固溶体催化CO2加氢制甲醇催化活性和反应机理研究

Study on catalytic activity and reaction mechanism of CO2 hydrogenation to methanol catalyzed by solid solution

  • 摘要: 固溶体催化剂应用于CO2加氢制甲醇研究具有较好的催化活性,得益于其固溶强化、晶格畸变和固溶体结构等性能的变化。固溶强化可以有效提高催化剂的热稳定性,能够在高温和高压的条件下保持稳定的催化性能。晶格畸变可以调整催化剂的电子结构和表面活性位点,增强界面结构间相互作用促进反应物分子的吸附和活化。固溶体结构可形成较多的氧空位和双金属位点协同效应,在高温活化CO2的过程中,使反应的关键中间体更加稳定,从而有效抑制CO的生成。CO2加氢制甲醇反应机理的争议主要集中在甲酸盐物种(HCOO*)和羧基物种(COOH*)2种中间体上。其中,固溶体催化剂更倾向于甲酸盐机理,认为甲酸盐(HCOO*)和甲氧基(CH3O*)是反应的关键中间体。镓锆、铟锆和锌锆是最为常见的3种固溶体催化剂,针对这3种催化剂CO2加氢制甲醇催化活性和反应机理进行总结。最后对固溶体催化剂在CO2加氢制甲醇领域存在的问题的进行了探讨和展望。

     

    Abstract: Solid solution catalyst has good catalytic activity in the study of CO2 hydrogenation to methanol, due to its changes of features like solid solution strengthening, lattice distortion and solid solution structure. Solid solution strengthening can effectively improve the thermal stability of the catalyst, so that it can maintain stable catalytic performance under high temperature and high pressure conditions. Lattice distortion can adjust the electronic structure and surface active site of the catalyst, enhance the interfacial structural interaction and promote the adsorption and activation of reactant molecules. The solid solution structure can create more oxygen vacancies and form bimetallic site synergistic effect, which makes the key intermediate of the reaction more stable in the process of activating CO2 at high temperature, so as to effectively inhibit the generation of CO. The controversy on the mechanism of CO2 hydrogenation to methanol mainly focuses on two intermediates: formate species (HCOO*) and carboxyl group species (COOH*). Among them, solid solution catalysts are more inclined to formate mechanism, which considers formate (HCOO*) and methoxy (CH3O*) as key intermediates in the reaction. Gallium zirconium, indium zirconium and zinc zirconium are the three most common solid solution catalysts. The catalytic activity and reaction mechanism of these three catalysts are summarized. Finally, the problems existing in the field of CO2 hydrogenation of solid solution catalyst to methanol are discussed and prospected.

     

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