Noble metal electrocatalysts (e.g., Pt, Ru, etc.) suffer from sluggish kinetics of water dissociation for the electrochemical reduction of water to molecular hydrogen in alkaline and neutral pH environments. Herein, we found that an integration of Ru nanoparticles (NPs) on oxygen-deficient WO 3-x manifested a 24.0-fold increase in hydrogen evolution reaction (HER) activity compared with commercial Ru/C electrocatalyst in neutral electrolyte. Oxygen-deficient WO 3-x is shown to possess large capacity for storing protons, which could be transferred to the Ru NPs under cathodic potential. This significantly increases the hydrogen coverage on the surface of Ru NPs in HER and thus changes the rate-determining step of HER on Ru from water dissociation to hydrogen recombination.
The electrocatalytic nitrate reduction reaction (NO 3 - RR) offers a promising route to sustainable ammonia synthesis, potentially replacing the energy-intensive Haber-Bosch process. While often studied in neutral or alkaline media, NO 3 - RR in acidic conditions is particularly relevant due to widespread industrial acidic nitrate wastewater, yet it remains challenging due to corrosion and dominant hydrogen evolution. To address this, we designed a corrosion-resistant Ru/WO 3- x heterostructure that spatially separates proton and nitrate adsorption sites. Here, we show that a reverse hydrogen spillover effect, where the WO 3- x support stores and transports protons to surface Ru active sites, dramatically enhances hydrogenation kinetics and suppresses parasitic hydrogen evolution. This catalyst achieves an ammonia Faradaic efficiency of 94.09% at a high current density of 500 mA cm −2 and a working potential of 0.026 V vs. reversible hydrogen electrode. Furthermore, we demonstrate a sulfide-nitrate “batterolyzer” with a discharge power density of 43.4 mW cm −2 . This work reveals an effective proton-management strategy for efficient acidic NO 3 - RR, advancing its potential for coupled ammonia synthesis and wastewater treatment.
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