A systematic investigation of the catalytic performances of monolayer carbon nitride nanosheets C1−xNx

Graphitic carbon nitrides (CNs) are potential candidate materials for the electro-catalytic industry due to their unique physical and chemical properties. However, to date, a full understanding of the electro-catalytic properties of CNs is still lacking. Herein, by using density functional theory calculations, we systematically investigate the catalytic performances in the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), N2 reduction reaction (NRR), and CO2 reduction reaction (CO2RR) of monolayer graphitic carbon nitrides (C1−xNx), C3N (x = 1/4), C2N (x = 1/3), and g-C3N4 (x = 4/7). We also evaluated the NRR activity of B doped C1−xNx, and the CO2RR activity of Cu and Pd modified C1−xNx. The cohesive energy and ab initio molecular dynamics (AIMD) results show that C3N, C2N, and g-C3N4 are stable at room temperature. The C3N–C1 site is predicted to deliver the best HER catalytic performance with a reaction Gibbs free energy (ΔGH*) of −0.03 eV (close to the ideal value (0 eV)). Among the studied C1–xNx materials, the C3N–C2 site is predicted to possess a favorable ηOER of 0.82 V for OER. Pure C3N, C2N, and g-C3N4 are not suitable for NRR and CO2RR. Due to the strong hybridization between the N 2p orbital and the B 2p orbital, the NRR performances of B doped BN–C2N, BN–C3N, and BN–g-C3N4 are greatly enhanced, with corresponding overpotential ηNRR of 0.57 V, 0.70 V, and 0.72 V, respectively. The transition metals Cu and Pd can enhance the CO2RR activity of C3N, C2N, and g-C3N4. The limiting potentials UL of pure C3N, C2N, and g-C3N4 are 0.96 V, 0.86 V, and 2.37 V, respectively, while these values are 0.63 V, 0.68 V, and 0.77 V with Cu or Pd modification. This work provides deep understanding of the catalytic properties of monolayer C1−xNx and guidance for synthesizing higher activity catalysts in the future.