度高于{100}晶面,这种晶面依赖性差异存在的原因在于{001}晶面比{100}晶面具有更高的吸附位点和电化学活性.3 赤铁矿在吸附反应中的晶面效应吸附反应是影响环境中营养物质和污染物迁移转化的重要途径,具有重要的环境和地球化学意义.赤铁矿纳米晶体具有活性位点多、在自然界含量丰富等特点,是环境中重要的吸附剂,同时不同的暴露晶面对重金属、类金属和有机物等各类污染物都表现出了不同的吸附能力(见表2).3.1 对重金属的吸附有毒重金属离子广泛存在于大气溶胶、土壤沉积物、地表水和地下水中,对环境和生态系统造成了严重的威胁,赤铁矿对环境中的各类重金属离子[如Cr(Ⅵ)、Pb(Ⅱ)、Hg(Ⅱ)等]都表现出了晶面依赖性吸附.表1 不同暴露晶面赤铁矿的合成方法Tab.1 Synthesis of hematite with different exposed facets反应物氯化铁、乙醇、醋酸钠、水乙酰丙酮铁、氢氧化钠、油酸、乙醇、水氯化铁、水-乙醇混合液(体积比1∶30)氯化铁、氢氧化钠、油酸、乙醇、水氯化铁、油酸钠、油酸、乙醇、水乙酰丙酮铁、氢氧化钠、油酸、乙醇、水(搅拌)水铁矿纳米颗粒、氢氧化钠(pH=12)氯化铁、无机盐(氯化铵/氯化钾/硫酸钠)硝酸铁、PVP、DMF乙酰丙酮铁、氢氧化钠、油酸、乙醇、水(不搅拌)氯化铁、水、氟化钠、氨水氯化铁、氨水、乙醇反应温度与时间180 ℃,12 h180 ℃,12 h180 ℃,12 h180 ℃,10 h180 ℃,12 h180 ℃,24 h30~90 h,热处理(300 ℃,1 h)120 ℃,12 h,热处理(520 ℃,8 h)180 ℃,30 h180 ℃,24 h180 ℃,24 h180 ℃,24 h形貌六方纳米片六方纳米片六方纳米片纳米立方体纳米立方体纳米立方体纳米棒纳米棒立方体六方双锥六方双锥菱面体优势晶面{001}{001}、{012}{001}、{113}{012}{012}{012}{110}、{001}{110}、{001}{110}{113}{113}、{104}{104}参考文献[36][38][43][45][46][38][47][48][44][38][43,49][43]309第 43 卷中南民族大学学报(自然科学版)研究表明,赤铁矿对Cr(Ⅵ)在环境中的归趋和迁移有着显著影响.CAO等[60]的研究指出Cr(Ⅵ)在赤铁矿表面可以形成单齿和双齿内层络合物,但对于Cr(Ⅵ)在赤铁矿特定表面吸附机制的分子层面的认识仍然有限.HUANG等[19]通过EXAFS和ATR-FTIR光谱技术证实Cr(Ⅵ)在赤铁矿{001}和{110}晶面上分别形成了单齿单核和双齿双核内层络合物,通过批次吸附实验得到Cr(Ⅵ)在赤铁矿{001}和{110}晶面的吸附量分别为5.39和10.79 #Cr‧nm-2.这表明赤铁矿表面络合物的类型决定了它们的吸附容量,{110}晶面比{001}晶面表现出更好的吸附性能.Pb(Ⅱ)在赤铁矿纳米晶体的不同暴露晶面上也存在选择性吸附.NOERPEL等[55]的研究表明Pb(Ⅱ)在赤铁矿{001}、{012}和{110}晶面上都形成了双齿内球和外球配合物,但在不同晶面上的吸附性能存在显著差异.暴露晶面上特定吸附位点的数量及其对pH的依赖性可能影响Pb(Ⅱ)在赤铁矿表面的吸附.当pH为6时,Pb(Ⅱ)在赤铁矿晶面的吸附性能为{012}>{110}>{001};而当pH为4时,Pb (Ⅱ)在赤铁矿晶面的吸附性能为{110}>{012}>{001}.因此,在给定的pH条件下,赤铁矿{012}和{110}晶面比{001}晶面具有更好的吸附性能.同时,YUAN等[56]通过调节Mn的掺杂水平制备了三种不同结构的赤铁矿纳米晶体(见图2),随着Mn掺杂量的增加,赤铁矿晶体从各向同性的多面体纳米颗粒演变为{116}晶面占主导的碟形纳米片,进而演变为{001}晶面占主导的六边形纳米片.研究发现这三种赤铁矿纳米晶体对Pb(Ⅱ)、Cd(Ⅱ)和Hg(Ⅱ)等重金属离子的吸附表现出晶面效应.DFT理论计算进一步证实,{001}晶面的六方纳米片对Pb(Ⅱ)表现出高选择性吸附,而{116}晶面的碟形纳米片对Pb(Ⅱ)和Cd(Ⅱ)表现出强选择性吸附.