Abstract

Positively charged Pt can work as the active center for hydrogen evolution reaction (HER) but the corresponding design of state‐of‐the‐art electrocatalysts at high current densities has never been realized. Here the application of positively charged Pt in an effective Fe‐PtNiPO nanoreactor for highly efficient and stable HER is demonstrated. Synchrotron radiation X‐ray absorption spectroscopy confirms the formation of internal positively charged Pt and the in situ experiments reveal the quick charge transfer in the nanoreactor. Ni‐based materials around Pt are used to tune the electronic structure and promote the water dissociation to form locally enriched H+, while a porous Fe shell can both prevent the loss of active material and allow the efficient material transport. All the beneficial compositions work together to form an effective nanoreactor for HER. As a result, the Fe‐PtNiPO nanoreactor shows a low overpotential of 19 mV to achieve 10 mA cm−2 and exhibits a high mass activity of 10.93 A mgPt −1 (at 100 mV). Most importantly, it only needs an ultra‐low overpotential of 193 mV to achieve a high current density of 1000 mA cm−2 with an excellent stability over 300 h, which represents one of the best electrocatalysts for alkaline HER and might be used for large‐scale industrial application in the future.

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