Publication date: 15th December 2014
Efficient (photo)electrochemical water splitting to hydrogen and oxygen is a key technology to overcome our dependency on fossil fuels and to establish a carbon-neutral hydrogen economy. Although hydrogen is the desired end product, the very slow kinetics and high overpotential of the oxygen generation are the limiting factors for an efficient overall water splitting process. Therefore, searching for catalytic materials for photo/electrochemical oxygen generation is of great importance for improving the efficiency of water splitting.We present our work on ultrasmall and highly dispersible doped nickel and cobalt oxide-based nanocrystals that meet the substantial challenge of inexpensive, efficient and stable (photo)electrocatalysts for water splitting. A solvothermal synthesis in tert-butanol leads to the formation of crystalline nanoparticles already in solution, without the need for a subsequent high temperature treatment that would result in irreversible particle agglomeration. The particles prepared in this way are dispersible in ethanol thus forming stable colloidal dispersions.Using the successful tert-butanol synthesis method, we obtained ultrasmall cobalt oxide nanocrystals that can act as efficient co-catalyst for photoelectrochemical water oxidation on hematite photoanodes.The nickel oxide based nanoparticles demonstrate an extremely efficient catalytic behavior in electrochemical water splitting. The nanoparticles show very high turnover frequencies of 0.29 s‑1 at an overpotential of η = 300 mV, even outperforming expensive rare earth iridium oxide catalysts.
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