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Rh/CeO2催化剂中Rh负载量对CO2加氢生成甲醇及乙醇产物选择性的影响的研究

郑珂 刘冰 胥月兵 刘小浩

郑珂, 刘冰, 胥月兵, 刘小浩. Rh/CeO2催化剂中Rh负载量对CO2加氢生成甲醇及乙醇产物选择性的影响的研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60450-0
引用本文: 郑珂, 刘冰, 胥月兵, 刘小浩. Rh/CeO2催化剂中Rh负载量对CO2加氢生成甲醇及乙醇产物选择性的影响的研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60450-0
ZHENG Ke, LIU Bing, XU Yuebing, LIU Xiaohao. Study on the effects of Rh loading on the selectivity to methanol and ethanol in CO2 hydrogenation reaction over Rh/CeO2 catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60450-0
Citation: ZHENG Ke, LIU Bing, XU Yuebing, LIU Xiaohao. Study on the effects of Rh loading on the selectivity to methanol and ethanol in CO2 hydrogenation reaction over Rh/CeO2 catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60450-0

Rh/CeO2催化剂中Rh负载量对CO2加氢生成甲醇及乙醇产物选择性的影响的研究

doi: 10.1016/S1872-5813(24)60450-0
基金项目: 国家重点研发计划(2023YFB4103201)和国家自然科学基金 (22379053)资助
详细信息
    通讯作者:

    Tel: 13506186720, Fax: (+086)510-8591-7763, E-mail: liuxh@jiangnan.edu.cn

  • 中图分类号: O643.38

Study on the effects of Rh loading on the selectivity to methanol and ethanol in CO2 hydrogenation reaction over Rh/CeO2 catalyst

Funds: The project was supported by the National Key Research and Development program of China (2023YFB4103201) and the National Natural Science Foundation of China (22379053).
  • 摘要: 将二氧化碳(CO2)捕获并通过加氢转化为醇类等高价值的化学品是减少CO2排放并实现循环经济的重要途径之一。本工作研究了Rh负载量为0.1%−2.0%的Rh/CeO2催化剂在CO2加氢反应中的催化性能,并结合XRD、Raman、H2-TPR、CO2-TPD、CO-DRIFTS和XPS等表征方法,揭示了Rh负载量对催化剂CO2加氢活性和产物选择性的影响。结果表明,当反应压力为3.0 MPa、反应温度为250 ℃时,0.1% Rh/CeO2催化剂上CO2加氢的产物以乙醇为主;随着Rh含量的增加,CO2转化率增加,乙醇选择性降低,当Rh负载量为2.0%时,产物以甲醇为主。不同Rh负载量催化剂产物选择性的差异与催化剂中Rh的存在形式和电子性质有关。原子分散的Rh+有利于稳定CO*与CH3*进行C−C偶联形成乙醇,而金属态的Rh团簇则有利于CO*加氢形成甲醇。
  • 图  1  不同催化剂的XRD谱图

    Figure  1  XRD patterns of different catalysts

    图  2  不同催化剂的Raman谱图

    Figure  2  Raman spectra of different catalysts

    图  3  不同催化剂的H2-TPR谱图

    Figure  3  H2-TPR profiles of different catalysts

    图  4  不同催化剂的CO2-TPD谱图

    Figure  4  CO2-TPD profiles of different catalysts

    图  5  不同催化剂的原位CO吸附漫反射红外光谱谱图

    Figure  5  In situ CO-DRIFT spectra of various catalysts

    图  6  不同还原后催化剂的Ce 3d(a)、O 1s(b)和Rh 3d(c) XPS谱图

    Figure  6  Ce 3d (a), O 1s (b) and Rh 3d (c) XPS spectrum of of different reduced catalysts

    图  7  不同催化剂上CO2加氢反应催化性能(a)和甲醇与乙醇产率变化(b)

    Figure  7  CO2 hydrogenation reaction performance (a) and methanol and ethanol yield plots (b) over different catalysts

    图  8  0.1% Rh/CeO2催化剂上乙醇(a)和2.0% Rh/CeO2催化剂上甲醇(b)的时空产率与文献报道的催化剂的比较

    Figure  8  Comparison of the space-time yield of ethanol over 0.1% Rh/CeO2 (a) and methanol over 2.0% Rh/CeO2 (b) obtained in this work with other catalysts reported by literatures

    图  9  不同模型上CO加氢(a)和C−C偶联能力(b)对比

    Figure  9  Comparison of CO hydrogenation (a) and C−C coupling ability (b) on different models

    图  10  0.1% Rh/CeO2(a)和2.0% Rh/CeO2(b)催化剂的循环性能

    Figure  10  Recycled testing of 0.1% Rh/CeO2 (a) and 2.0% Rh/CeO2 (b) catalysts for reaction of 5 hours at five runs

    表  1  催化剂中的Rh含量

    Table  1  Rh contents in the catalysts

    Entry Catalyst Rh content w%
    1 0.1% Rh/CeO2 0.14
    2 0.5% Rh/CeO2 0.55
    3 2.0% Rh/CeO2 1.92
    下载: 导出CSV

    表  2  由XPS计算出催化剂表面组分的含量

    Table  2  Component on the surface of the studied samples calculated from XPS results

    Catalyst Ce3+/(Ce3++Ce4+) (%) Oads/(Oads+Olat) (%)
    0.1% Rh/CeO2 17.3 28.6
    0.5% Rh/CeO2 21.4 30.2
    2.0% Rh/CeO2 23.6 31.7
    下载: 导出CSV
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出版历程
  • 收稿日期:  2024-03-01
  • 修回日期:  2024-03-22
  • 录用日期:  2024-03-25
  • 网络出版日期:  2024-04-29

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