The scalable and sustainable production of hydrogen fuel through water splitting demands
efficient and robust Earth-abundant catalysts for the hydrogen evolution reaction
(HER). Building on promising metal compounds with high HER catalytic activity, such
as pyrite structure cobalt disulphide (CoS2), and substituting non-metal elements
to tune the hydrogen adsorption free energy could lead to further improvements in
catalytic activity. Here we present a combined theoretical and experimental study
to establish ternary pyrite-type cobalt phosphosulphide (CoPS) as a high-performance
Earth-abundant catalyst for electrochemical and photoelectrochemical hydrogen production.
Nanostructured CoPS electrodes achieved a geometrical catalytic current density of
10 mA cm(-2) at overpotentials as low as 48 mV, with outstanding long-term operational
stability. Integrated photocathodes of CoPS on n(+)-p-p(+) silicon micropyramids achieved
photocurrents up to 35 mA cm(-2) at 0 V versus the reversible hydrogen electrode (RHE),
onset photovoltages as high as 450 mV versus RHE, and the most efficient solar-driven
hydrogen generation from Earth-abundant systems.