Controlling atomic phosphorous-mounting surfaces of ultrafine W2C nanoislands monodispersed on the carbon frameworks for enhanced hydrogen evolution

Controllably mounting foreign atoms on the surfaces of earth-abundant electrocatalysts strongly improve their surface electronic properties for optimizing the catalytic performance of surficial sites to an unusual level, and provides a good platform to gain deep insights into catalytic reactions . The present work describes, employing ultrafine W 2 C nanoislands (average size: 2.3 nm) monodispersed on the N, P dual-doped carbon frameworks as a model system, how to regulate the atomic phosphorous-mounting effect on the surfaces of W 2 C to derive an active and stable P-mounting W 2 C (WCP) catalyst for both acidic and alkaline hydrogen evolution reaction (HER). Since in situ phosphorus substitution into carbon sites of preformed W 2 C nanoislands gradually proceeds from surfaces to solids, so that using a proper amount of phosphorus sources can readily control the surface mounting level to avoid the mass P-doping into the bulk. By this way, the activity per active site of WCP catalyst with robust stability can be optimized to 0.07 and 0.56 H 2 s −1 at –200 mV overpotential in acid and base, respectively, which reach up to the several-fold of pure-phase W 2 C (0.01 and 0.05 H 2 s −1 ). Theoretical investigations suggest that compared with solid P doping, the P mounting on W 2 C surface can more remarkably enhance its metallicity and decrease the hydrogen release barrier. This finding disclosed a key correlation between surface foreign atom-mounting and catalytic activity , and suggested a logical extension to other earth-abundant catalysts for various catalytic reactions .