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

doi:10.1088/1674-1056/ac6158

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 (1π_g) 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: weishihao@nbu.edu.cn

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

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