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负载型铟基催化剂二氧化碳加氢动力学研究

曹晨熙1 陈天元1 丁晓旭1 黄海1 徐晶1 韩一帆1

(1.化学工程联合国家重点实验室华东理工大学, 上海 200237)

【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。

【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;

【DOI】

【基金资助】 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);

Kinetics study on supported indium-based catalysts in carbon dioxide hydrogenation

CAO Chenxi1 CHEN Tianyuan1 DING Xiaoxu1 HUANG Hai1 XU Jing1 HAN Yifan1

(1.State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai, China 200237)

【Abstract】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 ⅣB metal (Ti, Zr and Hf) oxide supported indium-based catalysts have substantial catalytic activity. Particularly, In1/HfO2 and In1/ZrO2 catalysts show high methanol selectivity, while In1/TiO2 mainly catalyzes the reverse water-gas shift reaction. The steady-state kinetics, in-situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed experiments indicate that the key surface reaction intermediates 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 is detected under reaction conditions. The improved CO production might be related to the interfacial oxygen defects facilitating the redox cycle and decomposition of formate intermediate.

【Keywords】 carbon dioxide; catalysts; kinetics; methanol synthesis; in-situ DRIFTS; temperature-programmed experiments;

【DOI】

【Funds】 National Key R&D Program of China (2018YFB0605803); National Natural Science Foundation of China (21808058); "Yangfan" Project of Science and Technology of Shanghai (18YF1406100);

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This Article

ISSN:0438-1157

CN: 11-1946/TQ

Vol 70, No. 10, Pages 3985-3993+4100

October 2019

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Article Outline

Abstract

  • Introduction
  • 1 Experimental section
  • 2 Results and discussion
  • 3 Conclusions
  • References