Au Nanoparticle Modification Induces Charge-Transfer Channels to Enhance the Electrocatalytic Hydrogen Evolution Reaction of InSe Nanosheets

Electrocatalytic water splitting for hydrogen production is an efficient, clean, and sustainable strategy to solve energy and environmental problems. As the important alternative materials for noble metals (Pt, Ir, etc.), two-dimensional (2D) materials have been widely applied for electrocatalysis, although the practical performance is restricted by low carrier mobility and slow reaction kinetics. Here, we adopt the strategy of Au nanoparticle modification to achieve the enhanced hydrogen evolution reaction (HER) performance of InSe nanosheets. Experimental results prove that the HER performance of InSe nanosheets is significantly enhanced under the modification of Au nanoparticles, and the overpotential (392 mV) and Tafel slope (59 mV/dec) are significantly reduced compared to sole InSe nanosheets (580 mV and 148.2 mV/dec). First-principles calculations have found that the InSe/Au system exhibits metallicity because the free electrons provided by the Au particles are injected into the InSe, thereby improving its conductivity. The difference charge density and localized charge density of InSe/Au show that Au nanoparticle loading can induce the formation of Au–Se electron-transfer channels with electrovalent bond characteristics, which effectively promotes the charge transfer. Meanwhile, the standard free-energy calculation of the HER process shows that the InSe/Au heterojunction has a H* adsorption/desorption Gibbs free energy [(|ΔGH*|) = 0.59 eV] closer to the optimal value. This study reveals the theoretical mechanism of metal modification to improve the performance of electrocatalytic HER and is expected to motivate the development of a new strategy for enhancing the catalytic activity of 2D semiconductor materials.