此外,其他金属和放射性金属元素与赤铁矿暴露晶面间的相互作用也有不少研究.WANG等[57]对图2 Mn掺杂含量对赤铁矿纳米晶体的结构与性能的影响[56]Fig.2 Effect of Mn doping content on the crystal structure andproperties of hematite nanocrystals[56]表2 吸附质在赤铁矿不同暴露晶面上的吸附性能差异Tab.2 Differences in the adsorption properties of adsorbates on hematite with different exposed facets 吸附质金属类金属有机物Cr(Ⅵ)Pb(Ⅱ)Pb(Ⅱ)Cd(Ⅱ)Hg(Ⅱ)Al(Ⅲ)Sb(Ⅲ/V)U(Ⅵ)Se(Ⅵ)As(Ⅲ/V)苯胂酸抗坏血酸腐殖质吸附能力{110}>{001}{012}>{110}>{001}(pH=6){110}>{012}>{001}(pH=4){001}>{116}>{110}>{012}{116}>{001}>{110}>{012}{110}>{001}>{116}{110}>{012}>{001}{001}>{110}>{214}{012}>{001}{110}>{012}{214}>{110}>{001}{012}>{001}{001}>{012}{100}>{001}{110}>{001}优势晶面作用原理{110}晶面形成的双齿双核内层络合物比{001}晶面上形成的单齿单核内层络合物具有更大的吸附能力{012}和{110}晶面上有丰富的单配位和三配位氧原子Pb(Ⅱ)在{001}晶面上具有最大的吸附能(高达7.17 eV)Cd(Ⅱ)在{116}晶面上具有最大的吸附能Hg(Ⅱ)在{110}晶面上具有最大的吸附能表面电位{001}>{012}>{110},{110}晶面对Al(Ⅲ)的吸引力更大Sb(Ⅲ/V)在{001}晶面上优先形成共角络合物并促进了Sb2O3和NaSb(OH)6沉淀的形成{012}晶面上具有更丰富的单配位和三配位氧原子{110}晶面上形成双齿双核内层络合物比{012}晶面上形成双齿单核内层络合物具有更大的吸附能力{110}和{214}晶面上形成的双齿双核内层络合物比{001}晶面上形成的单齿单核内层络合物具有更大的吸附能力{012}晶面上形成的双齿双核络合物的吸附能低于{001}晶面上形成的单齿单核络合物{001}晶面上形成的双齿单核内层络合物比{012}晶面上形成的单齿单核内层络合物更有利于吸附{110}晶面具有更丰富的单个铁原子配位-OH位点{110}晶面具有比{001}晶面更负的吸附能参考文献[19][55][56][57][18][20][21][12][58][16][22][59]310第 3 期张胜男,等:赤铁矿在污染控制方面的晶面效应研究进展比了暴露{001}晶面的赤铁矿纳米片(HNPs)、暴露{001}和{110}晶面的纳米棒(HNRs)和暴露{012}晶面的纳米立方体(HNCs)对Al(Ⅲ)的晶面依赖吸附行为,证明Al(Ⅲ)在赤铁矿上的吸附密度按{110}>{012}>{001}的顺序递减.在不同的环境条件下,Al(Ⅲ)在这些合成的赤铁矿纳米晶体上的吸附密度按HNRs>HNCs>HNPs的顺序递减.YAN等[18]报道了赤铁矿不同晶面对Sb的吸附机制,Sb(Ⅲ/V)在{001}晶面上优先形成共角络合物并促进了Sb2O3和NaSb(OH)6沉淀的形成,因此与{110}和{214}两个晶面相比,{001}晶面更有利于Sb(Ⅲ/V)的去除. MEI等[20]通过吸附实验、光谱和理论计算研究了赤铁矿纳米晶体的晶面对U(Ⅵ)的吸附,结果表明赤铁矿{012}晶面具有更多的单配位和三配位的氧原子,而{001}晶面只存在双配位氧原子,因此{012}晶面(21.9 sites·nm-2)比{001}晶面(13.7 sites·nm-2)具有更高的表面吸附位点密度,所以{012}晶面对U(Ⅵ)的吸附能力大于{001}晶面.3.2 对类金属的吸附赤铁矿对环境中类金属的吸附也具有晶面效应. CATALANO等[61]利用EXFAS等手段研究了Se(Ⅳ)在赤铁矿{100}晶面上的配位模式,发现双齿内球配位是最稳定的吸附构型.LOUNSBURY等[21]研究了赤铁矿纳米晶体的形貌对Se吸附行为的影响,结果表明{012}晶面的存在促进了{110}晶面对Se的吸附,且对Se(Ⅵ)吸附的促进作用大于Se(Ⅳ);Se(Ⅳ)在{110}晶面形成双齿双核内层络合物,在{012}晶面形成双齿单核内层络合物.