A Theoretical Study of Fe Adsorbed on Pure and Nonmetal (N, F, P, S, Cl)-Doped Ti(3)C(2)O(2) for Electrocatalytic Nitrogen Reduction

The possibility of using transition metal (TM)/MXene as a catalyst for the nitrogen reduction reaction (NRR) was studied by density functional theory, in which TM is an Fe atom, and MXene is pure Ti(3)C(2)O(2) or Ti(3)C(2)O(2−x) doped with N/F/P/S/Cl. The adsorption energy and Gibbs free energy were calculated to describe the limiting potentials of N(2) activation and reduction, respectively. N(2) activation was spontaneous, and the reduction potential-limiting step may be the hydrogenation of N(2) to *NNH and the desorption of *NH(3) to NH(3). The charge transfer of the adsorbed Fe atoms to N(2) molecules weakened the interaction of N≡N, which indicates that Fe/MXene is a potential catalytic material for the NRR. In particular, doping with nonmetals F and S reduced the limiting potential of the two potential-limiting steps in the reduction reaction, compared with the undoped pure structure. Thus, Fe/MXenes doped with these nonmetals are the best candidates among these structures.