Boosting Hydrogen Evolution Reaction Activity of Amorphous Molybdenum Sulfide Under High Currents Via Preferential Electron Filling Induced by Tungsten Doping

通过钨掺杂诱导的优先电子填充增强非晶态硫化钼在高电流下的析氢反应活性

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Abstract

The lack of highly efficient, durable, and cost-effective electrocatalysts for the hydrogen evolution reaction (HER) working at high current densities poses a significant challenge for the large-scale implementation of hydrogen production from renewable energy. Herein, amorphous molybdenum tungsten sulfide/nitrogen-doped reduced graphene oxide nanocomposites (a-MoWS(x) /N-RGO) are synthesized by plasma treatment for use as high-performance HER catalysts. By adjusting the plasma treatment duration and chemical composition, an optimal a-MoWS(x) /N-RGO catalyst is obtained, which exhibits a low overpotential of 348 mV at a current density of 1000 mA cm(-2) and almost no decay after 24 h of working at this current density, outperforming commercial platinum/carbon (Pt/C) and previously reported heteroatom-doped MoS(2) -based catalysts. Based on density functional theory (DFT) calculations, it is found that with a reasonable tungsten doping level, the catalytic active site (2S(2 -) ) shows excellent catalytic performance working at high current densities because extra electrons preferentially fill at 2S(2 -) . The introduction of tungsten tends to lower the electronic structure energy, resulting in a closer-to-zero positive ΔGH∗ . Excessive tungsten introduction, however, can lead to structural damage and a worse HER performance under high current densities. The work provides a route towards rationally designing high-performance catalysts for the HER at industrial-level currents using earth-abundant elements.

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