lecture072FPN

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Lecture 7 DB

Lecture 7 DB

CONTAINS
PART
• part number • part description • unit cost
Generalisation
NAME ADDRESS EMPLOYEE NO. EMPLOYEE DATE HIRED
ISA
ISA
ISA
HOURLY EMPLOYEE
SALARIED EMPLOYEE
CONSULTANT
• EMPLOYEE NO •HOURLY RATE
•EMPLOYEE NO •ANNUAL SALARY •STOCK OPTION
•EMPLOYEE NO •CONTACT NO. •DAILY RATE
Data Modelling Exercise
University Student Recreation Centre Database Students can only use the centre if they have paid their recreation fees in full. The centre will also allow a faculty to purchase a membership as well. Members are allowed to check out sports equipment such as basketballs, softball bats and balls, tennis rackets, badminton rackets and table tennis rackets that can be used at the facility. When the members check out equipment, an equipment-issue form is completed listing the membership number and equipment being used. This form must list at least one piece of equipment in order to be retained in the file. Otherwise it is discarded. A member of staff is employed to monitor the checkout and the use of the sporting equipment. Every employee is assigned to one of two departments: maintenance or general staff. The centre has 10 tennis courts. These courts may be reserved up to one week in advance. Reservations can be made via the equipment checkout window. The centre also operates a small accessory shop where some sporting equipment and clothing is sold. The sporting goods include tennis balls, table tennis balls, bandages, etc. Sportswear bearing the university emblem and mascot as well as a limited assortment of some name-brand sportswear are sold. Finally, the centre sponsors a limited number of classes in officiating various sports . A general rule is that instructors often teach in more than one sport but there is never more than one class offered in a particular sport.

cs231n课程大纲

cs231n课程大纲

cs231n课程大纲CS231n是斯坦福大学开设的一门计算机视觉课程,以下是该课程的详细课程大纲:Lecture 1:计算机视觉的概述、历史背景以及课程计划。

Lecture 2:图像分类——包括数据驱动方法,K近邻方法和线性分类方法。

Lecture 3:损失函数和优化,分为三部分内容:1. 继续上一讲的内容介绍了线性分类方法;2. 介绍了高阶表征及图像的特点;3. 优化及随机梯度下降。

Lecture 4:神经网络,包括经典的反向传播算法、多层感知机结构以及神经元视角。

Lecture 5:卷积神经网络,分为三部分内容:1. 卷积神经网络的历史背景及发展;2. 卷积与池化;3. ConvNets的效果。

Lecture 6:如何训练神经网络I,介绍了各类激活函数,数据预处理,权重初始化,分批归一化以及超参优化。

Lecture 7:如何训练神经网络II,介绍了优化方法,模型集成,正则化,数据扩张和迁移学习。

Lecture 8:深度学习软件基础,包括详细对比了CPU和GPU,TensorFlow、Theano、PyTorch、Torch、Caffe实例的具体说明,以及各类框架的对比及用途分析。

Lecture 9:卷积神经网络架构,该课程从LeNet-5开始到AlexNet、VGG、GoogLeNet、ResNet等由理论到实例详细描述了卷积神经网络的架构与原理。

Lecture 10:循环神经网络,该课程先详细介绍了RNN、LSTM和GRU的架构与原理,再从语言建模、图像描述、视觉问答系统等对这些模型进行进一步的描述。

Lecture 11:检测与分割,在图像分类的基础上介绍了其他的计算机视觉任务,如语义分割、目标检测和实例分割等,同时还详细介绍了其它如R-CNN、Fast R-CNN、Mask R-CNN等架构。

Lecture 12:可视化和理解,讲述了特征可视化和转置,同时还描述了对抗性样本和像DeepDream 那样。

《傅里叶教程》课件

《傅里叶教程》课件

适用范围和应用注意事 项
指导使用傅里叶变换时需要 注意的事项和常见误区。
未来发展方向
展望傅里叶变换的未来发展 方向,探讨可能的应用领域 和创新方案。
示其背后的核心原理。
3
傅里叶级数和傅里叶变换的区别
对比傅里叶级数和傅里叶变换的异同,
离散傅里叶变换
4
理解它们各自的应用领域。
介绍离散傅里叶变换(DFT)及其在数字 信号处理中的重要性。
二、傅里叶级数
傅里叶级数的导出
推导傅里叶级数的基本原理和计算方法,为后续学习打下基础。
方波、三角波、锯齿波的傅里叶级数展开
五、相关算法
快速傅里叶变换
介绍快速傅里叶变换(FFT) 算法及其在傅里叶分析中的 高效计算优势。
批量傅里叶变换
学习批量傅里叶变换(DCT) 算法和其在图像和音频编码 中的应用。
傅里叶变换在数字信号 处理中的应用
解释傅里叶变换在实际数字 信号处理优缺点
总结傅里叶变换的优点和局 限性,帮助理解其适用范围 和局限性。
梳状函数和正弦高斯函数的傅里
叶变换
以梳状函数和正弦高斯函数为例,展示 傅里叶变换的具体计算方法。
四、应用举例
信号处理中的傅里叶变换
探索傅里叶变换在音频、图像和视频信号处理中的实际应用。
频谱分析
学习如何使用傅里叶变换对信号的频谱进行分析和特征提取。
图像处理中的傅里叶变换
了解傅里叶变换在图像增强、去噪和压缩等方面的广泛应用。
《傅里叶教程》PPT课件
欢迎来到《傅里叶教程》的PPT课件。在本课程中,我们将深入探讨傅里叶变 换的理论、应用和相关算法。让我们一起开始这段奇妙的数学之旅吧!
一、理论介绍
1

北师大版高中英语必修二《Information Technology》(第7课时)

北师大版高中英语必修二《Information Technology》(第7课时)
this is the end of printed books and
books are outdated and dull no longer can it be said that
we like to read
View and learn
Now please read the five lines in reverse.
Printed books cannot meet people’s various reading interests. The market for printed books is dying.
View and learn
Watch Part 1 of the video. Tick (√) the
View and learn
Watch Part 2 of the video. What is the speaker’s opinion of printed books?
Printed books will survive.
View and learn
Watch Part 2 of the video again. What advantages are mentioned?
Information Technology 第7课时
Publishing in the Digital Age Viewing Workshop
Lead in
Lead in
Do you prefer reading printed books or digital books? Do you agree with the saying “this is the end of printed books?” Give your reasons.

李宏毅-B站机器学习视频课件BP全

李宏毅-B站机器学习视频课件BP全
Backpropagation
Gradient Descent
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Compute Τ for all activation function inputs z
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function inputs z
Backpropagation – Forward pass

