Computational study of nitrogen-doped vanadium disulfide-loaded single-atom catalysts for the electrocatalytic reduction of CO2.

The diagram vividly depicts the reduction of CO 2 to CH 4 on the active sites of TM@N 3 -VS 2. [Display omitted] • The novel SACs (TM@N 3 -VS 2) were designed based on the properties of VS 2 nanosheets with unique electronic structure, and the outstanding performance of nitrogen adjusting the coordination environment of transition metal for CO 2 RR. • The catalytic performance of TM@N 3 -VS 2 and TM@VS 2 for CO 2 RR was systematically compared and investigated. • TM@N 3 -VS 2 possess excellent performance for reduction of CO 2 to CH 4 , especially for Cr@N 3 -VS 2 with the lowest limiting potential of 0.2 eV. • The reason why N-doping leads to the excellent electrocatalytic CO 2 reduction activity was explained. The electrocatalytic reduction of CO 2 using single-atom catalysts (SACs) has significant potential to make a substantial impact on energy regeneration and greenhouse effect control in the future. The novel SACs were designed based on the properties of vanadium disulfide (VS 2) nanosheets with large surface area and unique electronic structure, and the outstanding catalytic performance of transition metal atoms bonding with nitrogen atoms for CO 2 reduction reaction (CO 2 RR). In this work, the electrocatalytic performance of N-doped vanadium disulfide nanosheets loading a series of transition metal single atoms for CO 2 RR was systemically evaluated by density functional theory (DFT). The results showed that TM@N 3 -VS 2 (TM = Ti, V, Cr, Mn, Zr, Nb, Mo, Ru, Rh) possess excellent performance for reduction of CO 2 to CH 4 , with low limiting potential of 0.36 eV, 0.28 eV, 0.2 eV, 0.34 eV, 0.54 eV, 0.33 eV, 0.55 eV, 0.38 eV, and 0.25 eV, respectively. The calculation results indicated that the nitrogen atoms could adjust the coordination environment of transition metal atoms and modulate the ability of transition metal atoms and VS 2 nanosheets accepting and donating electrons, which makes CO 2 adsorb on TM@N 3 -VS 2 with moderate adsorption energy, and significantly reduces the reaction energy barrier. [ABSTRACT FROM AUTHOR]