Abstract
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.
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Acknowledgements
This research is supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Award DE-FG02-09ER46664. M.C.-A. thanks the NSF graduate Research Fellowship for support. J.R.S. is supported by the National Science Foundation Grant No. CHE-1362136 for the theoretical work here. H.-C.C., M.-L.T. and J.-H.H. are supported by KAUST baseline fund for design and fabrication of light-harvesting Si substrates.
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M.C.-A. and S.J. designed the experiments. M.C.-A. and M.L.S. carried out the synthesis of CoPS nanomaterials and electrochemical measurements. J.R.S. performed the density functional calculations and computational modelling. M.C.-A. and J.G.T. carried out the fabrication of photocathodes and photoelectrochemical measurements. Q.D. contributed to the photoelectrochemical performance optimization. H.-C.C., M.-L.T. and J.-H.H. designed and fabricated the n+–p–p+ micropyramid silicon substrates. M.C.-A. performed the structural characterization. M.C.-A. and S.J. wrote the manuscript and all authors commented on the manuscript.
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Cabán-Acevedo, M., Stone, M., Schmidt, J. et al. Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide. Nature Mater 14, 1245–1251 (2015). https://doi.org/10.1038/nmat4410
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DOI: https://doi.org/10.1038/nmat4410
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