文献类型：期刊文献

中文题名：负载型铟基催化剂二氧化碳加氢动力学研究

英文题名：Kinetics study on supported indium-based catalysts in carbon dioxide hydrogenation

作者：曹晨熙[1];陈天元[1];丁晓旭[1];黄海[1];徐晶[1];韩一帆[1]

机构：[1]化学工程联合国家重点实验室华东理工大学

年份：2019

卷号：70

期号：10

起止页码：3985

中文期刊名：化工学报

外文期刊名：CIESC Journal

收录：CSTPCD;;EI(收录号：20200107972550);Scopus;北大核心:【北大核心2017】；CSCD:【CSCD2019_2020】；

基金：国家重点研发计划项目(2018YFB0605803);国家自然科学基金项目(21808058);上海市青年科技英才扬帆计划项目(18YF1406100)

语种：中文

中文关键词：二氧化碳;催化剂;动力学;甲醇合成;原位红外;程序升温实验

外文关键词：carbon dioxide;catalysts;kinetics;methanol synthesis;in-situ DRIFTS;temperature-programed experiments

摘要：探讨了载体对铟基催化剂上CO2加氢动力学的影响。通过浸渍法制备了不同载体的负载型In基催化剂,仅ⅣB族元素(Ti,Zr,Hf)氧化物负载的In基催化剂表现出明显的CO2加氢活性,其中In1/HfO2和In1/ZrO2催化剂具有较高的甲醇选择性,而In1/TiO2催化剂主要起催化逆水气变换反应的作用。通过稳态动力学、高压原位漫反射红外和程序升温实验等动力学手段,证明反应条件下In1/ZrO2和In1/HfO2上的关键表面反应中间体是甲酸盐与甲氧基,甲醇主要通过表面甲酸盐的逐步加氢生成。In1/HfO2具有最强的氢解离与加氢能力,因此最有利于甲醇合成。In1/TiO2在CO2加氢中表面无明显含碳中间物种,高CO选择性可能与界面氧空缺位点促进redox循环以及甲酸盐中间体分解相关。
In this work,the effect of support materials on the kinetic behaviors of indium-based catalysts in carbon dioxide hydrogenation was studied.A series of supported indium-based catalysts were prepared and tested.Only group Ⅳ B metal (Ti,Zr and Hf) oxide supported indium-based catalysts had substantial catalytic activity. Particularly,In1/HfO2 and In1/ZrO2 catalysts showed high methanol selectivity,while In1/TiO2 mainly catalyzed the reverse water-gas shift reaction.Steady-state kinetics,in-situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed experiments indicate that the key surface reaction intermediate over In1/ HfO2 and In1/ZrO2 are formate and methoxy species,and methanol is produced via stepwise hydrogenation of the surface formate.In1/HfO2 possesses the strongest hydrogen splitting and hydrogenation ability,thus favoring methanol synthesis.Over In1/TiO2,no significant surface carbonaceous species was detected under reaction conditions.The improved CO production might be related to interfacial oxygen defects facilitating the redox cycle and decomposition of formate intermediate.