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    (自由来稿)载体(M1Zr4O2-δ)组成对铜基催化剂催化活性的影响

    The influence of the support (M1Zr4O2-δ) on the catalytic activity of Cu-based catalysts

    • 摘要: 制备高效催化剂以提升CO2加氢制甲醇的活性,是实现CO2资源化利用的有效途径。本研究制备了四种不同的锆基双金属氧化物为载体的铜基催化剂,分别为Cu/Ti1Zr4O2、Cu/Zn1Zr4O2、Cu/Ga1Zr4O2和Cu/Ce1Zr4O2,并进行了CO2加氢合成甲醇实验。结果表明,以Ti1Zr4O2氧化物为载体的Cu/Ti1Zr4O2催化剂具有良好的催化活性。表征分析表明,H2还原后的Cu/Ti1Zr4O2催化剂表面具有大量的不饱和Cu物种(Cu0),与丰富的氧空位和表面碱性位点相结合,促进了CO2和H2的吸附和活化。较小的Cu粒径、较大的Cu比表面积和分散度共同促进了H2的活化。优异的物理化学性质使得Cu/Ti1Zr4O2催化剂表现出良好的催化活性。此外反应机理表明甲酸盐物种是Cu/Ti1Zr4O2催化剂催化CO2加氢合成甲醇的关键中间体。

       

      Abstract: Efficient catalyst preparation is crucial for enhancing the activity of CO2 hydrogenation to methanol, facilitating the utilization of CO2 resources. In this study, four copper-based catalysts supported by zirconium bimetallic oxides, namely Cu/Ti1Zr4O2, Cu/Zn1Zr4O2, Cu/Ga1Zr4O2, and Cu/Ce1Zr4O2, were synthesized and tested in CO2 hydrogenation experiments for methanol production. The results showed that the Cu/Ti1Zr4O2 catalysts with Ti1Zr4O2 oxides as carriers had good catalytic activity. Characterization analyses showed that the H2 reduced Cu/Ti1Zr4O2 catalysts had a large number of unsaturated Cu species (Cu0) on the surface, which combined with abundant oxygen vacancies and surface alkaline sites to promote the adsorption and activation of CO2 and H2. The smaller Cu particle size, larger Cu specific surface area and dispersion combined to promote H2 activation. The excellent physicochemical properties enabled the Cu/Ti1Zr4O2 catalyst to exhibit good catalytic activity. In addition the reaction mechanism suggests that formate species are key intermediates in the synthesis of methanol from CO2 hydrogenation catalyzed by Cu/Ti1Zr4O2 catalysts.

       

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