Optimizing Interfacial Charge Dynamics and Quantum Effects in Heterodimensional Superlattices for Efficient Hydrogen Production

Abstract

Superlattice materials have emerged as promising candidates for water electrocatalysis due to their tunable crystal structures, electronic properties, and potential for interface engineering. However, the catalytic activity of transition metal-based superlattice materials for the hydrogen evolution reaction (HER) is often constrained by their intrinsic electronic band structures, which can limit charge carrier mobility and active site availability. Herein, a highly efficient electrocatalyst based on a VS₂-VS heterodimensional (2D-1D) superlattice with sulfur vacancies is designed addressing the limitations posed by the intrinsic electronic structure. The enhanced catalytic performance of the VS₂-VS superlattice is primarily attributed to the engineered heterojunction, where the work function difference between the VS₂ layer and VS chain induces a charge separation field that promotes efficient electron-hole separation. Introducing sulfur vacancies further amplifies this effect by inducing quantum localization of the separated electrons, thereby significantly boosting HER activity. Both theoretical and experimental results demonstrate that the superlattice achieves a ΔG_H* of −0.06 eV and an impressively low overpotential of 46 mV at 10 mA·cm⁻² in acidic media, surpassing the performance of commercial Pt/C while maintaining exceptional stability over 15 000 cycles. This work underscores the pivotal role of advanced material engineering in designing catalysts for sustainable energy applications.