Cu基CO2合成甲醇催化剂载体的研究进展

doi:10.16085/j.issn.1000-6613.2019-1546

摘要/Abstract

摘要：

氧化物载体与Cu之间的相互作用、CO₂的活化位点、表面反应机理、表面反应路径直接影响CO₂催化加氢的产物分布。因此，探明不同金属–载体的相互作用和界面微观结构至关重要。本文综述了CO₂催化加氢合成甲醇Cu基催化剂载体的研究现状，重点综述了ZnO、ZrO₂、CeO₂、TiO₂这4种具有氧空位的载体，并简单总结了SiO₂、Al₂O₃、Zn-Zr、Ce-Zr、钙钛矿等其他氧化物载体。Cu与ZnO之间的强金属相互作用（SMSI）所形成的Cu/ZnO_x是主要的活性位点，对其微观结构与反应机理研究得较为充分；对Cu/ZrO₂的研究主要集中在ZrO₂晶相的影响，不同的研究者所获得的结论尚存在争议；对Cu/CeO₂的机理研究停留在反向CeO₂/Cu(111)模型表面，负载型催化剂上不同晶面的CeO₂与Cu的相互作用强度不同，并影响反应性能；Cu/TiO₂中TiO₂的影响因素较多，如晶型、晶面等，目前对其研究尚不全面。最后，本文分析并展望了CO₂加氢制甲醇催化剂载体的研究方向，未来将采用与实际催化剂一致的正向模型表面进行基础研究，并基于原位表征手段对反应过程中催化剂的结构变化进行探索，最终设计高效、低成本的多元复合物载体的Cu基催化剂。

关键词: 二氧化碳, 催化, 加氢, 甲醇, 金属-载体相互作用, Cu基催化剂

Abstract:

In the hydrogenation of CO₂, the product distribution is mainly affected by the interaction between oxide supports and Cu, the active sites for CO₂ activation, surface reaction mechanism, and surface reaction pathway, where the microstructure of the metal-support interface is important. This paper summarized the progress in the Cu-based catalyst supports for methanol synthesis from CO₂, and the emphasis was placed on ZnO, ZrO₂, CeO₂, and TiO₂ which possess oxide vacancies during the reaction. Then the supports effects of SiO₂, Al₂O₃, Zn-Zr, Ce-Zr, and perovskite were briefly introduced. The Cu/ZnO_x interface formed by strong metal-support interaction(SMSI) is the main active site for CO₂ hydrogenation, and its microstructure and reaction mechanism have been extensively investigated. The researches on Cu/ZrO₂ have been focused on the crystalline phase of ZrO₂, but there remains debate in the conclusions. The reaction mechanism study of Cu/CeO₂ is still limited to the reverse CeO₂/Cu(111) model and the morphology of CeO₂ affects the interaction between Cu and the supports, and hence affects the product distribution. There are a variety of factors such as crystalline phase and facet that affect the catalytic properties of Cu/TiO₂ but the current research is not complete. Finally, this paper outlined the research should be conducted in future, i.e. The obverse model surface which are consistent with the real catalyst surface is used for fundamental research and the structural changes of the catalysts during reaction are explored via in-situ characterization so that the efficient and low-cost Cu based catalyst supported on multicomponent oxide can be ultimately designed.

Key words: carbon dioxide, catalysis, hydrogenation, methanol, metal-support interaction, Cu-based catalyst

中图分类号:

TQ426.65

侯瑞君, 邱瑞, 孙克宁. Cu基CO₂合成甲醇催化剂载体的研究进展[J]. 化工进展, 2020, 39(7): 2639-2647.

Ruijun HOU, Rui QIU, Kening SUN. Progress in the Cu-based catalyst supports for methanol synthesis from CO₂[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2639-2647.

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Cu基CO₂合成甲醇催化剂载体的研究进展

Progress in the Cu-based catalyst supports for methanol synthesis from CO₂

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