金纳米粒子在一些催化反应中的应用

金纳米粒子的应用
Catalysts Supports Nonlinear optics
Gold nano.
Sensors others
Drug
D. Astruc. Chem. Rev., 2004, 104, 293
目录
金纳米粒子在一些催化反应中的应用
Selective hydrogenations
Gold nano.
Oxidation reactions
C–C coupling
Other reactions
选择性氢化反应
1906
Bone, Wheeler uptake of hydrogen by gold
1950
1963
1973
Bond et al, Selective hydrogenation
选择性氢化反应
G. C. Bond et al., J. Chem. Soc. Chem. Commun. 1973, 444 – 445.
选择性氢化反应
These supported gold catalysts preferentially hydrogenated the C=O bond rather than the C=C bond. Thiophene promoted this selective hydrogenation. S-Au/SiO2 Con.%10% Selectivity >98% Graham J. Hutchings et al., Chem. Commun. 1999, 2151 – 2152. Au-In/ZnO catalyst gives enhanced selectivity for C=O hydrogenation in acrolein P. Claus, Appl. Catal. A 2005, 291, 222 – 229.
选择性氢化反应
A. Corma, P. Serna, Science, 2006, 313, 332
选择性氢化反应
Au/TiO2 3.8±1.5nm
Au/Fe2O3 3.7±0.9nm
Kinetic curves for 3-nitrostyrene hydrogenation
选择性氢化反应
A. Corma, P. Serna, Science, 2006, 313, 332
金纳米粒子在一些催化反应中的应用
目录
金纳米粒子背景介绍 金纳米粒子在一些催化反应中的应用 小结及展望
背景介绍
背景介绍
Before 1973
not any superior to other catalysts
1973
G. C. Bond, hydrogenation of olefins over supported gold catalysts.
背景介绍
Homogeneous ( Y. Ito, Y. Fukuda, A. S. K. Hashmi)
alkynylgold, vinylgold, arylgold, alkylgold and even pcoordinated gold complexes Very effective for constructing C-C and C-Heteroatom bond
选择性氢化反应
R1 CH3 CH3 N(CH3)2
R2 COCH3 COCH3 SO3Na
Time (h) 44 43 40
Con. (%) 100 87 99
Selectivity (%) 80 90 91
A. Corma, P. Serna, Science, 2008, 322, 1661
选择源自文库氢化反应
金属纳米粒子制备
4th AD, Lycurgus Cup 1857 , Michael Faraday 1951,Turkevich
1994, Brust
Late 1990’s, Halas 2006, Xia
金纳米颗粒的稳定方法
主要稳定剂
-+-- - +- - + --+ --- -d d + + + + d d -- d + d +d+ + + d d d + +- -- + a Electrostatic stabilizors b Steric stabilizors
CO 氧化反应
Masatake Haruta
CO conversion over various catalysts as a function of temperature. 1) Au/a-Fe2O3 (Au/Fe=1/19, co precipitation, 4000C), 2) 0.5 wt% Pd/g-Al2O3 (impregnation, 3000C), 3) fine Au powder, 4) Co3O4 (carbonate, 4000C), 5) NiO (hydrate, 2000C), 6) a-Fe2O3 (hydrate, 4000C), 7) 5 wt% Au/a-Fe2O3 (impregnation, 2000C), and 8) 5 wt% Au/g-Al2O3 (impregnation, 2000C)). M. Haruta et al, Chem. Lett. 1987, 16, 405 – 408. J. Catal. 1989, 115, 301 – 309
选择性氢化反应
H-U, Blaser Science, 2006, 313, 312
选择性氢化反应
Deposition–precipitation
Au/TiO2 3.8±1.5nm
Au/Fe2O3 3.7±0.9nm
A. Corma, P. Serna, Science, 2006, 313, 332
CO 氧化反应
what’s the mechanism?
CO 氧化反应
size and morphology
interface
Others
Active nature
oxidation state
support material
CO 氧化反应
Nature of the Active Site CO is activated by adsorption onto Au0 on the surface of the gold nanoparticles and that dioxygen is activated by the atoms at the boundary between the support and the gold nanocrystals.
