Computational design of ternary NiO/MPt interface active sites for H2O dissociation

The search for highly active and cost-effective catalysts of hydrogen evolution reaction is necessary to reduce energy losses in water-alkali electrolyser. Based on bifunctional effect, ternary NiO/MPt111 (M = Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu) interface sites were built to study the HER activity trend by DFT calculations. Transition metal atoms tuned the electronic properties of interface sites, regulated the H 2 O adsorption activation and lowered the H 2 O dissociation energy barrier. Especially, on NiO/NiPt111 and NiO/OsPt111 interface sites the energy barriers were largely reduced to be 0.33 and 0.35 eV compared to NiO/Pt111 (0.55 eV) and Pt111 (0.92 eV). Volcano shape relationship between OH∗ adsorption energy Δ E OH∗ and energy barriers indicated Δ E OH∗ could be used as a HER activity descriptor for oxide-metal interface active sites. The present work indicated a potential interface-engineering strategy for designing interface sites with multimetallic composition and the tuned electronic structures to achieve excellent HER activity. • Configuration and electronic properties of NiO/Pt interface sites was regulated by TM metals. • Energy barrier was greatly reduced to 0.33eV for NiO/NiPt interface active site. • Volcano shape relationship between Δ E OH∗ and Ea was established. • Δ E OH∗ can be used as a descriptor for ternary oxide-metal interface sites. • NiO/MPt catalyst could be produced by oxidative reaction in the air experimentally.