【托福听力资料】托福TPO7听力文本——Lecture 2

【托福听力资料】托福TPO7听力文本——Lecture 2

【托福听力资料】托福TPO7听力文本——Lecture 2众所周知,托福TPO材料是备考托福听力最好的材料。

相信众多备考托福的同学也一直在练习这套材料,那么在以下内容中我们就为大家带来托福TPO听力练习的文本,希望能为大家的备考带来帮助。

TPO 7 Lecture 2 BiologyNarrator:Listen to part of a lecture in a Biology class.Pro: So, that is how elephants use infrasound. Now, let’s talk about the other end of the acoustical spectrum, sound that is too high for humans to hear---ultrasound.Ultrasound is used by many animals that detect and some of them send out very high frequency sounds. So, what is a good example? Yes? Carol.Carol: Well, bats, since they are all blind, bats have to use sound for, you know, to keep from flying into things.Pro: That is echolocation. Echolocation is pretty self-explanatory; using echoes reflected sound waves to locate things. As Carol said, bats use it for navigation and orientation. And what else? Mike.Mike: Well, finding food is always important, and I guess not becoming food for other animals.Pro: Right, on both counts. Avoiding other predators, and locating prey, typically insects that fly around at night. Now before I go on, let me just respond to something Carol was saying--- this idea that bats are blind.Actually, there are some species of bats, the ones that don’t use echolocation that do rely on their vision for navigation, but it is true that for many bats,their vision is too weak to count on.Ok, so quick summary of how echolocation works. The bat emits theseultrasonic pulses, very high pitch sound waves that we cannot hear. And then, they analyze the echoes, how the waves bounce back. Here, let me finish this diagram I started before class. So the bat sends out these pulses, very focused bursts of sound, and echoes bounce back. You know, I don’t think I need to draw on the echoes, your reading assignment for the next class; it has a diagram that shows this very clearly.So, anyway, as I were saying, by analyzing these echoes, the bat candetermine, say, if there is wall in a cave that it needs to avoid, and how far away it is. Another thing it uses ultrasound to detect is the size and shape of objects. For example, one echo they quickly identify is the one they associate with a moth, which is common prey for a bat, particularly a moth beating its wings. However, moth happened to have a major advantage over most other insects.They can detect ultrasound; this means that when a bat approaches, the moth candetect the bat’s presence. So, it has time to escape to safety, or else they canjust remain motionless. Since, when they stop beating their wings, they’d be much harder for the bat to distinguish from, oh… a leaf or some otherobject.Now, we have tended to underestimate just how sophisticated the abilities of animals that use ultrasound are. In fact, we kind of assumed that they werefiltering a lot out, the way a sophisticated radar system can ignore echoes fromstationary objects on the ground. Radar does this to remove ground clutter, information about hills or buildings that it doesn’t need. But bats, we thoughtthey were filtering out this kind of information, because they simply couldn’tanalyze it. But, it looks as if we were wrong. Recently there was thisexperiment with trees and a specific species of bats. A bat called: the lesser spearnosed bat.Now, a tree should be a huge acoustical challenge for a bat, right? I mean it’s got all kinds of surfaces with different shapes and angles. So, well, the echoes from a tree are going to a mass of chaotic acoustic reflections, right, not like the echo from a moth. So, we thought for a long time that bats stop their evaluation at simply that is a tree. Yet, it turns out that bats or at least this particular species, cannot only tell that is a tree, but can also distinguish between, say, a pine tree, and a deciduous tree, like a maple or oak tree, just by their leaves. And when I say, leaves, I mean pine needles too. Any ideas on how it would know that?Stu: Well, like with the moth, could it be their shape?Pro: You are on the right track---it is actually the echo of all the leaves as whole that matters. Now, think, a pine tree with all those little densely packed needles. Those produce a large number of faint reflections in what’s...what’s called a ... a smooth echo. The wave form is very even, but an oak whichhas fewer but bigger leaves with stronger reflections, produces a jagged wave form, or what we called: a rough echo. And these bats can distinguish between the two, and not just with trees, but with any echo that comes in a smooth or rough shape.。

《金融计量学》课件 中国人民大学Lecture 7-02

《金融计量学》课件 中国人民大学Lecture 7-02
10.0 残差序列 实际序列 拟合序列 .10 .05 .00 -.05 -.10 -.15 9.5 9.0 8.5 8.0 7.5 7.0
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05 20
19
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去除线性时间趋势法 获得的差分序列的ACF图
图7-6 差分法获得的序列
7.3.3 去除趋势的方法比较 前面小节讨论了差分法和去除时间 趋势法,并且认识到不同的趋势非平稳 序列需要采用不同的去除趋势成分的方 法。实际上,去除含有趋势成分的非平 稳时间序列的方法还有很多滤波方法。 常见的有HP滤波、卡尔曼滤波,以及近 年来新发展起来的BK滤波和CF滤波。
图7-5 去除线性时间趋势法 获得的序列
图7-7 各种滤波给出的美国 真实GDP周期成分
8 4 0 -4 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 HP Filter Kalman Filter Baxter-King Filter Christiano-Fitzgerald Filter
25
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以上处理方法很容易拓展到高阶 单整序列。例如,假设 yt 是一个I(2) 过程,那么对其二次差分就可以获得 平稳序列,即:
yt (yt ) ( yt yt 1 ) ( yt 1 yt 2 ) yt yt 1 yt 2
2
其中:“ 2 ”表示二次差分符号。 依此类推,“ 3 ”表表示三次差分符 n 号,而“ ”表示n次差分符号。

高斯讲座Lecture 07

高斯讲座Lecture 07

The spin state of the molecule must also be specified when inputting an electronic structure calculation. •For closed shell systems, the spin state is a singlet (s=0) •For a system with a single dangling bond, the charge state is usually a doublet (s=1/2) •For a system with multiple unpaired electrons, the charge state is not often obvious.
QC Practical Issues
Lecture 7 Page 7
Methylene example
Methylene: Neutral molecule. Singlet or triplet? 2 CH bonds CH ~ 1.09Å 2 mirror planes. (C2V symmetry, like water).
3 Nodes
QC Practical Issues
Lecture 7 Page 2
Molecular Orbitals from SALC of Atomic Orbitals
We can make combinations of SALC of atomic orbitals to form molecular orbitals:
QC Practical Issues
Lecture 7 Page 6
Ethylene example

Lecture-7

Lecture-7

2 2 a b a b a 2 2 1. A A 2 2 2 2 b 2 2 a b a b a b a b
9
Example 3.
The full SVD is A U V
-5 -5 -14 -8 1 Let A -1 0 4 5 4 . 6 11 10 24 11 -6
8
Example 2.

a Let A . b
b a We can find A 2 , then 2 2 2 a b a b a a AA 2 2 b a b

a2 ab b a 2 b2 a 2 b2 , 2 2 2 b a b ba a 2 b2 a 2 b2
Lecture 7 : General Inverse, Least Square, Invariant subspaces.
R di assignment Reading i t
Section 3.1 3 1, 3.2 3 2, 7.3 7 3: (7 ), ) (8 )
1
7.1 Generalized Inverse, SVD representation, Least Square First , what is a generalized inverse o of f matrix A ? For Linear Equations of Ax b , if A is nonsingular, then we define the solution spa space ce through through x A-1b S Suppose A is i rectangular t l or singular i l - square, how h would ld we solve for x ? If there th exists i t a matrix t i G such h that th t x Gb is i a solution l ti of f Ax b , then it can be said that G behaves as the inverse of A. Hence G is called a generalized inverse of A.

optisystem7初级入门中文讲义(网络版)

optisystem7初级入门中文讲义(网络版)

OptiSystem 7入门讲义(中文)编译人:郑小歪E-mail:wellright@此讲义仅适用于OptiSystem光通信仿真软件的初学者。

(注:此讲义为个人闲暇所编,仅作个人学习与交流,不做他用,存在疏漏与翻译不妥之处在所难免,请诸位抱着批判且中肯<不装‘介于A与C之间的字母’>的态度给予指正。

自成稿之日起,除编译者本人外,请大家本着人道主义精神,三月内,请勿在各大光电论坛上传和分享该文稿。

另注:此讲义出自光通信仿真软件交流QQ群:49258352 群主:冷小漠,并感谢群成员:girl,小蟹*-*璟的不吝赐教。

郑小歪2009.11.01)前言-----OptiWave系列软件简介"As optical systems become more and more complex, scientists and enginee rs must increasingly adopt advanced software simulation techniques for vital assistance with design issues. OptiSystem’s power & flexibility facilitates effic ient & effective photonic designs."Dr. Govind P. Agrawal,Professor, Institute of Optics, University of RochesterAuthor of Fiber Optic Communications Systems“随着光学系统变得越来越复杂,科学家和工程师更加必须采用先进的软件仿真技术作为解决设计问题的必要辅助手段。

OptiSystem 的强大功能和高度灵活性能够有助于实现有效且高效的光子设计。

”罗切斯特大学光学学院教授,Fiber-Optics Communications Systems(《光纤通信系统》)作者Govind p. Agrawal 博士OPTIWA VE(/)公司成立于一九九四年,总部位于加拿大,是光纤通信领域中从事光通信系统、光纤与光子学元器件模拟设计软件开发的国际著名公司。

交流电机变频调速讲座(陈伯时)-第二讲

交流电机变频调速讲座(陈伯时)-第二讲

交流电机变频调速讲座Lectures on Variable Frequency Speed Control of ACMachines上海大学陈伯时第二讲静止式变压变频器(-2)Static VVVF Converters为了实现异步电动机的变压变频调速,必须具备能够同时控制电压幅值和频率的交流电源,而电网提供的是恒压恒频的电源,因此应该配置变压变频器,又称VVVF(Variable Voltage Variable Frequency)装置。

最早的VVVF装置是旋转变频机组,即由直流电动机拖动交流同步发电机构成的机组,调节直流电动机的转速就能控制交流发电机输出的电压和频率。

自从电力电子器件获得广泛应用以后,旋转变频机组便逐渐被淘汰,并形成了一系列通用型的静止式变压变频装置。

2.1静止式变压变频器的主要类型2.1.1交-直-交和交-交变压变频器从整体结构上看,静止式的电力电子变压变频器可分为交-直-交和交-交两大类。

(1)交-直-交变压变频器交-直-交变压变频器先将工频交流电源通过整流器变换成直流(可控电压或恒压),再通过逆变器变换成可控的交流(只控制频率或同时控制频率和电压),如图2-1所示。

图2-1交-直-交(间接)变压变频器由于这类变压变频器在恒频交流电源和变频交流输出之间有一个“中间直流环节”,所以又称间接式的变压变频器。

具体的整流和逆变电路种类很多,当前应用最广的是由二极管组成不控整流器和由全控型功率开关器件(P-MOSFET,IGBT等)组成的脉宽调制(PWM)逆变器,简称PWM变压变频器,如图2-2所示。

