Macroporous Carbon-Nitride-Supported Transition-Metal Single-Atom Catalysts for Photocatalytic Hydrogen Production from Ammonia Splitting

Abstract

Ammonia (NH3) splitting to hydrogen (H2) is a promising route for on-site production of green hydrogen energy; however, the application is limited due to high-cost noblemetal-based catalysts and high operating temperature of the endothermic nature. Herein, we develop a series of macroporous carbon nitride-supported single-atom transition metal (TMsMCN, TMs: Co, Mn, Fe, Ni, Cu) catalyst panels for solar light-driven photocatalytic gaseous NH3 splitting. Under ambient reaction conditions, the optimized Ni-MCN shows an H2 production rate of 35.6 μmol g−1 h−1 , much superior to that of MCN and other TMs-MCN. Such enhanced photoactivity is attributed to the presence of Ni−N4 sites, which improve the optical properties, accelerate charge carrier separation/ transfer, and boost NH3 splitting kinetics of the catalysts. Density functional theory calculations further reveal that the Ni−N4 sites can effectively modify the electronic structure of the carbon nitride. Compared with other metal sites, the Ni−N4 site possesses moderate NH3 binding strength and the lowest energy barrier to facilitate the formation of key intermediates *NH + *H. These findings provide valuable guidelines for the rational design of single-atom catalysts toward energy- and cost-effective photocatalytic NH3 splitting for H2 production.