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The Size and Doping Site Consideration in Methanol Synthesis on CuZr Nanoparticles

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Abstract

The conversion of CO2 to methanol (CH3OH) on Zr-doped Cu nanoparticle (NP) with icosahedral structure, is studied by density functional theory. The atom number of CuZr NPs is taken 13, 55 and 147, respectively and one Zr atom is doped at vertex (‘v’), edge (‘e’) or facet (‘f’) site on the CuZr NPs’ surfaces. The calculation results of the adsorption energies Eads of the concerned adsorbates, the activation energy Ea and the reaction energy (ΔE) at each reaction step, reflect the obvious influences of Zr doping site and the size of CuZr NPs on CO2 reduction activation. All the adsorption and reaction processes are found to perform around Zr atom, and except CO, the larger CuZr NP usually possesses the weaker adsorption for the adsorbates. On all the CuZr NPs, the rate determining step (RDS) occurs in the process of H3CO → CH3OH and the calculated Ea value at this step is found to be more closely related with Zr doping site. So, when Zr atom is doped at edge site on these CuZr NPs’ surfaces, the activation of CO2 is be well improved. Through comparing these CuZr NPs, Cu147Zre shows it’s better performance as the superior catalyst for CO2 reduction to CH3OH.

Graphical Abstract

The comparison of the energy barrier at the rate determining step (RDS) with a sequence in Ea values is Cu146Zre < Cu54Zre < Cu146Zrv < Cu54Zrv = Cu146Zrf < Cu12Zrv. The larger size of Cu nanoparticles or Zr doping at edge site on the surface of Cu nanoparticles will be in favor of enhancement in catalytic activation, and so Cu146Zre NP shows it’s superior catalytic properties in the reaction of CO2 conversion to CH3OH

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Authors and Affiliations

  1. College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan, 030024, China

    H. Li, X. S. Luan & Y. Y. Shen

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  1. H. Li
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  2. X. S. Luan
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Li, H., Luan, X.S. & Shen, Y.Y. The Size and Doping Site Consideration in Methanol Synthesis on CuZr Nanoparticles. Catal Lett 153, 1036–1045 (2023). https://doi.org/10.1007/s10562-022-04041-z

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