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不同方法制备的Cu-Mn-La-Zr催化剂上二氧化碳加氢制甲醇反应机理研究

王世强 杨金海 赵宁 肖福魁

王世强, 杨金海, 赵宁, 肖福魁. 不同方法制备的Cu-Mn-La-Zr催化剂上二氧化碳加氢制甲醇反应机理研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60079-3
引用本文: 王世强, 杨金海, 赵宁, 肖福魁. 不同方法制备的Cu-Mn-La-Zr催化剂上二氧化碳加氢制甲醇反应机理研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60079-3
WANG Shi-qiang, YANG Jin-hai, ZHAO Ning, XIAO Fu-kui. Mechanistic study on the reaction of CO2 hydrogenation to methanol over Cu-Mn-La-Zr catalysts prepared by different methods[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60079-3
Citation: WANG Shi-qiang, YANG Jin-hai, ZHAO Ning, XIAO Fu-kui. Mechanistic study on the reaction of CO2 hydrogenation to methanol over Cu-Mn-La-Zr catalysts prepared by different methods[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60079-3

不同方法制备的Cu-Mn-La-Zr催化剂上二氧化碳加氢制甲醇反应机理研究

doi: 10.1016/S1872-5813(22)60079-3
详细信息
    通讯作者:

    E-mail: zhaoning@sxicc.ac.cn

    xiaofk@sxicc.ac.cn

  • 中图分类号: O643.36;O623.411

Mechanistic study on the reaction of CO2 hydrogenation to methanol over Cu-Mn-La-Zr catalysts prepared by different methods

  • 摘要: 通过原位红外和H2-TPD表征,研究了由共沉淀法(CMLZ-CP)、溶胶凝胶法(CMLZ-S)、水热法(CMLZ-H)制备的Cu-Mn-La-Zr催化剂上二氧化碳加氢的反应历程。结果表明,表面羟基对二氧化碳加氢制甲醇反应有一定的促进作用,并且所有催化剂均遵循甲酸盐(HCOO*)和羧酸盐(COOH*)路径。CMLZ-CP和CMLZ-H催化剂更倾向于羧酸盐路径,而CMLZ-S催化剂更倾向于甲酸盐路径。CMLZ-CP催化剂有最强的活化H2的能力,从而表现出最高的CO2转化率和甲醇产率,而CMLZ-H催化剂有更高的中强碱性位点和氧缺陷占比,使得中间物种更倾向于加氢合成甲醇,从而表现出最高的甲醇选择性。
  • 图  1  共沉淀法制备的Cu-Mn-La-Zr催化剂CO2吸附(a)和吸附过程中羟基浓度随时间变化原位红外谱图(b)

    Figure  1  In-situ DRIFT spectra of CO2 adsorption (a) and consumption of hydroxyl groups during adsorption with time (b) of Cu-Mn-La-Zr catalysts prepared by co-precipitation method

    图  2  不同方法制备的CMLZ-CP(a)、CMLZ-S(b)、CMLZ-H(c)催化剂在混合气下反应中间物种浓度随时间变化的原位红外光谱

    Figure  2  In-situ DRIFT spectra of CMLZ-CP(a),CMLZ-S(b) and CMLZ-H(c) catalysts with wave numbers of 1000-2200 cm−1 under CO2 and H2 gas mixture with time

    图  3  不同方法制备的CMLZ-CP(a)、CMLZ-S(b)、CMLZ-H(c)催化剂在混合气下反应中间物种浓度随时间变化的原位红外光谱

    Figure  3  In-situ DRIFT spectra of CMLZ-CP(a),CMLZ-S(b) and CMLZ-H(c) catalysts with wave numbers of 2700-3000 cm−1 under CO2 and H2 gas mixture with time

    图  4  不同方法制备的CMLZ-CP、CMLZ-S、CMLZ-H催化剂在300 ℃还原后的H2-TPD曲线(a)和H2脱附量比较(b)

    Figure  4  Comparison of H2-TPD curves (a) and H2 desorption amount (b) of CMLZ-CP, CMLZ-S and CMLZ-H catalysts prepared by different methods after reduction at 300 ℃

    图  5  催化剂的反应机理图

    Figure  5  Reaction mechanism over the catalysts

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  • 收稿日期:  2022-11-08
  • 录用日期:  2022-12-14
  • 修回日期:  2022-12-14
  • 网络出版日期:  2022-12-26

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