Enhanced N2 fixation on V2C by transition metal doping: First-principles calculation

Abstract

Electrocatalytic nitrogen fixation provides an alternative approach to replace the Haber-Bosch process for ammonia synthesis. We systematically investigated transition metal atoms (Fe, Co, Mo, Ru) anchored on defected V 2 C for electrocatalytic nitrogen fixation based on first-principles calculation. The calculated results show that the overpotential of NRR on Mo doped V 2 C is only 0.49 eV along the mixed enzyme pathway, which is much lower than that of pristine V 2 C (0.61 eV). Such low overpotential is related to the cooperation of the diatom of Mo and V, which promotes the activation of nitrogen molecules. Besides, the adsorption of nitrogen on Mo doped V 2 C is significantly greater than that of H + . Therefore, HER can be effectively inhibited. The extremely low overpotential and good selectivity make Mo/V 2 C a potential catalyst for NRR. • Transition metal atoms (Fe, Co, Mo, Ru) are anchored on two dimensional V2C for nitrogen (N2) reduction. • Mo doped V2C has the best performance with an overpotential of only 0.49 eV. • The free energy of adsorption of N2 is much greater than that of hydrogen ions on Mo/V2C. • The cooperation of the diatom of Mo and V promotes the activation of nitrogen molecule.