Local structural evolutions of CuO/ZnO/Al2O3 catalyst for methanol synthesis under operando conditions studied by in situ quick X-ray absorption spectroscopy  

作　　者：Xue-Ping Sun Fan-Fei Sun Song-Qi Gu Jing Chen Xian-Long Du Jian-Qiang Wang Yu-Ying Huang Zheng Jiang 

机构地区：[1]Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Zhangjiang Campus, Shanghai 201204, China [2]University of Chinese Academy of Sciences, Beijing 100049,China

出　　处：《Nuclear Science and Techniques》2017年第2期35-43,共9页核技术（英文）

基　　金：supported by the National Basic Research Program of China(973 Program,2013CB933104);the National Natural Science Foundation of China(Nos.11275258 and 11135008)

摘　　要：In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for methanol synthesis. In this work, the catalyst, whose activity increases with the reaction temperature and pressure, was studied at calcined, reduced, and reacted conditions. TEM and EDX images for the calcined and reduced catalysts showed that copper was distributed uniformly at both conditions. TPR profile revealed two reduction peaks at 165 and 195 °C for copper species in the calcined catalyst. QXAFS results demonstrated that the calcined form consisted mainly of a mixed Cu O and Zn O, and it was progressively transformed into Cu metal particles and dispersed Zn O species as the reduction treatment. It was demonstrated that activation of the catalyst precursor occurred via a Cu^+intermediate, and the active catalyst predominantly consisted of metallic Cu and Zn O evenunder higher pressures. Structure of the active catalyst did not change with the temperature or pressure, indicating that the role of the Zn was mainly to improve Cu dispersion.This indicates the potential of QXAFS method in studying the structure evolutions of catalysts in methanol synthesis.In situ quick X-ray absorption spectroscopy (QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al₂O₃ catalyst for methanol synthesis. In this work, the catalyst, whose activity increases with the reaction temperature and pressure, was studied at calcined, reduced, and reacted conditions. TEM and EDX images for the calcined and reduced catalysts showed that copper was distributed uniformly at both conditions. TPR profile revealed two reduction peaks at 165 and 195 °C for copper species in the calcined catalyst. QXAFS results demonstrated that the calcined form consisted mainly of a mixed CuO and ZnO, and it was progressively transformed into Cu metal particles and dispersed ZnO species as the reduction treatment. It was demonstrated that activation of the catalyst precursor occurred via a Cu⁺ intermediate, and the active catalyst predominantly consisted of metallic Cu and ZnO even under higher pressures. Structure of the active catalyst did not change with the temperature or pressure, indicating that the role of the Zn was mainly to improve Cu dispersion. This indicates the potential of QXAFS method in studying the structure evolutions of catalysts in methanol synthesis.

关 键 词：In SITU Quick X-ray ABSORPTION spectroscopy CuO/ZnO/Al2O3 CATALYST OPERANDO condition 

分 类 号：O643.36[理学—物理化学] TQ223.121[理学—化学]