Nitriding Nickel-Based Cocatalyst: A Strategy To Maneuver Hydrogen Evolution Capacity for Enhanced Photocatalysis

Seeking earth-abundant cocatalysts for boosting the photocatalytic performance of the host semiconductor is of great significance. Here, enlightened by the structural optimization strategy concerning nitridation treatment on various advanced materials, the nickel nitride (Ni3N) nanocrystals were prepared. To understand the catalytic behavior and structure-performance correlation, the Ni3N was loaded on the surface of two-dimensional carbon nitride (2D-C3N4), forming a typical 0D-2D architecture. The well-assembled 0D-2D nanohybrids ultimately achieved the high efficiency catalysis of H-2 evolution rate reaching similar to 1347.8 mu mol/g/h (external quantum efficiency = 2.3% at 420 nm), ranking at the forefront among the 2D-C3N4 supported Ni-based cocatalysts and noble metals (e.g., Au, Ag, Pd). Combined with theoretical calculation and spectrum characterization, we propose that the enhanced hydrogen evolution performance can be ascribed to the improved charge transport ability and optimized H* adsorption/desorption capacity. Ultimately, the balance between the surface of Ni3N and protons is conducive to the boosted hydrogen evolution reaction performance. This work demonstrates the potential of transition-metal nitrides to establish highefficiency photocatalytic cell without using noble metals for water splitting.