Exploring advanced electrocatalysts for electrocatalytic hydrogen evolution is highly desired but remains a challenge due to the lack of an efficient preparation method and reasonable structural design. Herein, we deliberately designed novel Ag/WO heterostructures through a supercritical CO -assisted exfoliation-oxidation route and the subsequent loading of Ag nanoparticles. The ultrathin and oxygen vacancies-enriched WO nanosheets are ideal substrates for loading Ag nanoparticles, which can largely increase the active site density and improve electron transport. Besides, the resultant WO nanosheets with porous structure can form during the electrochemical cycling process induced by an electric field. As a result, the exquisite Ag/WO heterostructures show an enhanced hydrogen evolution reaction (HER) activity with a low onset overpotential of ≈30 mV, a small Tafel slope of ≈40 mV dec at 10 mA cm , and as well as long-term durability. This work sheds light on material design and preparation, and even opens up an avenue for the development of high-efficiency electrocatalysts.
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