动态现场原位（operando）表征技术在多相催化反应中的应用与进展

doi:10.16085/j.issn.1000-6613.2018-1196

化工进展 ›› 2019, Vol. 38 ›› Issue (01): 260-277.DOI: 10.16085/j.issn.1000-6613.2018-1196

动态现场原位（operando）表征技术在多相催化反应中的应用与进展

孙杨¹(),丁豆豆¹,林昌¹,刘向林¹,张超¹,田鹏飞¹,曹晨熙¹,杨子旭¹,徐晶¹(),韩一帆^1,²()

1. 华东理工大学化学工程联合国家重点实验室，上海 200237
2. 郑州大学化工与能源学院，河南郑州 450001

收稿日期:2018-06-07 修回日期:2018-09-26 出版日期:2019-01-05 发布日期:2019-01-05
通讯作者: 徐晶,韩一帆
作者简介:孙杨（1994—），女，博士研究生，研究方向为高级氧化法污水处理技术。E-mail：<email>296329490@qq.com</email>。|徐晶，教授，博士生导师。E-mail：<email>xujing@ecust.edu.cn</email>|韩一帆，教授，博士生导师，研究方向为工业催化。E-mail:<email>yifanhan@ecust.edu.cn</email>
基金资助:
国家重点研发计划(2018YFB0604501);国家自然科学基金(21576084，91534127);国家重点研发计划（2018YFB0604501）；国家自然科学基金（21576084，91534127）。

Advances in operando techniques for the heterogeneous catalytic reactions

Yang SUN¹(),doudou DING¹,Chang LIN¹,Xianglin LIU¹,Chao ZHANG¹,Pengfei TIAN¹,Chenxi CAO¹,Zixu YANG¹,Jing XU¹(),Yifan HAN^1,²()

1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
2. School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, Henan, China

Received:2018-06-07 Revised:2018-09-26 Online:2019-01-05 Published:2019-01-05
Contact: Jing XU,Yifan HAN

摘要/Abstract

摘要：

动态现场原位（operando）表征是在接近过程工业反应条件下，揭示催化反应机理及工业催化剂结构演变的新兴动态结构解析技术。本文综述了operando表征技术在多相催化反应中的应用及发展趋势，从operando红外、operando拉曼、operando X射线衍射、operando穆斯堡尔谱、operando X射线吸收谱及operando X射线光电子能谱6个方面概述了operando技术的最新进展。此外，还介绍了正在兴起的operando联用技术，该技术综合多种operando技术为一体，能够在反应过程中对催化剂的结构全貌进行深度表征，实现工业催化剂的理性设计，将成为未来多相催化研究的重要手段。然而，目前operando技术的时间分辨率和空间分辨率仍需进一步提升，其巨大潜力依然有待开发。

关键词: 动态现场原位技术, 催化, 原位表征, 催化剂构-效关系, 反应, 表面

Abstract:

Operando characterization is a cutting-edge technique for revealing the catalytic reaction mechanism and the dynamic structure evolution of industrial catalysts under the conditions close to industrial reaction. The development of operando technique and its application on heterogeneous catalysis have been reviewed, and the latest progress on operando infrared spectroscopy (IR), operando Raman, operando X-ray diffraction (XRD), operando M?ssbauer, operando X-ray adsorption spectra (XAS), and operando X-ray photoelectron spectroscopy (XPS) have been summarized. In addition, the coupling of various operando characterizations has also been introduced. Through this technique, the overall structure of the catalyst during reaction process can be characterized more deeply, and thus can realize the rational design of industrial catalysts. Therefore, we believe this coupling technique will become an important and prospective way to study heterogeneous catalysis. Nevertheless, the time and space resolution of current operando technique needs to be improved, and its enormous potential still requires to be further developed.

Key words: operando, catalysis, in-situ, structure-performance relationship, reaction, surface

中图分类号:

TQ02
TQ03

孙杨, 丁豆豆, 林昌, 刘向林, 张超, 田鹏飞, 曹晨熙, 杨子旭, 徐晶, 韩一帆. 动态现场原位（operando）表征技术在多相催化反应中的应用与进展[J]. 化工进展, 2019, 38(01): 260-277.

Yang SUN, doudou DING, Chang LIN, Xianglin LIU, Chao ZHANG, Pengfei TIAN, Chenxi CAO, Zixu YANG, Jing XU, Yifan HAN. Advances in operando techniques for the heterogeneous catalytic reactions[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 260-277.

图/表 29

图1 理想operando装置[9]

图2 两种典型的operando反应器示意图

图3 operando透射红外反应器的拆解图与所得构-效关系[15]

图4 operando DRIFTS光谱研究Sn改性Co/Al2O3催化剂

图5 operando DRIFTS光谱研究Mn1Ce1催化剂在CO氧化反应构-效关系

图6 operando反射吸收红外（RAIRS）用于Pt（111）单晶表面进行乙烯加氢体系的研究

图7 operando高温高压Raman反应装置

图8 不同气氛下催化剂活化过程中的operando Raman光谱及其催化性能[27]

图9 丙烯环氧化反应的operando UV-Raman反应池[31]

图10 两种以紫外共振Raman光谱为特征的钛物种[31]

图11 两种活性中心（TiO4和TiO6）的丙烯氧化催化反应过程[31]

图12 3%Cr2O3/Fe2O3在4个反应阶段的XRD谱图[34]

图13 α-Fe2O3和γ-Fe2O3在二氧化碳加氢反应中的构-效关系[28]

图14 operando M?ssbauer电化学反应池的顶视图及横截面侧视图[36]

图15 NiFe层状氢氧化物（蓝色）和含水铁氧化物（绿色）的循环伏安曲线和不同电势下operando M?ssbauer谱图[36]

图16 Fe-ZSM-5催化剂在operando XANES光谱及对应构-效关系[43]

图17 operando EXAFS装置示意图[6]

图18 1.3% PtO x /CeO2 NWs-350催化CO(2%/5%O2/75%He)氧化反应的operando EXAFS谱图[44]

图19 CO氧化原理图[44]

图20 operando反应器结构简图[46]

图21 由原位XPS和operando AP-XPS得到的未负载的Rh-Pd纳米催化剂和RhPd/CeO2表面相对原子百分比[48]

图22 CHx团簇诱导Cu70Ni70表面Ni析出的示意图[49]

图23 郑州大学韩一帆课题组NAP-XPS实物图

图24 XRD/Raman-GC联用装置示意图[52]

图25 常压、523K下，15%Co/TiO2在费托合成中的活性以及operando XRD和Raman谱图[52]

图26 10bar、523K下，15%Co/TiO2在费托合成中的活性以及operando XRD[52]

图27 XANES/DRIFTS-MS联合技术研究5%CuO/CeO2用于CO/O2循环反应[53]

图28 operando EPR/UV-vis/Raman-GC联用装置示意图[57]

图29 多孔材料Fe-ZSM-5中Fe在不同位置示意图[58]

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动态现场原位（operando）表征技术在多相催化反应中的应用与进展

Advances in operando techniques for the heterogeneous catalytic reactions

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