图2-2交-直-交PWM变压变频器C——滤波电容PWM变压变频器的应用之所以如此广泛,是由于它具有如下的一系列优点:1)在主电路整流和逆变两个变流单元中,只有逆变单元是可控的,采用全控型的功率开关器件,通过驱动电压脉冲进行控制,可同时调节变频器的输出电压和频率,结构简单,效率高。

中英双语狭义相对论公开课

中英双语狭义相对论公开课

关于狭义相对论的公开课,以下是一些推荐的选项:Here are some recommended options for an open class on special relativity:MIT公开课:物理学-狭义相对论:这门课程由MIT提供,涵盖了狭义相对论的核心概念,包括长度收缩、时间膨胀、洛伦兹变换、相对论运动学和多普勒频移等。

共计52条视频,适合对狭义相对论有深入了解需求的学习者。

MIT Open Course: Physics - Special Relativity: This course is provided by MIT and covers the core concepts of special relativity, including length contraction, time dilation, Lorentz transformation, relativistic kinematics, and Doppler shift. A total of 52 videos are suitable for learners who have a deep understanding of special relativity.北京师范大学公开课:相对论:这是由梁灿彬教授讲解的公开课,涵盖了相对论的广泛内容。

该课程共有148集,适合初学者和进阶学习者。

Beijing Normal University Open Course: Relativity: This is an open course taught by Professor Liang Canbin, covering a wide range of topics in relativity. This course has a total of 148 episodes, suitable for beginners and advanced learners.狭义相对论简明教程:这个教程适用于初中生和高中生,旨在让他们能够听懂相对论的基本概念。

lecture7

lecture7

第七讲 载流子的漂移和扩散(续)9月16,2001内容:1.漂移2.扩散3.传输时间阅读作业del Alamo Ch. 4,§4.2-4.4主要问题●在电场中,载流子如何移动?漂移速度主要由什么决定?●能带图如何表示一个电场的存在?●浓度梯度如何影响载流子?●平均起来,一个载流子通过漂移或扩散从半导体的一个区域移动另一个区域要花多长时间?⒈ 漂移存在电场时载流子发生移动:□ 漂移速度-电场:ε-加在电子上的电场力:q ε−-碰撞间的加速度:ceq m ε∗−-在时间ce τ获得的速度:drift cee ce q m ετυ∗=−或 drift ee υµε=− e µ电子迁移率[2/cm V s ]迁移率表明载流子响应ε的容易程度。

drift e e υµε=−drift h h υµε=−迁移率取决于掺杂水平以及是多数载流子还是少数载流子类型。

Si 在300K 时:●在低的N时:由声子散射所限制●在高的N时:由离化杂质散射所限制□ 速度饱和隐含的假定:准平衡,也就是说,散射率不太受平衡的影响。

drift drift thυευυ:=只在对高的ε:载流子从ε许多能量→光子发射显著增强→散射率1/ε:→漂移速度饱和sat υ;对Si 在300K 时,710/sat cm s υ;漂移速度与电场的关系由下式很好的表示: 1drift satµευµευ=+m 速度饱和时所要求的电场: satsat υεµ=在现代器件中速度饱和是至关重要的:如果2500/cm V s µ=,4210/sat V cm ε=(1m µ上2V )因为µ取决于掺杂,sat ε也取决于掺杂。

□ 粒子流和电流密度粒子流#粒子通过单位的表面(与流动方向正交)每单位时间[21cm s −−]电流密度电荷通过单位的表面(与流动方向正交)每单位时间[21cm s −−]e e J qF =−e e e n dt F n dt υυ==那么e e J qn υ=− h hJ qn υ=−漂移电流(低电场)e e J q n µε=h h J q n µε=总的为:()e h J q n p εµµε=+电导率[()1cm −Ω]:()e h q n p σµµ=+电阻率[cm Ω]:()1e h q n p ρµµ=+检查符号:()1e h q n p ρµµ=+ρ强烈的依赖于掺杂经常被硅片供应商用来表明衬底的掺杂水平 -对n 型:1n e D q N ρµ; -对p 型:1p h A q N ρµ;Si 在300K 时:漂移电流(高电场):esat esatJ qn υ= hsat hsatJ qn υ=得到更大电流的唯一方法是增加载流子浓度。

电压逆变器试题及答案答案

电压逆变器试题及答案答案

Courseware template
119. 电压型逆变器的直流端(
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121. 逆变器根据对无功能量的处理方法不同,分
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(X )8. 在电压型逆变器中,是用大电感来缓冲无 功能量的。
On the evening of July 24, 2021
Courseware template
电压逆变器试题及答案答案
It is applicable to work report, lecture and teaching
Courseware template
On the evening of July 24, 2021
Courseware template
• 单相桥式逆变电路的原理(R负载)
On the evening of July 24, 2021
Courseware template
• 66. 在并联谐振式晶闸管逆变器中,为求得较
高的功率因数和效率,应使晶闸管触发脉冲的
频率( C )负载电路的谐振频率。
A、远大于
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C、接近于
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141. 单相半桥逆变器(电压型)的每个导电臂由
119. 单相半桥逆变器(电压型)的每个导电
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A、电容器来缓冲有功能量

B、电容器来缓冲无功能Biblioteka 的C、电感器来缓冲有功能量

D、电感器来缓冲无功
On the evening of July 24, 2021

汽车专业英语教程多媒体教学课件Unit 7 section 2

汽车专业英语教程多媒体教学课件Unit 7 section 2

11 10
9 8 7
6 5 4
3 2 1
1—Oil Strainer;机油集滤器 2—Oil Dipsti1c2k;机油尺 3—Oil P1a3n;油底壳 4—Turbocharger;涡轮增压器 5—Waste Gate;废气旁通阀 6—to Exhaust Manifold;到排 气歧管 7—Intake Man1if4old;进气歧管 8—Valve;气门 9—Injector;喷1油5 器 10—Cylinder Head Cover;缸 盖罩 11—Camshaft;16凸轮轴
Section 2 Engine Fuel System 发动机燃油系统
The fuel system is critical to operation of engine . The fuel system
has the job of supplying a combu-
stible mix-ture of air and fuel to the engine.All auto-mobile have some forms of fuel supply system.There
化油器系统的主要 区别在于,燃油进 入进气歧管测量采 用几个燃料喷射器。 现代汽油喷射系统 使用计算机和传感 器,以确定不同的 发动机工况所需的 燃油量,计算机和 传感器读节气门位 置、发动机进气温 度、发动机冷却液 温度、排气管中氧 的浓度及其他重要 的指标(参见图78)。图7-9所示为 一共轨喷射柴油机。
Second,it must be able to move the
fuel from the fuel tank to the engine. Third,it must mix the fuel with

1-2007_-_Y_F_Han_-_PreparationofnanosizedMn3O4SBA15catalystforcomplet[retrieved-2016-11-15]

1-2007_-_Y_F_Han_-_PreparationofnanosizedMn3O4SBA15catalystforcomplet[retrieved-2016-11-15]

