Nonmetallic Active Sites on Nickel Phosphide in Oxygen Evolution Reaction.

Efficient and durable catalysts are crucial for the oxygen evolution reaction (OER). The discovery of the high OER catalytic activity in NiP has attracted a great deal of attention recently. Herein, the microscopic mechanism of OER on the surface of NiP is studied using density functional theory calculations (DFT) and ab initio molecular dynamics simulation (AIMD). Our results demonstrate that the HO molecule is preferentially adsorbed on the P atom instead of on the Ni atom, indicating that the nonmetallic P atom is the active site of the OER reaction. AIMD simulations show that the dissociation of H from the HO molecule takes place in steps; the hydrogen bond changes from O-H⋯O to O⋯H-O, then the hydrogen bond breaks and an H is dissociated. In the OER reaction on nickel phosphides, the rate-determining step is the formation of the OOH group and the overpotential of NiP is the lowest, thus showing enhanced catalytic activity over other nickel phosphides. Moreover, we found that the charge of Ni and P sites has a linear relationship with the adsorption energy of OH and O, which can be utilized to optimize the OER catalyst.