Metal−Organic Framework-Derived Sulfide−Selenide Heterostructure as an Efficient Electrocatalyst for Alkaline Hydrogen Evolution Reaction

Abstract

Heterostructure engineering has emerged as an effective strategy for developing efficient and durable non-precious-metal electrocatalysts for the hydrogen evolution reaction (HER) to enable sustainable hydrogen production. However, the development of MOF-derived heterostructures remains relatively underexplored, despite the unique opportunities offered by interfacial engineering to modulate electronic structures and accelerate catalytic kinetics. In this work, we designed a strategy to construct a heterostructured electrocatalyst comprising zeolitic imidazolate framework (ZIF)-derived Co3S4 coupled with Ni3Se4. The MOF-derived Co3S4 provides abundant catalytically active sites and structural stability, while Ni3Se4 enhances electrical conductivity and facilitates hydrogen adsorption/desorption kinetics. The intimate Co3S4/Ni3Se4 heterointerface generates strong electronic interactions that effectively modulate the electronic structure and accelerate interfacial charge transfer. As a result, the Co3S4/Ni3Se4 heterostructure exhibits superior HER activity in an alkaline electrolyte, requiring only an overpotential of 205 mV to reach a current density of 10 mA cm−2 and displaying a low Tafel slope of 63 mV dec−1. Moreover, the catalyst demonstrates excellent electrochemical durability during prolonged operation. The enhanced catalytic performance is attributed to the synergistic coupling between Co3S4 and Ni3Se4, which promotes water dissociation and optimizes hydrogen evolution kinetics. This study underscores the effectiveness of heterointerface engineering and MOF-derived architectures in the design of high-performance, earth-abundant electrocatalysts for sustainable hydrogen generation.