Preparation of nanosized Mn 3O 4/SBA-15catalyst for complete oxidation of low concentration EtOH in aqueous solution with H 2O 2Yi-Fan Han *,Fengxi Chen,Kanaparthi Ramesh,Ziyi Zhong,Effendi Widjaja,Luwei ChenInstitute of Chemical and Engineering Sciences,1Pesek Road,Jurong Island 627833,Singapore Received 11May 2006;received in revised form 18December 2006;accepted 29May 2007Available online 2June 2007AbstractA new heterogeneous Fenton-like system consisting of nano-composite Mn 3O 4/SBA-15catalyst has been developed for the complete oxidation of low concentration ethanol (100ppm)by H 2O 2in aqueous solution.A novel preparation method has been developed to synthesize nanoparticles of Mn 3O 4by thermolysis of manganese (II)acetylacetonate on SBA-15.Mn 3O 4/SBA-15was characterized by various techniques like TEM,XRD,Raman spectroscopy and N 2adsorption isotherms.TEM images demonstrate that Mn 3O 4nanocrystals located mainly inside the SBA-15pores.The reaction rate for ethanol oxidation can be strongly affected by several factors,including reaction temperature,pH value,catalyst/solution ratio and concentration of ethanol.A plausible reaction mechanism has been proposed in order to explain the kinetic data.The rate for the reaction is supposed to associate with the concentration of intermediates (radicals: OH,O 2Àand HO 2)that are derived from the decomposition of H 2O 2during reaction.The complete oxidation of ethanol can be remarkably improved only under the circumstances:(i)the intermediates are stabilized,such as stronger acidic conditions and high temperature or (ii)scavenging those radicals is reduced,such as less amount of catalyst and high concentration of reactant.Nevertheless,the reactivity of the presented catalytic system is still lower comparing to the conventional homogenous Fenton process,Fe 2+/H 2O 2.A possible reason is that the concentration of intermediates in the latter is relatively high.#2007Elsevier B.V .All rights reserved.Keywords:Hydrogen peroxide;Fenton catalyst;Complete oxidation of ethanol;Mn 3O 4/SBA-151.IntroductionRemediation of wastewater containing organic constitutes is of great importance because organic substances,such as benzene,phenol and other alcohols may impose toxic effects on human and animal anic effluents from pharmaceu-tical,chemical and petrochemical industry usually contaminate water system by dissolving into groundwater.Up to date,several processes have been developed for treating wastewater that contains toxic organic compounds,such as wet oxidation with or without solid catalysts [1–4],biological oxidation,supercritical oxidation and adsorption [5,6],etc.Among them,catalytic oxidation is a promising alternative,since it avoids the problem of the adsorbent regeneration in the adsorption process,decreases significantly the temperature and pressure in non-catalytic oxidation techniques [7].Generally,the disposalof wastewater containing low concentration organic pollutants (e.g.<100ppm)can be more costly through all aforementioned processes.Thus,catalytic oxidation found to be the most economical way for this purpose with considering its low cost and high efficiency.Currently,a Fenton reagent that consists of homogenous iron ions (Fe 2+)and hydrogen peroxide (H 2O 2)is an effective oxidant and widely applied for treating industrial effluents,especially at low concentrations in the range of 10À2to 10À3M organic compounds [8].However,several problems raised by the homogenous Fenton system are still unsolved,e.g.disposing the iron-containing waste sludge,limiting the pH range (2.0–5.0)of the aqueous solution,and importantly irreversible loss of activity of the reagent.To overcome these drawbacks raised from the homogenous Fenton system,since 1995,a heterogeneous Fenton reagent using metal ions exchanged zeolites,i.e.Fe/ZSM-5has proved to be an interesting alternative catalytic system for treating wastewater,and showed a comparable activity with the homogenous Fenton system [9].However,most reported heterogeneous Fenton reagents still need UV radiation during/locate/apcatbApplied Catalysis B:Environmental 76(2007)227–234*Corresponding author.Tel.:+6567963806.E-mail address:han_yi_fan@.sg (Y .-F.Han).0926-3373/$–see front matter #2007Elsevier B.V .All rights reserved.doi:10.1016/j.apcatb.2007.05.031oxidation of organic compounds.This might limit the application of homogeneous Fenton system.Exploring other heterogeneous catalytic system considering the above disadvantages,is still desirable for this purpose.Here,we present an alternative catalytic system for the complete oxidation of organic com-pounds in aqueous solution using supported manganese oxide as catalyst under mild conditions,which has rarely been addressed.Mn-containing oxide catalysts have been found to be very active for the catalytic wet oxidation of organic effluents (CWO)[10–14],which is operated at high air pressures(1–22MPa)and at high temperatures(423–643K)[15].On the other hand,manganese oxide,e.g.MnO2[16],is well known to be active for the decomposition of H2O2in aqueous solution to produce hydroxyl radical( OH),which is considered to be the most robust oxidant so far.The organic constitutes can be deeply oxidized by those radicals rapidly[17].The only by-product is H2O from decomposing H2O2.Therefore,H2O2is a suitable oxidant for treating the wastewater containing organic compounds.Due to the recent progress in the synthesis of H2O2 directly from H2and O2[18,19],H2O2is believed to be produced through more economical process in the coming future.So,the heterogeneous Fenton system is economically acceptable.In this study,nano-crystalline Mn3O4highly dispersed inside the mesoporous silica,SBA-15,has been prepared by thermolysis of organic manganese(II)acetylacetonate in air. We expect the unique mesoporous structure may provide add-itional function(confinement effect)to the catalytic reaction, i.e.occluding/entrapping large organic molecules inside pores. The catalyst as prepared has been examined for the complete oxidation of ethanol in aqueous solution with H2O2,or to say, wet peroxide oxidation.Ethanol was selected as a model organic compound because(i)it is one of the simplest organic compounds and can be easily analyzed,(ii)it has high solu-bility in water due to its strong hydrogen bond with water molecule and(iii)the structure of ethanol is quite stable and only changed through catalytic reaction.Presently,for thefirst time by using the Mn3O4/SBA-15catalyst,we investigated the peroxide ethanol oxidation affected by factors such as temperature,pH value,ratio of catalyst(g)and volume of solution(L),and concentration of ethanol in aqueous solution. In addition,plausible reaction mechanisms are established to explain the peroxidation of ethanol determined by the H2O2 decomposition.2.Experimental2.1.Preparation and characterization of Mn3O4/SBA-15 catalystSynthesis of SBA-15is similar to the previous reported method[20]by using Pluronic P123(BASF)surfactant as template and tetraethyl orthosilicate(TEOS,98%)as silica source.Manganese(II)acetylacetonate([CH3COCH C(O)CH3]2Mn,Aldrich)by a ratio of2.5mmol/gram(SBA-15)werefirst dissolved in acetone(C.P.)at room temperature, corresponding to ca.13wt.%of Mn3O4with respect to SBA-15.The preparation method in detail can be seen in our recent publications[21,22].X-ray diffraction profiles were obtained with a Bruker D8 diffractometer using Cu K a radiation(l=1.540589A˚).The diffraction pattern was taken in the Bragg angle(2u)range at low angles from0.68to58and at high angles from308to608at room temperature.The XRD patterns were obtained by scanning overnight with a step size:0.028per step,8s per step.The dispersive Raman microscope employed in this study was a JY Horiba LabRAM HR equipped with three laser sources(UV,visible and NIR),a confocal microscope,and a liquid nitrogen cooled charge-coupled device(CCD)multi-channel detector(256pixelsÂ1024pixels).The visible 514.5nm argon ion laser was selected to excite the Raman scattering.The laser power from the source is around20MW, but when it reached the samples,the laser output was reduced to around6–7MW after passing throughfiltering optics and microscope objective.A100Âobjective lens was used and the acquisition time for each Raman spectrum was approximately 60–120s depending on the sample.The Raman shift range acquired was in the range of50–1200cmÀ1with spectral resolution1.7–2cmÀ1.Adsorption and desorption isotherms were collected on Autosorb-6at77K.Prior to the measurement,all samples were degassed at573K until a stable vacuum of ca.5m Torr was reached.The pore size distribution curves were calculated from the adsorption branch using Barrett–Joyner–Halenda(BJH) method.The specific surface area was assessed using the BET method from adsorption data in a relative pressure range from 0.06to0.10.The total pore volume,V t,was assessed from the adsorbed amount of nitrogen at a relative pressure of0.99by converting it to the corresponding volume of liquid adsorbate. The conversion factor between the volume of gas and liquid adsorbate is0.0,015,468for N2at77K when they are expressed in cm3/g and cm3STP/g,respectively.The measurements of transmission electron microscopy (TEM)were performed at Tecnai TF20S-twin with Lorentz Lens.The samples were ultrasonically dispersed in ethanol solvent,and then dried over a carbon grid.2.2.Kinetic measurement and analysisThe experiment for the wet peroxide oxidation of ethanol was carried out in a glass batch reactor connected to a condenser with continuous stirring(400rpm).Typically,20ml of aqueous ethanol solution(initial concentration of ethanol: 100ppm)wasfirst taken in the round bottomflask(reactor) together with5mg of catalyst,corresponding to ca.1(g Mn)/30 (L)ratio of catalyst/solution.Then,1ml of30%H2O2solution was introduced into the reactor at different time intervals (0.5ml at$0min,0.25ml at32min and0.25ml at62min). The total molar ratio of H2O2/ethanol is about400/1. Hydrochloric acid(HCl,0.01M)was used to acidify the solution if necessary.NH4OH(0.1M)solution was used to adjust pH to9.0when investigating the effect of pH.The pH for the deionized water is ca.7.0(Oakton pH meter)and decreased to 6.7after adding ethanol.All the measurements wereY.