Citation: Dan LUO, Xingcheng LIU, Dong LI, Tong CHANG. Metal-support interaction effects on CO activation over Co_n/SiO₂ catalysts[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(11): 2337-2344. doi: 10.11862/CJIC.20250003 shu

Metal-support interaction effects on CO activation over Co_n/SiO₂ catalysts

Dan LUO ¹ ,
Xingcheng LIU ^{2, 3} ,
Dong LI ¹ ,
Tong CHANG ^1,,

1.
Shanxi Key Laboratory of Ecological Protection and Resources Utilization of Yuncheng Salt Lake, Department of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi 044000, China
2.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Tong CHANG, luodan@ycu.edu.cn
Received Date: 17 February 2025
Revised Date: 18 September 2025

Figures(8)

Employing the first-principles density functional theory (DFT), an in-depth investigation was conducted into the structure, electronic properties, and CO activity of hydroxylated SiO₂(001) surface-supported Co_n (where n is the number of cobalt atoms, n=1-6) materials [Co_n/SiO₂(001)]. Here, n=1 represents a single Co atom, while n=2-6 denotes Co_n clusters composed of n Co atoms. The findings revealed that the binding energy (E_{b-Co₅/SiO₂(001)}) of Co₅/SiO₂(001) was the highest at 1.88 eV, suggesting that the Co₅ cluster exhibits the greatest stability when interfaced with the SiO₂(001). A direct linear correlation (y=0.11x-0.23) was observed in the connection between E_{b-Co_n/SiO₂(001)} and the average Bader charge (Q_ave-Bader) of the Co_n/SiO₂(001). The greater Q_ave-Bader value transferred between the Co_n clusters and the SiO₂ support, the stronger the binding and the higher the structural stability. As the Co_n cluster size increased, the d band center gradually moved away from the Fermi level, with the d band center energy for the Co₅/SiO₂(001) being the lowest at -0.96 eV. The most favorable reaction pathway for CO activation on the Co₃/SiO₂(001) is CO*+H*→CHO*→CH*+O*, with an effective energy barrier of 2.39 eV, whereas for Co₅/SiO₂(001), the optimal path is CO*→C*+O*, with an effective energy barrier of 1.19 eV, and Co₅ cluster, the optimal path is CO*+H*→CHO*→CH*+O*, with an effective energy barrier of 2.72 eV. Notably, the introduction of Co₅ clusters onto the hydroxylated SiO₂ surface proves to be more conducive to the activation of CO. By employing differential charge analysis and crystal orbital hamilton population (COHP) calculations, it was discernible that in the Co₃/SiO₂(001)-CO, Co₅/SiO₂(001)-CO and Co₅-CO, the transfer of electrons from Co to C amounted to 0.20, 0.15, and 0.24, respectively, the integrated COHP (ICOHP) values for the Co—C bond were -1.46, -0.91, and -1.70 eV, respectively, which are indicated a more robust interaction between C and Co in Co₅-CO and Co₃/SiO₂(001)-CO compared to Co₅/SiO₂(001)-CO. Notably, the intense interaction between CO and Co in the latter hinders the activation of CO.
- Co_n cluster,
- SiO₂(001),
- CO activity,
- electronic property
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Metal-support interaction effects on CO activation over Con/SiO2 catalysts

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通讯作者: 陈斌, bchen63@163.com

Metal-support interaction effects on CO activation over Co_n/SiO₂ catalysts