Density functional theory evaluation of Fe, Co, Ni, Ir, and Pt as dopants in (CuO)3/SnO2 catalysts for selective methane-to-methanol
Xianya Zheng , Dong Tian , Yuxin Wang , Zeshan Wang , Kongzhai Li , Hua Wang
The selective oxidation of CH4 to CH3OH is an attractive approach for CH4 valorization. To systematically investigate this reaction, the pristine (CuO)3/SnO2(110) catalyst was modeled using density functional theory calculations. Building on this baseline, models featuring 3% substitutional doping with Fe, Co, Ni, Ir, and Pt were investigated to determine how doping affects catalytic performance. Across all six catalyst models, the most thermodynamically favorable pathway involved CH4 adsorption and activation to generate *CH3, followed by OH-assisted CH3OH formation and subsequent desorption. Catalytic activity follows the descending order of Fe-doped > Co-doped > Ni-doped > pristine > Pt-doped > Ir-doped, corresponding to maximum uphill Gibbs free energy changes of 0.60, 0.68, 0.70, 0.74, 0.84, and 1.24 eV, respectively. The Fe-, Co-, and Ni-doped catalysts exhibit superior performance because strong M−O ionic interactions between the dopant and O atoms enhance d-p orbital hybridization, activate lattice oxygen, facilitate reactant activation, and improve the surface redox properties of the catalysts. These findings provide valuable mechanistic insights for the rational design of metal-doped, supported oxide catalysts for efficient CH4-to-CH3OH conversion.
density functional theory / metal-doped catalysts / methane to methanol / activation of CH4 / (CuO)3/SnO2
Higher Education Press 2027
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