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Chin. Phys. B, 2022, Vol. 31(10): 107306    DOI: 10.1088/1674-1056/ac6158

Transition metal anchored on C9N4 as a single-atom catalyst for CO2 hydrogenation: A first-principles study

Jia-Liang Chen(陈嘉亮)1, Hui-Jia Hu(胡慧佳)2, and Shi-Hao Wei(韦世豪)1,†
1. Department of Microelectronic Science and Engineering, School of Physical Science and Technology, Ningbo University, Ningbo 315211, China;
2. Department of Electronic and Information Engineering, School of Electrical Engineering and Computer Science, Ningbo University, Ningbo 315211, China
Abstract  To alleviate the greenhouse effect and maintain the sustainable development, it is of great significance to find an efficient and low-cost catalyst to reduce carbon dioxide (CO2) and generate formic acid (FA). In this work, based on the first-principles calculation, the catalytic performance of a single transition metal (TM) (TM = Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au, or Hg) atom anchored on C9N4 monolayer (TM@C9N4) for the hydrogenation of CO2 to FA is calculated. The results show that single TM atom doping in C9N4 can form a stable TM@C9N4 structure, and Cu@C9N4 and Co@C9N4 show better catalytic performance in the process of CO2 hydrogenation to FA (the corresponding maximum energy barriers are 0.41 eV and 0.43 eV, respectively). The partial density of states (PDOS), projected crystal orbital Hamilton population (pCOHP), difference charge density analysis and Bader charge analysis demonstrate that the TM atom plays an important role in the reaction. The strong interaction between the 3d orbitals of the TM atom and the non-bonding orbitals (1πg) of CO2 allows the reaction to proceed under mild conditions. In general, our results show that Cu@C9N4 and Co@C9N4 are a promising single-atom catalyst and can be used as the non-precious metals electrocatalyst for CO2 hydrogenation to formic acid.
Keywords:  first-principles calculation      CO2 hydrogenation      catalysts      electronic structure      reaction mechanisms      reaction paths  
Received:  30 December 2021      Revised:  23 March 2022      Accepted manuscript online: 
PACS:  73.22.-f (Electronic structure of nanoscale materials and related systems)  
  82.20.Kh (Potential energy surfaces for chemical reactions)  
Fund: Project supported by the National Natural Science Foundation of China (Grant No. 51871126) and the K. C. Wong Magna Fund in Ningbo University. The computation was performed in the Supercomputer Center of NBU.
Corresponding Authors:  Shi-Hao Wei     E-mail:

Cite this article: 

Jia-Liang Chen(陈嘉亮), Hui-Jia Hu(胡慧佳), and Shi-Hao Wei(韦世豪) Transition metal anchored on C9N4 as a single-atom catalyst for CO2 hydrogenation: A first-principles study 2022 Chin. Phys. B 31 107306

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