-F.Han et al./Applied Catalysis B:Environmental76(2007)227–234 228performed under the similar conditions described above if without any special mention.For comparison,the reaction was also carried out with a typical homogenous Fenton reagent[17], FeSO4(5ppm)–H2O2,under the similar reaction conditions.The conversion of ethanol during reaction was detected using gas chromatography(GC:Agilent Technologies,6890N), equipped with HP-5capillary column connecting to a thermal conductive detector(TCD).There is no other species but ethanol determined in the reaction system as evidenced by the GC–MS. Ethanol is supposed to be completely oxidized into CO2and H2O.The variation of H2O2concentration during reaction was analyzed colorimetrically using a UV–vis spectrophotometer (Epp2000,StellarNet Inc.)after complexation with a TiOSO4/ H2SO4reagent[18].Note that there was almost no measurable leaching of Mn ion during reaction analyzed by ICP(Vista-Mpx, Varian).3.Results and discussion3.1.Characterization of Mn3O4/SBA-15catalystThe structure of as-synthesized Mn3O4inside SBA-15has beenfirst investigated with powder XRD(PXRD),and the profiles are shown in Fig.1.The profile at low angles(Fig.1a) suggests that SBA-15still has a high degree of hexagonal mesoscopic organization even after forming Mn3O4nanocrys-tals[23].Several peaks at high angles of XRD(Fig.1b)indicate the formation of a well-crystallized Mn3O4.All the major diffraction peaks can be assigned to hausmannite Mn3O4 structure(JCPDS80-0382).By N2adsorption measurements shown in Fig.2,the pore volume and specific surface areas(S BET)decrease from 1.27cm3/g and937m2/g for bare SBA-15to0.49cm3/g and 299m2/g for the Mn3O4/SBA-15,respectively.About7.7nm of mesoporous diameter for SBA-15decreases to ca.6.3nm for Mn3O4/SBA-15.The decrease of the mesopore dimension suggests the uniform coating of Mn3O4on the inner walls of SBA-15.This nano-composite was further characterized by TEM. Obviously,the SBA-15employed has typical p6mm hex-agonal morphology with the well-ordered1D array(Fig.3a). The average pore size of SBA-15is ca.8.0nm,which is very close to the value(ca.7.7nm)determined by N2adsorption. Along[001]orientation,Fig.3b shows that the some pores arefilled with Mn3O4nanocrystals.From the pore A to D marked in Fig.3b correspond to the pores from empty to partially and fullyfilled;while the features for the SBA-15 nanostructure remains even after forming Mn3O4nanocrys-tals.Nevertheless,further evidences for the location of Mn3O4inside the SBA-15channels are still undergoing in our group.Raman spectra obtained for Mn3O4/SBA-15is presented in Fig.4a.For comparison the Raman spectrum was also recorded for the bulk Mn3O4(97.0%,Aldrich)under the similar conditions(Fig.4b).For the bulk Mn3O4,the bands at310,365, 472and655cmÀ1correspond to the bending modes of Mn3O4, asymmetric stretch of Mn–O–Mn,symmetric stretch of Mn3O4Fig.1.XRD patterns of the bare SBA-15and the Mn3O4/SBA-15nano-composite catalyst.(a)At low angles:(A)Mn3O4/SBA-15,(B)SBA-15;and (b)at high angles of Mn3O4/SBA-15.Fig.2.N2adsorption–desorption isotherms:(!)SBA-15,(~)Mn3O4/SBA-15.Y.-F.Han et al./Applied Catalysis B:Environmental76(2007)227–234229groups,respectively [24–26].However,a downward shift ($D n 7cm À1)of the peaks accompanying with a broadening of the bands was observed for Mn 3O 4/SBA-15.For instance,the distinct feature at 655cm À1for the bulk Mn 3O 4shifted to 648cm À1for the nanocrystals.The Raman bands broadened and shifted were observed for the nanocrystals due to the effect of phonon confinement as suggested previously in the literature [27,28].Furthermore,a weak band at 940cm À1,which should associate with the stretch of terminal Mn O,is an indicative of the existence of the isolated Mn 3O 4group [26].The assignment of this unique band has been discussed in our previous publication [22].3.2.Kinetic study3.2.1.Blank testsUnder a typical reaction conditions,that is,20ml of 100ppm ethanol aqueous solution (pH 6.7)mixed with 1ml of 30%H 2O 2,at 343K,there is no conversion of ethanol was observed after running for 120min in the absence of catalyst or in the presence of bare SBA-15(5mg).Also,under the similar conditions in H 2O 2-free solution,ethanol was not converted for all blank tests even with Mn 3O 4/SBA-15catalyst (5mg)in the reactor.It suggests that a trace amount of oxygen dissolved in water or potential dissociation of adsorbed ethanol does not have any contribution to the conversion of ethanol under reaction conditions.To study the effect of low temperature evaporation of ethanol during reaction,we further examined the concentration of ethanol (100ppm)versus time at different temperatures in the absence of catalyst and H 2O 2.Loss of ca.5%ethanol was observed only at 363K after running for 120min.Hence,to avoid the loss of ethanol through evaporation at high temperatures,which may lead to a higher conversion of ethanol than the real value,the kinetic experiments in this study were performed at or below 343K.The results from blank tests confirm clearly that ethanol can be transformed only by catalytic oxidation during reaction.3.2.2.Effect of amount of catalystThe effect of amount of catalyst on ethanol oxidation is presented in Fig.5.Different amounts of catalyst ranging from 2to 10mg were taken for the same concentration of ethanol (100ppm)in aqueous solution under the standard conditions.It can be observed that the conversion of ethanol increases monotonically within 120min,reaching 15,20and 12%for 2,5and 10mg catalysts,respectively.On the other hand,Fig.5shows that the relative reaction rates (30min)decreased from 0.7to ca 0.1mmol/g Mn min with the rise of catalyst amount from 2to 10mg.Apparently,more catalyst in the system may decrease the rate for ethanol peroxidation,and a proper ratio of catalyst (g)/solution (L)is required for acquiring a balance between the overall conversion of ethanol and reaction rate.In order to investigate the effects from other factors,5mg (catalyst)/20ml (solution),corresponding to 1(g Mn )/30(L)ratio of catalyst/solution,has been selected for the followedexperiments.Fig.4.Raman spectroscopy of the Mn 3O 4/SBA-15(a)and bulk Mn 3O 4(b).Fig.3.TEM images recorded along the [001]of SBA-15(a),Mn 3O 4/SBA-15(b):pore A unfilled with hexagonal structure,pores B and C partially filled and pore D completely filled.Y.-F .Han et al./Applied Catalysis B:Environmental 76(2007)227–2342303.2.3.Effect of temperatureAs shown in Fig.6,the reaction rate increases with increasing the reaction temperature.After 120min,the conversion of ethanol increases from 12.5to 20%when varying the temp-erature from 298to 343K.Further increasing the temperature was not performed in order to avoid the loss of ethanol by evaporation.Interestingly,the relative reaction rate increased with time within initial 60min at 298and 313K,but upward tendency was observed above 333K.3.2.4.Effect of pHIn the pH range from 2.0to 9.0,as illustrated in Fig.7,the reaction rate drops down with the rise of pH.It indicates that acidic environment,or to say,proton concentration ([H +])in the solution is essential for this reaction.With considering our target for this study:purifying water,pH approaching to 7.0in the reaction system is preferred.Because acidifying the solution with organic/inorganic acids may potentially causea second time pollution and result in surplus cost.Actually,there is almost no effect on ethanol conversion with changing pH from 5.5to 6.7in this system.It is really a merit comparing with the conventional homogenous Fenton system,by which the catalyst works only in the pH range of 2.0–5.0.3.2.5.Effect of ethanol concentrationThe investigation of the effect of ethanol concentration on the reaction rate was carried out in the ethanol ranging from 50to 500ppm.The results in Fig.8show that the relative reaction rate increased from 0.07to 2.37mmol/g Mn min after 120min with increasing the concentration of ethanol from 50to 500ppm.It is worth to note that the pH value of the solution slightly decreased from 6.7to 6.5when raising the ethanol concentration from 100to 500ppm.paring to a typical homogenous Fenton reagent For comparison,under the similar reaction conditions ethanol oxidation was performed using aconventionalFig.5.The ethanol oxidation as a function of time with different amount of catalyst.Conversion of ethanol vs.time (solid line)on 2mg (&),5mg (*)and 10mg (~)Mn 3O 4/SBA-15catalyst,the relative reaction rate vs.time (dash line)on 2mg (&),5mg (*)and 10mg (~)Mn 3O 4/SBA-15catalyst.Rest conditions:20ml of ethanol (100ppm),1ml of 30%H 2O 2,708C and pH of6.7.Fig.6.The ethanol oxidation as a function of temperature.Conversion of ethanol vs.time (solid line)at 258C (&),408C (*),608C (~)and 708C (!),the relative reaction rate vs.time (dash line)at 258C (&),408C (*),608C (~)and 708C (5).Rest conditions:20ml of ethanol (100ppm),1ml of 30%H 2O 2,pH of 6.7,5mg ofcatalyst.Fig.7.The ethanol oxidation as a function of pH value.Conversion of ethanol vs.time (solid line)at pH value of 2.0(&),3.5(*),4.5(~),5.5(!),6.7(^)and 9.0("),the relative reaction rate vs.time (dash line)at pH value of 2.0(&),3.5(*),4.5(~),5.5(5),6.7(^)and 9.0(").Rest conditions:20ml of ethanol (100ppm),1ml of 30%H 2O 2,708C,5mg ofcatalyst.Fig.8.The ethanol oxidation as a function of ethanol concentration.Conver-sion of ethanol vs.time (solid line)for ethanol concentration (ppm)of 50(&),100(*),300(~),500(!),the relative reaction rate vs.time (dash line)for ethanol concentration (ppm)of 50(&),100(*),300(~),500(5).Condi-tions:20ml of ethanol,pH of 6.7,1ml of 30%H 2O 2,708C,5mg of catalyst.Y.