Electrochemical amorphous-to-1T-phase reconfiguration of Ru–W bimetallic sulfide for sustainable hydrogen evolution

Abstract

Electrochemical reconfiguration of amorphous metallic materials offers exceptional opportunities for catalyst design. Here, we demonstrate a distinctive reconfiguration route toward highly active crystalline 1T-phase in amorphous Ru–W bimetallic sulfide. A micellar film-mediated strategy is developed to facilely fabricate large-area mesoporous films of the amorphous composite, involving sequential accumulation and association of Ru³⁺ and WS₄²⁻ precursors through hierarchical “pyridyl–Ru³⁺–WS₄²⁻” coordination, followed by crystallization-retarding pyrolysis. The resulting catalyst reveals appealing hydrogen evolution performance, with a low initial overpotential of 11 mV at 10 mA cm⁻² and high sustainability at 1.0 A cm⁻² over 1600 h. Notably, sustained electrochemical stimuli trigger a distinctive amorphous-to-crystalline reconfiguration, gradually generating crystalline Ru–W bimetallic sulfide with a metastable 1T-phase. This substantially endows the catalyst with a remarkable long-term stability while further enhancing the catalytic activity (overpotential of only 4 mV at 10 mA cm⁻²). Theoretical calculations reveal an electrochemical-dependent structural reorganization process, where external electron injection triggers charge redistribution that drives the atomic rearrangement, while the sulfur-bridged structure promotes efficient cooperative charge transfer and ensures the structural robustness of the metastable 1T-phase during the reconfiguration.