Dual CoxSy-Modified Tungsten Disulfide Double-Heterojunction Electrocatalyst for Efficient Hydrogen Evolution in All-pH Media

The rational design and preparation of a heterogeneous electrocatalyst for hydrogen evolution reaction (HER) has become a research hotspot, while applicable and pH-universal tungsten disulfide (WS2)-based hybrid composites are rarely reported. Herein, we propose a novel hybrid catalyst (WS2/Co9S8/Co4S3) comprising two heterojunctions of WS2/Co4S3 and WS2/Co9S8, which grow on the porous skeleton of Co, N-codoped carbon (Co/NC) flexibly applicable to all-pH electrolytes. The effect of double heterogeneous coupling on HER activity is explored as the highly flexible heterojunction is conducive to tune the activity of the catalyst, and the synergistic interaction of the double heterojunctions is maximized by adjusting the proportion of heterojunction components. Theoretical calculations show that both WS2/Co9S8 and WS2/Co4S3 heterojunctions have a Gibbs free energy of H reaction (|ΔGH*|) close to 0.0 eV and a facile decomposition water barrier. As collective synergy of dual CoxSy-modified WS2 double heterojunction, WS2/Co9S8/Co4S3 greatly enhances HER activity compared to bare Co9S8/Co4S3 or single heterojunction (WS2/Co9S8) in all-pH media. Besides, we have elucidated the unique HER mechanism of the double heterojunction to decompose H2O and confirm its excellent activity under alkaline and neutral conditions. Thus, this work provides new insights into WS2-based hybrid materials potentially applied to sustainable energy.