-F .Han et al./Applied Catalysis B:Environmental 76(2007)227–234231homogenous reagent,Fe 2+(5ppm)–H 2O 2(1ml)at pH of 5.0.It has been reported to be an optimum condition for this system [17].As shown in Fig.9,the reaction in both catalytic systems exhibits a similar behavior,that is,the conversion of ethanol increases with extending the reaction time.Varying reaction temperature from 298to 343K seems not to impact the conversion of ethanol when using the homogenous Fenton reagent.Furthermore,the conversion of ethanol (defining at 120min)in the system of Mn 3O 4/SBA-15–H 2O 2is about 60%of that obtained from the conventional Fenton reagent.There are no other organic compounds observed in the reaction mixture other than ethanol suggesting that ethanol directly decomposing to CO 2and H 2O.3.2.7.Decomposition of H 2O 2In the aqueous solution,the capability of metal ions such as Fe 2+and Mn 2+has long been evidenced to be effective on the decomposition of H 2O 2to produce the hydroxyl radical ( OH),which is oxidant for the complete oxidation/degrading of organic compounds [9,17].Therefore,ethanol oxidation is supposed to be associated with H 2O 2decomposition.The investigation of H 2O 2decomposition has been performed under the reaction conditions (in an ethanol-free solution)with different amounts of catalyst.H 2O 2was introduced into the reaction system by three steps,initially 0.5ml followed by twice 0.25ml at 32and 62min,the pH of 6.7is set for all experiments except pH of 5.0for Fe 2+.As shown in Fig.10,H 2O 2was not converted in the absence of catalyst or presence of bare SBA-15(5mg);in contrast,by using the Mn 3O 4/SBA-15catalyst we observed that ca.Ninety percent of total H 2O 2was decomposed in the whole experiment.It can be concluded that that dissociation of H 2O 2is mainly caused by Mn 3O paratively,the rate of H 2O 2decomposition is relatively low with the homogenous Fenton reagent,total conversion of H 2O 2,was ca.50%after runningfor 120min.Considering the fact that H 2O 2decomposition can be significantly enhanced with the rise of Fe 2+concentration,however,it seems not to have the influence on the reaction rate for ethanol oxidation simultaneously.The similar behavior of H 2O 2decomposition was also observed during ethanol oxidation.The rate for ethanol oxidation is lower for Mn 3O 4/SBA-15comparing to the conventional Fenton reagent.The possible reasons will be discussed in the proceeding section.3.3.Plausible reaction mechanism for ethanol oxidation with H 2O 2In general,the wet peroxide oxidation of organic constitutes has been suggested to proceed via four steps [15]:activation of H 2O 2to produce OH,oxidation of organic compounds withOH,recombination of OH to form O 2and wet oxidation of organic compounds with O 2.It can be further described by Eqs.(1)–(4):H 2O 2À!Catalyst =temperture 2OH(1)OH þorganic compoundsÀ!Temperatureproduct(2)2 OHÀ!Temperature 12O 2þH 2O(3)O 2þorganic compoundsÀ!Temperature =pressureproduct(4)The reactive intermediates produced from step 1(Eq.(1))participate in the oxidation through step 2(Eq.(2)).In fact,several kinds of radical including OH,perhydroxyl radicals ( HO 2)and superoxide anions (O 2À)may be created during reaction.Previous studies [29–33]suggested that the process for producing radicals could be expressed by Eqs.(5)–(7)when H 2O 2was catalytically decomposed by metal ions,such asFeparison of ethanol oxidation in systems of typical homogenous Fenton catalyst (5ppm of Fe 2+,20ml of ethanol (100ppm),1ml of 30%H 2O 2,pH of 5.0acidified with HCl)at room temperature (~)and 708C (!),and Mn 3O 4/SBA-15catalyst (&)under conditions of 20ml of ethanol (100ppm),pH of 6.7,1ml of 30%H 2O 2,708C,5mg ofcatalyst.Fig.10.An investigation of H 2O 2decomposition under different conditions.One milliliter of 30%H 2O 2was dropped into the 20ml deionized water by three intervals,initial 0.5ml followed by twice 0.25ml at 32and 62min.H 2O 2concentration vs.time:by calculation (&),without catalyst (*),SBA-15(~),5ppm of Fe 2+(!)and Mn 3O 4/SBA-15(^).Rest conditions:5mg of solid catalyst,pH of 7.0(5.0for Fe 2+),708C.Y.-F .Han et al./Applied Catalysis B:Environmental 76(2007)227–234232and Mn,S þH 2O 2!S þþOH Àþ OH (5)S þþH 2O 2!S þ HO 2þH þ(6)H 2O $H þþO 2À(7)where S and S +represent reduced and oxidized metal ions,both the HO 2and O 2Àare not stable and react further with H 2O 2to form OH through Eqs.(8)and (9):HO 2þH 2O 2! OH þH 2O þO 2(8)O 2ÀþH 2O 2! OH þOH ÀþO 2(9)Presently, OH radical has been suggested to be the main intermediate responsible for oxidation/degradation of organic compounds.Therefore,the rate for ethanol oxidation in the studied system is supposed to be dependent on the concentra-tion of OH.Note that the oxidation may proceed via step four (Eq.(4))in the presence of high pressure O 2,which is so-called ‘‘wet oxidation’’and usually occurs at air pressures (1–22MPa)and at high temperatures (423–643K)[15].However,it is unlikely to happen in the present reaction conditions.According to Wolfenden’s study [34],we envisaged that the complete oxidation of ethanol may proceed through a route like Eq.(10):C 2H 5OH þ OH À!ÀH 2OC 2H 4O À! OHCO 2þH 2O(10)Whereby,it is believed that organic radicals containing hydroxy-groups a and b to carbon radicals centre can eliminate water to form oxidizing species.With the degrading of organic intermediates step by step as the way described in Eq.(10),the final products should be CO 2and H 2O.However,no other species but ethanol was detected by GC and GC–MS in the present study possibly due to the rapid of the reaction that leads to unstable intermediate.Fig.5indicates that a proper ratio of catalyst/solution is a necessary factor to attain the high conversion of ethanol.It can be understood that over exposure of H 2O 2to catalyst will increase the rate of H 2O 2decomposition;but on the other hand,more OH radical produced may be scavenged by catalyst with increasing the amount of catalyst and transformed into O 2and H 2O as expressed in Eq.(3),instead of participating the oxidation reaction.In terms of Eq.(10),stoichiometric ethanol/H 2O 2should be 1/6for the complete oxidation of ethanol;however,in the present system the total molar ratio is 1/400.In other words,most intermediates were extinguished through scavenging during reaction.This may explain well that the decrease of reaction rate with the rise of ratio of catalyst/solution in the system.The same reason may also explain the decrease of reaction rate with prolonging the time.Actually,H 2O 2decomposition (ca.90%)may be completed within a few minutes over the Mn 3O 4/SBA-15catalyst as illustrated in Fig.10,irrespective of amount of catalyst (not shown for the sake of brevity);in contrast,the rate for H 2O 2decomposition became dawdling for Fe 2+catalyst.As a result,presumably,the homogenous system has relatively high concentration ofradicals.It may explain the superior reactivity of the conventional Fenton reagent to the presented system as depicted in Fig.9.Therefore,how to reduce scavenging,especially in the heterogeneous Fenton system [29],is crucial for enhancing the reaction rate.C 2H 5OH þ6H 2O 2!2CO 2þ9H 2O(11)On the other hand,as illustrated by Eqs.(1)–(4),all steps in the oxidation process are affected by the reaction temperature.Fig.6demonstrates that increasing temperature remarkably boosts the reactivity of ethanol oxidation in the system of Mn 3O 4/SBA-15–H 2O 2possibly,due to the improvement of the reactions in Eqs.(2)and (4)at elevated temperatures.In terms of Eqs.(6)and (7),acidic conditions may delay the H 2O 2decomposition but enhance the formation of OH (Eqs.(5),(8)and (9)).This ‘‘delay’’is supposed to reduce the chance of the scavenging of radicals and improve the efficiency of H 2O 2in the reaction.The protons are believed to have capability for stabilizing H 2O 2,which has been elucidated well previously [18,19].Consequently,it is understandable that the reaction is favored in the strong acidic environment.Fig.7shows a maximum reactivity at pH of 2.0and the lowest at pH of 9.0.As depicted in Fig.8,the reaction rate for ethanol oxidation is proportional to the concentration of ethanol in the range of 50–500ppm.It suggests that at low concentration of ethanol (100ppm)most of the radicals might not take part in the reaction before scavenged by catalyst.With increasing the ethanol concentration,the possibility of the collision between ethanol and radicals can be increased significantly.As a result,the rate of scavenging radicals is reduced relatively.Thus,it is reasonable for the faster rate observed at higher concentration of ethanol.Finally,it is noteworthy that as compared to the bulk Mn 3O 4(Aldrich,98.0%of purity),the reactivity of the nano-crystalline Mn 3O 4on SBA-15is increased by factor of 20under the same typical reaction conditions.Obviously,Mn 3O 4nanocrystal is an effective alternative for this catalytic system.The present study has evidenced that the unique structure of SBA-15can act as a special ‘‘nanoreactor’’for synthesizing Mn 3O 4nanocrystals.Interestingly,a latest study has revealed that iron oxide nanoparticles could be immobilized on alumina coated SBA-15,which also showed excellent performance as a Fenton catalyst [35].However,the role of the pore structure of SBA-15in this reaction is still unclear.We do expect that during reaction SBA-15may have additional function to trap larger organic molecules by adsorption.Thus,it may broaden its application in this field.So,relevant study on the structure of nano-composites of various MnO x and its role in the Fenton-like reaction for remediation of organic compounds in aqueous solution is undergoing in our group.4.ConclusionsIn the present study,we have addressed a new catalytic system suitable for remediation of trivial organic compound from contaminated water through a Fenton-like reaction withY.-F .Han et al./Applied Catalysis B:Environmental 76(2007)227–234233。

