官能团修饰的UiO-66负载Rh催化剂合成及其催化CO2加氢制乙醇性能

石油炼制与化工 ›› 2024, Vol. 55 ›› Issue (9): 13-23.

官能团修饰的UiO-66负载Rh催化剂合成及其催化CO2加氢制乙醇性能

郑珂,胥月兵,刘冰,刘小浩

江南大学化学与材料工程学院

收稿日期:2024-03-04 修回日期:2024-05-29 出版日期:2024-09-12 发布日期:2024-08-28
通讯作者: 郑珂 E-mail:zkashin@163.com
基金资助:
国家重点研发计划;国家自然科学基金

SYNTHESIS OF FUNCTIONAL GROUP MODIFIED UiO-66 SUPPORTED Rh CATALYST AND ITS CATALYTIC PERFORMANCE FOR CO2 HYDROGENATION TO ETHANOL

Received:2024-03-04 Revised:2024-05-29 Online:2024-09-12 Published:2024-08-28
Contact: Ke Zheng E-mail:zkashin@163.com
Supported by:
National Key Research and Development Program of China;National Nat- ural Science Foundation of China

摘要/Abstract

摘要： 二氧化碳（CO₂）通过加氢转化为乙醇等高附加值的化学品是实现“双碳”目标的重要途径之一。制备不同官能团（—OH和—NH₂）修饰的UiO-66负载Rh催化剂Rh/UiO-66，在间歇高压反应釜中评价所制备催化剂对CO₂加氢制乙醇反应的催化性能，并结合X射线衍射、扫描电子显微镜、透射电子显微镜等表征方法，探究官能团改性对Rh基催化剂上CO₂加氢反应性能的影响。结果表明：与Rh/UiO-66催化剂相比，经官能团修饰后催化剂的催化性能明显增强，尤其是经—NH₂修饰的催化剂（Rh/UiO-66-NH₂）表现出了优异的催化活性、乙醇选择性和循环稳定性；—NH₂修饰后，催化剂中Rh⁺含量明显增加，有利于稳定CO*，并促进其与CH_x*发生C-C偶联和加氢反应生成乙醇；在压力为3.0 MPa、温度为250 ℃的条件下，Rh/UiO-66-NH₂催化CO₂加氢反应的CO₂转化率为5.6%，乙醇选择性高达84.7%，且5次循环反应后催化剂性能基本不变。

关键词: CO₂加氢, 乙醇, Rh催化剂, 官能团, 电子性质

Abstract: The hydrogenation of carbon dioxide (CO₂) to ethanol and other value-added chemicals is one of the important routes to achieve "dual-carbon" goals economy. Rh-based catalysts supported on UiO-66 modified with different functional groups (—OH and —NH₂) were prepared, their catalytic performance for CO₂ hydrogenation was tested in a batch reactor, and the effect of functional group modification on the performance of Rh-based catalysts for CO₂ hydrogenation was investigated by XRD, SEM, TEM, FT-IR, ICP, BET, TG, CO pulse, XPS and CO₂-TPD. The results showed that the catalytic performance of the catalyst modified with functional groups was significantly enhanced compared with that of Rh/UiO-66 catalyst. In particular, the Rh/UiO-66-NH₂ catalyst modified with —NH₂ exhibited excellent catalytic activity, ethanol selectivity and catalytic stability; while the Rh⁺ content in catalyst increased obviously after —NH₂ modification, which was beneficial to the stabilization of CO*, C-C coupling and hydrogenation with CH_x* were promoted to produce ethanol. At the pressure of 3.0 MPa and the temperature of 250 ℃, Rh/UiO-66-NH₂ exhibited the highest catalytic activity (5.6%) and ethanol selectivity (84.7%) with basically unchanged catalytic performance after five cycles.

Key words: CO₂ hydrogenation, ethanol, Rh catalyst, functional group, electronic property

郑珂胥月兵刘冰刘小浩. 官能团修饰的UiO-66负载Rh催化剂合成及其催化CO2加氢制乙醇性能[J]. 石油炼制与化工, 2024, 55(9): 13-23.

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