此外,赤铁矿对As的吸附固定也极为重要. CATALANO等[62]研究表明砷酸盐在赤铁矿{012}晶面上形成了桥联双齿络合物.WAYCHUNAS等[63]利用EXAFS光谱研究了砷酸盐在赤铁矿{001}和{102}晶面上的吸附,发现在赤铁矿{001}和{102}晶面上均形成了共边砷酸盐表面络合物.YAN等[12]对比探究了As(Ⅲ/V)在赤铁矿{001}、{110}和{214}晶面上的吸附,发现As(Ⅲ)和As(V)在赤铁矿晶面上的吸附能力都表现为{214}>{110}>{001}.通过光谱表征和DFT理论计算证实了As(Ⅲ/V)在{001}晶面上形成了单齿单核内层络合物,在{110}和{214}晶面上形成了双齿双核内层络合物. 3.3 对有机物的吸附赤铁矿特定晶面对有机污染物的吸附机制已被深入研究.CAO等[58]探究了苯胂酸在赤铁矿{001}和{012}晶面上的吸附.开路电位测量分析表明苯胂酸在这两个晶面上的界面电荷转移能力不同,FTIR光谱和理论计算表明苯胂酸分子在赤铁矿的{001}和{012}晶面上分别形成了单齿单核和双齿双核络合物[见图3(a)、3(b)],由于形成双齿双核结构的吸附能低于单齿单核结构的吸附能,导致{012}晶面比{001}晶面更有利于苯胂酸的吸附.类似地,HUANG等[16]发现抗坏血酸在赤铁矿{001}和{012}晶面上分别形成了双齿单核和单齿单核内层络合物[见图3(c)、3(d)],导致抗坏血酸在赤铁矿{001}晶面的吸附量比{012}晶面大.有机物在赤铁矿纳米晶体表面形成的络合物类型显著影响了吸附性能,表现为双齿络合物>单齿络合物.另外,LV等[22]利用电喷雾电离-傅里叶变换离子回旋共振质谱(ESI-FT-ICR-MS)研究了两种典型腐殖质的吸附和分子分级,发现赤铁矿{100}晶面对胡敏酸和富里酸的吸附能力远高于{001}晶面.同时,SHEN等[59]发现赤铁矿{110}晶面对腐殖质的吸附能力优于{001}晶面.对于重金属、类金属和有机物等各类污染物的吸附,赤铁矿都表现出了明显的晶面效应,这与特定暴露晶面的赤铁矿纳米晶体在吸附机制、吸附位点密度、原子配位数等方面存在的差异密切相关,同时这种晶面依赖性吸附受环境中多种因素的影响,如pH、无机盐、温度和吸附质浓度等.图3 苯胂酸和抗坏血酸在赤铁矿{001}和{012}晶面上的吸附构型Fig.3 Adsorption configurations of phenylarsonic acid and ascorbic acid on hematite {001} and {012} crystal faces311第 43 卷中南民族大学学报(自然科学版)4 赤铁矿在环境催化反应中的晶面效应4.1 有机污染物的光催化降解赤铁矿作为一种天然的光活性半导体材料,具有较窄的禁带宽度和很强的可见光吸收能力,在有机污染物的降解方面具有重要的应用价值[64-65].通过光照的激发,在赤铁矿纳米晶体的表面会产生高活性的自由基(如SO4-·和·OH),随后降解多种有机污染物,不同的暴露晶面表现出不同的降解活性(见表3).CHAN等[43]比较了赤铁矿{104}、{113}和{001}三个晶面的非均相光芬顿反应活性,发现其对亚甲基蓝光降解的顺序为{113}>{104}>{001}.他们通过DFT理论计算发现赤铁矿表面原子排列方式和表面─OH官能团的类型在催化反应过程中起着关键作用,其中三配位Fe原子可能是光芬顿反应最活跃的位点.ZONG等[24]研究了赤铁矿{001}和{012}晶面在H2O2存在下对亚甲基蓝光催化降解,表明亚甲基蓝在{001}晶面的光降解速率约为{012}晶面上的14.5倍,一方面由于亚甲基蓝在{001}晶面上的吸附容量比{012}晶面上的吸附容量大,DFT理论计算也证实亚甲基蓝在{001}晶面上的吸附能比在{012}上低,因此亚甲基蓝更倾向于吸附在{001}晶面上;另一方面也归因于{001}晶面上更高浓度的Fe3+位点,它能捕获光生电子而被还原为Fe2+,进而催化H2O2的分解产生高活性的·OH以促进亚甲基蓝的降解.在催化罗丹明B的光降解方面,ZHOU等[66]比较了赤铁矿{110}、{012}和{001}三种晶面的性能差异,结果表明反应活性趋势为{110}>{012}≥{001}.对于相同的反应,WAN等[67]使用另外三种赤铁矿纳米晶体,提出了{101}>{012}>{001}的顺序.HUANG等[23]对比分析了赤铁矿{001}和{012}晶面光催化降解罗丹明B的效果,结果显示{001}晶面光催化降解罗丹明B的速率远高于{012}晶面,说明这种晶面的特异性差异似乎与简单的空位阳离子密度无直接关联,而是与它们的不完全配位程度有关.