普林斯顿计算机公开课(原书第2版)

普林斯顿计算机公开课(原书第2版)

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普林斯顿计算机公开课(原书第2版)
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从1999年开始,作者在普林斯顿大学开设了一门名为“我们世界中的计算机”的课程(COS 109: Computers in Our World),这门课向非计算机专业的学生介绍计算机的基本常识,多年来大受学生追捧。本 书就是基于这门课程的讲义编写而成的,书中不仅解释了计算机和通信系统的工作原理,还分析了新技术带来的 隐私和安全问题。第2版的新增章节讨论了Python编程、人工智能、机器学习以及大数据等内容。本书适合所有 希望了解数字世界的读者阅读,通过了解技术的工作原理、起源和未来发展趋势,更好地理解并改变我们身处的 世界。
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Lecture Notes7Fixed Pattern NoiseEE392B Handout#20 Prof.A.El Gamal and H.-S.P.Wong Spring05•Definition•Sources of FPN•Analysis of FPN in PPS and APS•Total Noise Model•Correlated Double SamplingEE392B:Fixed Pattern Noise7-1Fixed Pattern Noise(FPN)•FPN(also called nonuniformity)is the spatial variation in pixel outputvalues under uniform illumination due to device and interconnectparameter variations(mismatches)across the sensor•It isfixed for a given sensor,but varies from sensor to sensor,so if v o isthe nominal pixel output value(at unifrom illumination),and the output pixel values(excluding temporal noise)from the sensor are v ij for1≤i≤n and1≤j≤m,then thefixed pattern noise is the set of values ∆v oij=v oij−v o•FPN consists of offset and gain components–increases with illumination, but causes more degradation in image quality at low illumination•FPN for CCD image sensors appears random•CMOS(PPS and APS)sensors have higher FPN than CCDs and sufferfrom column FPN,which appears as“stripes”in the image and can result in significant image quality degradationEE392B:Fixed Pattern Noise7-2FPN ImagesFor CCD sensor For CMOS sensorEE392B:Fixed Pattern Noise7-3Sources of FPN•CCD image sensors only suffer from pixel FPN due to spatial variation in photodetector device parameters and dark current–neither the CCDs nor the output amplifier(which is shared by all pixels)cause FPN(additional nonuniformity can result if more than one output amplifier is used,however)•In CMOS image sensors pixel transistors cause additional pixel FPN and column amplifiers cause column FPN.As a result FPN is in general higher than in CCDsEE392B:Fixed Pattern Noise7-4•Main sources of FPN in PPS:i dcA D v T ,C olv ov REF +v op osC f◦Pixel FPN is mainly due to the variation in the photodetectorparameters (e.g.,area A D )and dark current◦Column FPN is due to the variation in the column amplifierparameters,e.g.,offset voltage v op os ,feedback capacitor value,resettransistor threshold voltage and overlap capacitance value C olEE 392B:Fixed Pattern Noise 7-5•InAPSi dcA DoC D v ◦In addition to variation in the photodetector parameters and dark current,pixel FPN is caused also by variations in transistorparameters◦Column FPN is mainly due to variation i biasEE 392B:Fixed Pattern Noise 7-6PPS and APS FPN•APS suffers from higher pixel FPN than PPS but PPS generally suffersfrom higher column FPNPPS APSEE392B:Fixed Pattern Noise7-7Quantifying FPN•FPN is quantified by the standard deviation of the spatial variation inpixel outputs under uniform illumination(not including temporal noise).It is typically reported as a%of voltage swing(or well capacity)◦FPN standard deviation values of<0.1%to>4%of well capacityhave been reported•Experimentally,FPN is measured as follows:◦Set a constant uniform illumination level(including no illumination)◦Take many images◦For each pixel compute the average output value(to average outtemporal noise)◦Estimate the standard deviation of the average pixel values◦Repeat the procedure for several uniform illumination levelsEE392B:Fixed Pattern Noise7-8Analysis of FPN•Suppose we are given the standard deviation of each parameter that casues FPN,we now show how to compute its contribution to the total FPN•Assume the parameter values to be random variables Z1,Z2,...,Z k expressed asZ i=z i+∆Z i,where z i is the mean of Z i(i.e.,nominal value of the device parameter) and∆Z i is the variation of Z i from its mean,and has zero mean and standard deviationσZi•Assuming sufficiently small device parameter variations,we can approximate the pixel output voltage(for a given illumination)as a function of the device parameters using the Taylor series expansion,asV o(Z1,Z2,...,Z k)≈v o(z1,z2,...z k)+ki=1∂v o∂z i z1,z2,...z k·∆Z iEE392B:Fixed Pattern Noise7-9 where v o(z1,z2,...z k)is the nominal output voltage and∂v o/∂z i is thesensitivity of v o w.r.t.the i th parameter(evaluated at the nominalparameter values)•So the variation in V o can be represented by the random variable∆V o=ki=1∂v o∂z i z1,z2,...z k·∆Z i•To quantify FPN,wefind the standard deviation of the output voltage,σVo,i.e.,the standard deviation of the r.v.∆V o•Assuming that the∆Z i s are uncorrelated(may not be a good assumption in general),we can writeσVo= k i=1 ∂v o∂z i z1,z2,...z k 2·σ2Z iEE392B:Fixed Pattern Noise7-10Column and Pixel FPN•For a CMOS(PPS or APS)image sensor,let the column device parameters be Z1,Z2,...,Z l and the rest be the pixel device parameters, we can define the column variation asY=li=1∂v o∂z i z1,z2,...z k·∆Z iand the pixel variation asX=ki=l+1∂v o∂z i z1,z2,...z k·∆Z i•We quantify column FPN byσY and pixel FPN byσX(vary withillumination)•Since(by assumption)X and Y are uncorrelatedσ2Vo=σ2Y+σ2XEE392B:Fixed Pattern Noise7-11Offset and Gain FPN•The pixel output voltage v o and FPNσVovary with illumination •The nominal output voltage from a pixel can be expressed in terms of the photocurrent density asv o=hj ph+v oswhere h is the pixel gain in V·cm2/A(not to be confused with sensorconversion gain g)and v os is the pixel offset(which includes the dark signal as well as the offset voltages due to the amplifiers used,e.g.,v op os for PPS)•Assuming all photodetectors have the same QE,and thus under uniform illumination,they have the same photocurrent density,we can now write the pixel output voltage variation as∆V o= k i=1∂h∂z i z1,z2,...z k∆Z i j ph+ k i=1∂v os∂z i z1,z2,...z k∆Z i=∆H j ph+∆V osEE392B:Fixed Pattern Noise7-12•We quantify offset FPN byσVand gain FPN byσH·j phos•Offest FPN is reported as%of well capacity•Gain FPN is referred to as Pixel Response Nonuniformity(PRNU)and is reported as%of gain factor variation,i.e.,100σH/h•Note that∆H and∆V os are not necessarily uncorrelated,since somedevice parameters can affect both offset and gainEE392B:Fixed Pattern Noise7-13Analysis of FPN in PPS•Thefigure shows the device parameters consideredi dcA D v,C olTC fv ov REF+v oposA D is the photodiode area,i dc is its dark current,v op os is the opamp offsetvoltage,C ol is the overlap capacitance,and v T is the threshold voltageEE392B:Fixed Pattern Noise7-14•The output voltage in steady state is given byv o=(Q+C ol