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An investigation of the CH3OH and CO selectivity of CO2 hydrogenation over Cu−Ce−Zr catalysts

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Abstract

A series of Cu−Ce−Zr catalysts with different Ce contents are applied to the hydrogenation of CO2 to CO/CH3OH products. The Cu−Ce−Zr catalyst with 2 wt% Ce loading shows higher CO selectivity (SCO = 0.0%–87.8%) from 200–300 °C, while the Cu−Ce−Zr catalyst with 8 wt% Ce loading presents higher CO2 conversion \(({X_{{\rm{C}}{{\rm{O}}_2}}} = 5.4\% - 15.6\% )\) and CH3OH selectivity \(({S_{{\rm{C}}{{\rm{H}}_3}{\rm{OH}}}} = 97.8\% - 40.6\% )\). The number of hydroxyl groups and solid solution nature play a significant role in changing the reaction pathway. The solid solution enhances the CO2 adsorption ability. At the CO2 adsorption step, a larger number of hydroxyl groups over the Cu−Ce−Zr catalyst with 8 wt% Ce loading leads to the production of H-containing adsorption species. At the CO2 hydrogenation step, a larger number of hydroxyl groups assists in encouraging the further hydrogenation of intermediate species to CH3OH and improving the hydrogenation rate. Hence, the Cu−Ce−Zr catalyst with 8 wt% Ce loading favors CH3OH selectivity and CO2 activation, while CO is preferred on the Cu−Ce−Zr catalyst with 2 wt% Ce loading, a smaller number of hydroxyl groups and a solid solution nature. Additionally, high-pressure in situ diffuse reflectance infrared Fourier transform spectroscopy shows that CO is produced from formate decomposition and that both monodentate formate and bidentate formate are active intermediate species of CO2 hydrogenation to CH3OH.

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Acknowledgements

This work was financially supported by National Natural Science Foundation of China (Grant No. 22122807), Education and Scientific Research Project of Young and Middle-aged Teachers in Fujian Province (Science and Technology, JAT200979), National and Provincial College Students’ Innovation and Entrepreneurship Training Plan (Grant No. 202112992003), Doctoral Initiation Fund for Liaoning (Grant No. 2019-BS-054), Liao Ning Revitalization Talents Program (Grant No. XLYC1807245) and Natural Science Foundation of Shanghai (Grant No. 21ZR1425700).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Life Science and Chemistry, MinNan Science and Technology University, Quanzhou, 362332, China

    Weiwei Wang & Min Guo

  2. Sinochem Quanzhou Petrochemical Co., Ltd., Quanzhou, 362100, China

    Xiaoyu Zhang

  3. School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Jianan Li

  4. Department of Instrument Science and Engineering, School of Electronic Information and Electrical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China

    Chong Peng

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  1. Weiwei Wang
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  2. Xiaoyu Zhang
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  3. Min Guo
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  4. Jianan Li
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  5. Chong Peng
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Correspondence to Weiwei Wang or Chong Peng.

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Wang, W., Zhang, X., Guo, M. et al. An investigation of the CH3OH and CO selectivity of CO2 hydrogenation over Cu−Ce−Zr catalysts. Front. Chem. Sci. Eng. 16, 950–962 (2022). https://doi.org/10.1007/s11705-022-2162-2

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  • DOI: https://doi.org/10.1007/s11705-022-2162-2

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