赤铁矿对不同污染物的催化降解差异可能还与反应物分子选择性吸附到特定晶面的倾向有关[70],ZHOU等[68]研究了赤铁矿晶面对甲基橙和罗丹明B混合水溶液的光降解,发现甲基橙更容易被选择性降解,且赤铁矿{012}晶面的效果优于{001},这种光催化选择性的结果可以解释为不同晶面结构差异和优先分子吸附的影响.同时,赤铁矿的晶表3 赤铁矿在光催化降解污染物的应用Tab.3 Application of hematite in photocatalytic degradation of pollutants污染物亚甲基蓝罗丹明B甲基橙和罗丹明B 混合溶液甲基橙过硫酸盐催化剂α-Fe2O3-{113}/{104}/{001}α-Fe2O3-{001}/{012}α-Fe2O3-{110}/{012}/{001}α-Fe2O3-{101}/{012}/{001}α-Fe2O3-{012}/{001}α-Fe2O3-{012}/{001}α-Fe2O3-{012}/{001}α-Fe2O3-{012}/{001}/{110}反应条件500 W卤素灯200 W氙弧灯,420 nm300 W氙灯,420 nm紫外光200 W氙弧灯,420 nm300 W氙灯,420 nm白光(λ>420 nm)100 W LED灯(λ=365、420、610 nm)晶面活性{113}>{104}>{001}{001}>{012}{110}>{012}≥{001}{101}>{012}>{001}{001}>{012}{012}>{001}{001}>{012}{001}>{012}>{110}优势晶面作用原理{113}晶面被H2O2氧化的概率最高,同时生成的Fe(3+x)+位点具有更高的电负性,更易接受染料分子的电子{001}晶面具有更负的吸附能和更高浓度的Fe3+位点,可以捕获光生电子而被还原为Fe2+,进而催化H2O2分解产生高活性的·OH{110}和{012}晶面上具有更多数量的低配位表面铁阳离子{101}晶面具有更多的不饱和配位数,可能会对罗丹明B产生更高的静电吸附能力{001}晶面比{012}晶面的配位饱和程度更低甲基橙和罗丹明B在{012}晶面上的吸附能大于{001}晶面{001}晶面比{012}晶面具有更高的Fe3+密度{001}晶面上具有更丰富的低配位Fe(Ⅲ)表面位点参考文献[43][24][66][67][23][68][69][25]312第 3 期张胜男,等:赤铁矿在污染控制方面的晶面效应研究进展面效应也体现在芬顿反应中.如HUANG 等[16,71]发现由于铁原子排列方式的不同,抗坏血酸在赤铁矿纳米晶体的晶面上形成不同的络合物,如图4所示,其中{001}晶面上的Fe 3c 位点有利于内层Fe -抗坏血酸络合物的形成,而{012}晶面的Fe 5c 由于空间位阻效应,不利于络合物的形成.在H 2O 2存在时,抗坏血酸在赤铁矿{001}晶面上形成的内层Fe -抗坏血酸络合物有利于界面电子转移过程产生Fe 2+,进而催化H 2O 2分解产生更多的·OH 从而促进甲草胺的降解,因此暴露{001}晶面的赤铁矿纳米片比暴露{012}晶面的赤铁矿纳米立方体对降解甲草胺具有更好的催化性能.同样地,PATRA 等[69]也发现赤铁矿{001}晶面比{012}晶面对甲基橙光降解具有更高的催化活性.此外,GUO 等[25]研究了在可见光照射下赤铁矿纳米晶体活化过硫酸盐降解污染物的晶面效应.在赤铁矿纳米晶体-过硫酸盐-可见光体系中,过硫酸盐分子吸附在赤铁矿纳米晶体表面形成了过硫酸盐-Fe (Ⅲ)络合物,并通过光生电子进一步还原为过硫酸盐-Fe (Ⅱ)络合物,产生SO 4-·和·OH 自由基从而降解有机污染物.与赤铁矿{012}和{110}晶面相比,暴露{001}晶面的赤铁矿表现出更好的污染物降解能力.ASIF 等[72]采用水热/溶剂热法合成了主要暴露晶面为{012}和{120}的菱形、主要暴露晶面{001}和{120}的板状以及没有优势暴露晶面的球状和米粒状4种形貌的赤铁矿纳米晶体.具有不同形状和暴露晶面的赤铁矿在表面能和原子构型上存在差异,导致催化性能的显著差异;赤铁矿纳米晶体表现出暴露晶面依赖的光催化活性,顺序为{120}>{012}>{001},对羟基苯甲酸和磺胺氯哒嗪的光芬顿降解效果为板状>米粒状>球状>菱形,板状结构的赤铁矿纳米晶体更高的光催化性能归因于{001}和{120}暴露面和比表面积的协同作用.4.2 CO 的催化氧化前人研究了赤铁矿纳米晶体的晶面对CO 催化氧化性能的影响.LIU 等[26]的研究发现,暴露{110}晶面的赤铁矿纳米棒具有相对较高的Fe 原子密度,因此表现出比其他晶面更高的CO 催化氧化活性.