| Summary: | Abstract Developing efficient (co-)catalysts with optimized interfacial mass and charge transport properties is essential for enhanced oxygen evolution reaction (OER) via electrochemical water splitting. Here we report one-atom-thick hexagonal boron nitride (hBN) as an attractive co-catalyst with enhanced OER efficiency. Various electrocatalytic electrodes are encapsulated with centimeter-sized hBN films which are dense and impermeable so that only the hBN surfaces are directly exposed to reactive species. For example, hBN covered Ni-Fe (oxy)hydroxide anodes show an ultralow Tafel slope of ~30 mV dec−1 with improved reaction current by about 10 times, reaching ~2000 mA cm−2 (at an overpotential of ~490 mV) for over 150 h. The mass activity of hBN co-catalyst is found exceeding that of commercialized catalysts by up to five orders of magnitude. Using isotope experiments and simulations, we attribute the results to the adsorption of oxygen-containing intermediates at the insulating co-catalyst, where localized electrons facilitate the deprotonation processes at electrodes. Little impedance to electron transfer is observed from hBN film encapsulation due to its ultimate thickness. Therefore, our work also offers insights into mechanisms of interfacial reactions at the very first atomic layer of electrodes.
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