v T)·1C f+v REF+v op os,where C ol v T is the“feedthrough”charge(when the reset transistor isturned off),and the charge Q accumulated on the photodiode capacitanceQ=(j ph A D+i dc)t int•The following table lists the absolute values of the parameter senitivities ∂v oiand effect on FPNParameter Sensitivity Effect on FPNA D t intC f·j ph pixel/gaini dc t intC fpixel/offsetv op os1column/offsetC f i dc t int+C ol v TC2fcolumn/offset+A D t intC2f·j ph column/gainv T C olC fcolumn/offsetC ol v TC fcolumn/offsetEE392B:Fixed Pattern Noise7-15•Offset FPNσVos= t int fσi dc 2+σ2v op os+ i dc t int+C ol v T2f σC f 2+ v T fσC ol 2+ C ol fσv T 2•Gain FPNσH·j ph=j ph t int C fσA D 2+ A D t int C2fσC f 2•Pixel FPNσX= j ph t int C fσA D 2+ t int C fσi dc 2•Column FPNσY= σ2v op os+ i dc t int+C ol v T+A D j ph t int2f σC f 2+ v T fσC ol 2+ C ol fσv T 2•Note that the FPN varianceσ2V o=σ2X+σ2Y can be written as the sum of three terms,a term that is independent of the signal,a term thatincreases linearly with the signal,and a term that increases quadratically with the signalEE392B:Fixed Pattern Noise7-16Example•Assume the following device parameter means,standard deviations,and that t int=30msParameter MeanσSensitivityA D50µm20.4%A D15×103j ph V/µm2i dc5fA2%i dc1.5mV/fAv op os0V2mV1C f20fF0.2%C f11.6×1011V/F37500j ph V/fFv T R0.8V0.2%v T R0.02C ol0.4fF0.4%C ol0.04V/fFEE392B:Fixed Pattern Noise7-17•Offset FPNParameter Contribution toσVosi dc0.15mVv op os2mVC f0.0464mVv T R0.032mVC ol0.064mVand≈2mV,σVosvaluewhich is basically equal to the opamp offsetσv opos•Gain FPN at j ph=2.64×10−6A/cm2(high illumination)Parameter Contribution toσH·j phA D7.92mVC f3.96mVandσH·j ph=8.85mVEE392B:Fixed Pattern Noise7-18•The followingfigure plots total FPNσVo,pixel FPNσX,and column FPN σY,assuming monochromatic illumination F0photons/cm2.s at quantum efficiency QE=0.3EE392B:Fixed Pattern Noise7-19Analysis of FPN in APSi dcA DC D•In steady state and assuming soft reset,the output voltage is given byv o=v DD−v T R−QC D− v T F+ F k n W F i bias , where the charge accumulted on the photodiode is given byQ=(A D j ph+i dc)t int+C olR v DDThe C olR v DD term is the“feedthrough”charge(when the reset transistor is turned off)EE392B:Fixed Pattern Noise7-20Example•Consider the following parameter means and standard deviations parameter meanσeffect on FPNi dc5fA2%i dc pixel/offsetA D50µm20.4%A D pixel/gainC D20fF0.4%CD pixel/offset,gainv T R 1.1V0.2%v T R pixel/offsetC olR0.4fF0.4%C olR pixel/pffsetv T F0.9V0.2%v T F pixel/offsetW F L F 420.2%W FFpixel/offseti bias1.88µA1%i bias column/offset•You will compute the FPN component values in the homeworkEE392B:Fixed Pattern Noise7-21Image Sensor Total Noise Model•Combining temporal noise and FPN,we can express the total inputreferred noise charge asQ n=Q shot+Q reset+Q readout+Q fpn,where◦Q shot is the r.v.representing the noise charge due to photodetectorphoto and dark current shot noise and is Gaussian with zero meanand variance1q(i ph+i dc)t int electrons2◦Q reset is the r.v.representing the reset noise and is basicallyindependent of the signal◦Q readout is the r.v.representing the readout circuit noise(possiblyincluding quantization)and is basically independent of the signalEE392B:Fixed Pattern Noise7-22◦Q fpn is the r.v.representing FPN(in electrons),and can be represented either as a sum of pixel and column componentsQ fpn=1g(X+Y)where g is the sensor conversion gain in V/electron, or offset and gain componentsQ fpn=1g(∆Hj ph+∆V os)Thus it has one component that is independent of signal and onethat grows with the signal◦The noise components are assumed independent•Thus the total average noise power is the sum of three components:◦One that does not depend on the signal(due to reset and readoutnoise and offset FPN)◦One that increases linearly with the signal(i ph or j ph)(due to shotnoise and gain FPN)◦One that increases quadratically in the signal(due to gain FPN)EE392B:Fixed Pattern Noise7-23 Noise as Function of PhotocurrentEE392B:Fixed Pattern Noise7-24Correlated Double Sampling (CDS)•CDS is a multiple sampling technique commonly used in image sensors to reduce FPN and reset noise •You sample the output twice;once right after reset and a second time with the signal present.The output signal is the difference between the two samples◦CDS only reduces offset FPN (does not reduce gain FPN)◦CDS does not cancel offset FPN due to dark current variation ◦In CCDs,PPS,photogate and pinned diode APS,CDS cancels reset noise.In photodiode APS it increases itEE 392B:Fixed Pattern Noise 7-25CDS inPPSReset SR oSoRWord,SSEE 392B:Fixed Pattern Noise7-26•Cancells,v T,and C ol◦FPN due to v oposand V2o3in our analysis)◦Temporal noise due to reset(terms V2o2◦Readout noise due to op-amp1/f noise•Does not cancel◦Offset FPN due to i dc variation.This is called Dark SignalNon-uniformity(DSNU)◦Gain FPN(or PRNU)◦Other temporal noise components•Addsterm)◦Opamp noise due to reset read(Vo4◦KTnoise due to SS and SR transistorsCEE392B:Fixed Pattern Noise7-27•To summarize,the total noise charge for the two samples are given by:Q n1=Q reset+Q read1+Q fpn1Q n2=Q shot+Q reset+Q readout2+Q fpn2Note that Q fpn1is simply an offset FPN whereas Q fpn2is the sum of offset and gain FPN(PRNU).However,Q fpn1does not include the offset FPN due to dark current variation(DSNU),whereas the offset part of Q fpn1includes itThe difference between the two samples is thus:Q n2−Q n1=Q shot+(Q readout2−Q readout1)+Q prnu+Q dsnuEE392B:Fixed Pattern Noise7-28PPS FPN With and Without CDS•The following figure plots PPS FPN with and without CDS (assumingthat v op,v T ,and C ol are eliminated)EE 392B:Fixed Pattern Noise 7-29PPS Offset FPN With and Without CDS102030405060102030405060102030405060102030405060without CDS with CDSEE 392B:Fixed Pattern Noise 7-30CDS in 3TAPSWord ResetReset SS SRoSoREE 392B:Fixed Pattern Noise7-31•Cancells◦All offset FPN terms involving v T R ,v T F ,C olR ,W F L F ,and i bias•Does not cancel◦DSNU ◦Reset noise ◦PRNU ◦Readout noise •Adds◦Reset noise kT 2C D (reset noise component during reset readout independent of that during signal readout)◦Readout noise during reset readout ◦kT Cdue to SS and SR transistorsEE 392B:Fixed Pattern Noise 7-32•To summarize,the total noise charge for the two samples are given by:Q n1=Q shot+Q reset1+Q readout1+Q fpn1Q n2=Q reset2+Q readout2+Q fpn2The difference is:Q n1−Q n2=Q shot+(Q reset1−Q reset2)+(Q read1−Q read2)+Q prnu+Q dsnu•An important advantage of photogate and pinned diode APS is that reset noise is eliminated using CDS instead of doubledEE392B:Fixed Pattern Noise7-33。

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