此外,OUYANG 等[38]发现由于CO 和氧物种在赤铁矿晶面上的吸附能力存在差异,赤铁矿纳米晶体对CO 氧化的催化活性表现出晶面效应,活性顺序为{012}>{113}>{001};对有机气体的传感能力也表现出晶面效应,其顺序遵循{113}>{012}>{001}.在催化反应中,赤铁矿纳米晶体的催化活性存在明显的晶面效应.导致这种晶面依赖性催化活性差异的因素包括表面不饱和配位原子数、催化活性位点、空位数、表面能和原子构型等,更高的不完全配位程度、催化活性位点、空位阳离子密度会导致更好的催化活性.5 赤铁矿在污染物水解反应中的晶面效应赤铁矿可以催化有机污染物的水解,如抗生素[73]和有机磷酯[74].赤铁矿的催化活性与其晶面结构密切相关.LI 等[29]的研究表明赤铁矿的{110}晶面相对于{001}晶面具有更高的Lewis 酸性位点密度,因此对4-硝基苯磷酸的水解反应具有更高的催化活性.JIN 等[28]发现具有特定晶面的赤铁矿纳米晶体在环境湿度条件下可以高效催化邻苯二甲酸酯的水解反应,发现赤铁矿对邻苯二甲酸酯(DMP )水解的催化性能表现出明显的晶面依赖性,其反应活性顺序为{012}>{104}>{001},这与表面低配位Fe 的原子排列有关(见图5).{012}和{104}晶面可以与邻苯二甲酸酯发生双齿配位,从而诱导更强的Lewis 酸催化.6 晶面依赖的赤铁矿耦合Fe (Ⅱ)对污染物的降解在自然土壤和沉积物中,赤铁矿常与Fe (Ⅱ)共图4 赤铁矿{001}和{012}晶面上的原子排列[71]Fig.4 Atomic arrangements on {001} and {012} facets of hematite [71]313。

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This motivates us to ask how much entanglement exists in a realistic system such as a solid (the likely final arena for quantum computing [8]) at a finite temperature. The 1D Heisenberg model [9,10] is a simple but realistic [11] and extensively studied [12–15] solid state system. We analyze the dependence of entanglement in this system on temperature and external field. We find that the entanglement between two spins in an antiferromagnetic solid can be increased by increasing the temperature or the external field. Increasing the field to a certain value can also create entanglement between otherwise disentangled spins. We show that the presence entanglement can be confirmed by observing the violation of Bell’s inequalities. However, on exceeding a critical value of the field, the entanglement vanishes at zero temperature and decays off at a finite temperature. In the ferromagnetic solid, on the other hand, entanglement is always absent. We compare the entanglement in these systems to the total correlations.
