Multi-Elemental Electronic Coupling for Enhanced Hydrogen Generation.

A robust polyaniline-assisted strategy is developed to construct a self-supported electrode constituting a nitrogen, phosphorus, sulfur tri-doped thin graphitic carbon layer encapsulated sulfur-doped molybdenum phosphide nanosheet array (NPSCL@S-MoP NSs/CC) with accessible nanopores, desirable chemical compositions, and stable composite structure for efficient hydrogen evolution reaction (HER). The multiple electronic coupling effects of S-MoP with N, P, S tri-dopants afford effective regulation on their electrocatalytic performance by endowing abundant accessible active sites, outstanding charge-transfer property, and d-band center downshift with a thermodynamically favorable hydrogen adsorption free energy (ΔGH* ) for efficient hydrogen evolution catalysis. As a result, the NPSCL@S-MoP NSs/CC electrode exhibits overpotentials as low as 65, 114, and 49 mV at a geometric current density of 10 mA cm-2 and small Tafel slopes of 49.5, 69.3, and 53.8 mV dec-1 in 0.5 m H2 SO4 , 1.0 m PBS, and 1.0 m KOH, respectively, which could maintain 50 h of stable performance, almost outperforming all MoP-based catalysts reported so far. This study provides a valuable methodology to produce interacted multi-heteroatomic doped graphitic carbon-transition metal phosphide electrocatalysts with superior HER performance in a wide pH range.