负载型铟基催化剂二氧化碳加氢动力学研究

曹晨熙; 陈天元; 丁晓旭; 黄海; 徐晶; 韩一帆

doi:10.11949/j.issn.0438-1157.20190570

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负载型铟基催化剂二氧化碳加氢动力学研究

催化、动力学与反应器 | 更新时间：2026-07-24

- 负载型铟基催化剂二氧化碳加氢动力学研究
- Kinetics study on supported indium-based catalysts in carbon dioxide hydrogenation
- 化工学报 2019年70卷第10期页码：3985-3993
- 作者机构：
  
  化学工程联合国家重点实验室，华东理工大学，上海 200237
- 作者简介：
  
  曹晨熙（1989—），男，讲师，caocx@ecust.edu.cn
  徐晶（1974—），女，博士，教授，xujing@ecust.edu.cn
- 基金信息：
  
  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)
- DOI：10.11949/j.issn.0438-1157.20190570
  中图分类号： TQ 018
- 收稿：2019-05-27，
  
  修回：2019-06-26，
  
  网络首发：2026-07-24，
  
  纸质出版：2019-10-05
- 稿件说明：
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曹晨熙, 陈天元, 丁晓旭, 黄海, 徐晶, 韩一帆. 负载型铟基催化剂二氧化碳加氢动力学研究[J]. 化工学报, 2019, 70(10): 3985-3993

CAO Chenxi, CHEN Tianyuan, DING Xiaoxu, HUANG Hai, XU Jing, HAN Yifan. Kinetics study on supported indium-based catalysts in carbon dioxide hydrogenation[J]. CIESC Journal, 2019, 70(10): 3985-3993
曹晨熙, 陈天元, 丁晓旭, 黄海, 徐晶, 韩一帆. 负载型铟基催化剂二氧化碳加氢动力学研究[J]. 化工学报, 2019, 70(10): 3985-3993 DOI： 10.11949/j.issn.0438-1157.20190570.

CAO Chenxi, CHEN Tianyuan, DING Xiaoxu, HUANG Hai, XU Jing, HAN Yifan. Kinetics study on supported indium-based catalysts in carbon dioxide hydrogenation[J]. CIESC Journal, 2019, 70(10): 3985-3993 DOI： 10.11949/j.issn.0438-1157.20190570.

摘要

探讨了载体对铟基催化剂上CO

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

Hf）氧化物负载的In基催化剂表现出明显的CO

加氢活性，其中In

/HfO

和In

/ZrO

催化剂具有较高的甲醇选择性，而In

/TiO

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In

/ZrO

和In

/HfO

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。In

/HfO

具有最强的氢解离与加氢能力，因此最有利于甲醇合成。In

/TiO

在CO

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。

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 had substantial catalytic activity. Particularly

/HfO

and In

/ZrO

catalysts showed high methanol selectivity

while In

/TiO

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 In

/HfO

and In

/ZrO

are formate and methoxy species

and methanol is produced

via

stepwise hydrogenation of the surface formate. In

/HfO

possesses the strongest hydrogen splitting and hydrogenation ability

thus favoring methanol synthesis. Over In

/TiO

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.

关键词

Keywords

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