ten less than and at most equal to the average of the entanglement of these states.
1
0.8
0.6
E
0.4
0.2
B = 4.6 0 0
2
4
B
6 88
7
6
5
4
kT
3
2
1
0
FIG. 1. We have plotted the entanglement E between two
The entanglement of formation [5] is a computable en-
tanglement
measure
for
two
spin-
1 2
systems
(qubits)
[16].
We will use this measure to compute the entanglement
R ≡ ρ(σy ⊗ σy)ρ∗(σy ⊗ σy).
(2)
Now concurrence is defined by
C = max{λ1 − λ2 − λ3 − λ4, 0}
(3)
where the λi are the square roots of the eigenvalues of R,
in decreasing order. In this method the standard basis,
between
different
ns
in
the
1D
isotropic
spin-
1 2
Heisen-
berg model. This model describes a system of an arbi-
trary number of linearly arranged spins, each interacting
2 Optics Section, Blackett Laboratory, Imperial College, Prince Consort Road, London SW7 2BZ, England
We investigate the entanglement between any two spins in a one dimensional Heisenberg chain as a function of temperature and the external magnetic field. We find that the entanglement in an antiferromagnetic chain can be increased by increasing the temperature or the external field. Increasing the field can also create entanglement between otherwise disentangled spins. This entanglement can be confirmed by testing Bell’s inequalities involving any two spins in the solid.
0 as B crosses the critical value of Bc = 4. E always becomes
zero for values of T exceeding Tc = 8/k ln 3
1
We first examine the 2 qubit antiferromagnetic chain. We will use the entanglement of formation [5,16,17] to calculate the entanglement of the two qubits. To calculate this entanglement measure, starting from the density matrix ρ, we first need to define the product matrix R of the density matrix and its time-reversed matrix
Heisenberg antiferromagnet has been computed. But en-
tanglement in the natural state of a system as a function
of its temperature remains to be studied and the pos-
sibilities of increasing this entanglement by an external
magnetic field remains to be explored. The Hamiltonian
for the 1D Heisenberg chain in a constant external mag-
only with its nearest neighbors. Recently, entanglement
in linear arrays of qubits have attracted interest [18–20]
and in Ref. [19] the entanglement in the ground state of a
arXiv:quant-ph/0009060v2 9 Mar 2001
It is well known that distinct quantum systems can be correlated in a ”stronger than classical” manner [1–3]. This ”excess correlation”, called entanglement, has recently become an important resource in quantum information processing [4]. Like energy, it is quantifiable [5–7].
The state of the above system at thermal equilibrium (temperature T ) is ρ(T ) = e−H/kT /Z where Z is the partition function and k is Boltzmann’s constant. To find the entanglement between any two qubits in the chain, the reduced density matrix ρr(T ) of those two qubits is obtained by tracing out the state of the other qubits from ρ(T ). Entanglement is then computed from ρr(T ) following Ref. [16]. As ρ(T ) is a thermal state, we refer to this
coupling J = 1. The B = 4.6 line pointed out in the figure
shows that for certain values of B it is possible to increase E
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