Electrochemical CO₂ Reduction to C₁ Products on Single Nickel/Cobalt/Iron-Doped Graphitic Carbon Nitride: A DFT Study

Electrocatalytic CO₂ reduction reaction (CRR) is one of the most promising strategies to convert greenhouse gases to energy sources. Herein, the CRR was applied towards making C₁ products (CO, HCOOH, CH₃ OH, and CH₄ ) on g-C₃ N₄ frameworks with single Ni, Co, and Fe introduction; this process was investigated by density functional theory. The structures of the electrocatalysts, CO₂ adsorption configurations, and CO₂ reduction mechanisms were systematically studied. Results showed that the single Ni, Co, and Fe located from the corner of the g-C₃ N₄ cavity to the center. Analyses of the adsorption configurations and electronic structures suggested that CO₂ could be chemically adsorbed on Co-C₃ N₄ and Fe-C₃ N₄ , but physically adsorbed on Ni-C₃ N₄ . The H₂ evolution reaction (HER), as a suppression of CRR, was investigated, and results showed that Ni-C₃ N₄ , Co-C₃ N₄ , and Fe-C₃ N₄ exhibited more CRR selectivity than HER. CRR proceeded via COOH and OCHO as initial protonation intermediates on Ni-C₃ N₄ and Co/Fe-C₃ N₄ , respectively, which resulted in different C₁ products along quite different reaction pathways. Compared with Ni-C₃ N₄ and Fe-C₃ N₄ , Co-C₃ N₄ had more favorable CRR activity and selectivity for CH₃ OH production with unique rate-limiting steps and lower limiting potential.