Abstract
Developing earth‐abundant and efficient electrocatalysts for photoelectrochemical water splitting is critical to realizing a high‐performance solar‐to‐hydrogen energy conversion process. Herein, phosphorus‐rich colloidal cobalt diphosphide nanocrystals (CoP2 NCs) are synthesized via hot injection. The CoP2 NCs show a Pt‐like hydrogen evolution reaction (HER) electrocatalytic activity in acidic solution with a small overpotential of 39 mV to achieve −10 mA cm−2 and a very low Tafel slope of 32 mV dec−1. Density functional theory (DFT) calculations reveal that the high P content both physically separates Co atoms to prevent H from over binding to multiple Co atoms, while simultaneously stabilizing H adsorbed to single Co atoms. The catalytic performance of the CoP2 NCs is further demonstrated in a metal–insulator–semiconductor photoelectrochemical device consisting of bottom p‐Si light absorber, atomic layer deposition Al–ZnO passivation layers, and the CoP2 cocatalyst. The p‐Si/AZO/TiO2/CoP2 photocathode shows a photocurrent density of −16.7 mA cm−2 at 0 V versus reversible hydrogen electrode (RHE) and an output photovoltage of 0.54 V. The high performance and stability are attributed to the junction between p‐Si and AZO, the corrosion‐resistance of the pinhole‐free TiO2 protective layer, and the fast HER kinetics of the CoP2 NCs.