CO 氧化反应
Deposition–precipitation
(x ) 0.47% Au/TiO2 (pHinitial=4 and pHfinal=9) (.) 0.55% Au/TiO2 (pHinitial=11 andpHfinal=8.5
F. Moreau, G. C. Bond, A. O. Taylor, J. Catal. 2005, 231, 105 – 114.
gold nanoparticles, Catalyst
背景介绍
QUANTUM SIZE EFFECT
GOLD NANOPARTICLES
LITTLE SIZE EFFECT
SURFACE EFFECT
D. Astruc. Chem. Rev., 2004, 104, 293
PRONE TO AGGREGATE AND PRECIPITATE STABILIZORS NEEDED!
选择性氢化反应
R OCH3 CH3
Time( Y:2 h) 5 3 89 98
Y:3 3 0
Y:4 6 2
Con.% 99 99
Selectivity % 90 98
Cl
COCH3 N(CH3)2
23
31 16
64
44 99
0
1 0
0
0.5 0
65
50 99
99
96 99
A. Corma, P. Serna, Science, 2008, 322, 1661
c
Electro-steric stabilizors
d
Ligand stablilizors
金属纳米粒子制备
Mostafa A. El-Sayed et al., Chem. Soc. Rev., DOI:10.1039/c1cs15237h
金属纳米粒子表征
Iwasawa, Y. Ed., Tailored Metal Catalysts Kluwer, Dordrecht, 1986 XP spectra of the Au4f7/2 level recorded for gold nanoparticles supported on nanoparticulate ceria A. Corma et al., Angew.Chem., Int. Ed., 2005, 44, 4066–4069.
选择性氢化反应
A. Corma, P. Serna, Science, 2008, 322, 1661
选择性氢化反应
Time-conversion plot for aniline oxidation, 1.5% Au/TiO2, 100°C.
A. Corma, P. Serna, Science, 2008, 322, 1661
Cat.
1.5% Au/TiO2
T (0C) P (bar)
120 100 9, H2 5, O2 6 9
Time (h)
Yield (%)
94.6 92
Con. (%) 98.5
100
Selectivit y(%)
96 92
A. Corma, P. Serna, Science, 2008, 322, 1661
G. J. Hutchings, Acetylene hydrochlorination M. Haruta, Low temperature CO oxidation
1985
1987
Up to now
Gold is not just a good catalyst, it is the best.
Couper , Eley Erkelens , Kemball, parahydrogen Galwey into ortho hydrogen alkene hydrogenation
Gold surfaces can activate hydrogen.
Graham J. Hutchings et al., Angew. Chem. Int. Ed. 2006, 45, 7896 – 7936
Gerald B. Hammond et al., Chem. Soc. Rev., DOI: 10.1039/c2cs15318a
背景介绍
Heterogeneous (most gold nanoparticles)
纳米颗粒，又称纳米尘埃，纳米尘末，指纳米量级的微观 颗粒。它被定义为至少在一个维度上小于200纳米的颗粒。 小于10纳米的半导体纳米颗粒，由于其电子能级量子化， 又被称为量子点。
目录
Selective hydrogenations
Gold nano.
Oxidation reactions
C–C coupling
Other reactions
CO 氧化反应
polymer electrolyte fuel cells (PEFC)
CO, O2, H2, CO2, H2O, and N2, and be capable of reducing the CO concentration from about 1% to below 50 ppm. at about 800C.
Au/a-Fe2O3 calcined at 1000C showing the presence of cuboctahedral goldparticles with diameters of 2–5 nm
G. C. Bond, D. T. Thompson, Gold Bull. 2000, 33, 41 – 52. H. H. Kung et al., J. Catal. 2003, 216, 425 – 432. M. Haruta et al., Angew. Chem. Int. Ed. 2004, 43, 1546 –1548
选择性氢化反应
100%con., selectivity 90%
A. Corma, P. Serna, Science, 2006, 313, 332
选择性氢化反应
H-U, Blaser Science, 2006, 313, 312
选择性氢化反应
A. Corma, P. Serna, Science, 2008, 322, 1661