The introduction of an abiological catalytic group into the binding pocket of a protein host allows for the expansion of enzyme chemistries. Here, we report the generation of an artificial enzyme by genetic encoding of a non-canonical amino acid t...
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Enhancing Ni/Co Activity by Neighboring Pt Atoms in NiCoP/MXene Electrocatalyst for Alkaline Hydrogen Evolution
Von Wiley-VCH zur Verfügung gestellt
Hydrogen evolution reaction (HER) activity of Ni/Co can be improved by neighboring Pt atoms in alkaline electrolyte, which can increase water adsorption and decrease dramatically water dissociation energy barrier by interface electron transfer, and even change catalytic route from Heyrovsky to faster Tafel step.
Abstract
Density functional theory (DFT) calculations demonstrate neighboring Pt atoms can enhance the metal activity of NiCoP for hydrogen evolution reaction (HER). However, it remains a great challenge to link Pt and NiCoP. Herein, we introduced curvature of bowl-like structure to construct Pt/NiCoP interface by adding a minimal 1 ‰-molar-ratio Pt. The as-prepared sample only requires an overpotential of 26.5 and 181.6 mV to accordingly achieve the current density of 10 and 500 mA cm−2 in 1 M KOH. The water dissociation energy barrier (E a) has a ~43 % decrease compared with NiCoP counterpart. It also shows an ultrahigh stability with a small degradation rate of 10.6 μV h−1 at harsh conditions (500 mA cm−2 and 50 °C) after 3000 hrs. X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and X-ray absorption fine structure (XAFS) verify the interface electron transfer lowers the valence state of Co/Ni and activates them. DFT calculations also confirm the catalytic transition step of NiCoP can change from Heyrovsky (2.71 eV) to Tafel step (0.51 eV) in the neighborhood of Pt, in accord with the result of the improved Hads at the interface disclosed by in situ electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) tests.
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