Highly Dispersed Cobalt Oxide on TaON as Efficient Photoanodes for Long-Term Solar Water Splitting

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School of Chemistry and the ARC Centre of Excellence for Electromaterials Science, Monash University, Clayton, Victoria 3800, Australia
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan
§ Monash Centre for Electron Microscopy, Monash University, Clayton, Victoria 3800, Australia
*E-mail for A.N.S.: [email protected]
*E-mail for R.A.: [email protected]
*E-mail for L.S.: [email protected]
Cite this: ACS Catal. 2016, 6, 5, 3404–3417
Publication Date (Web):April 13, 2016
Copyright © 2016 American Chemical Society
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Photoelectrochemical water splitting into H2 and O2 over a semiconductor-based photocatalyst offers a promising way to achieve the sustainable harvesting and storage of solar energy. However, short diffusion lengths and inefficient separation of the charge carriers in the semiconductors following light absorption result in fast recombination of holes and electrons and eventually poor performance. Herein, we address this problem by integrating an efficient and robust water oxidation catalyst, cobalt oxide (CoOx), into screen-printed TaON photoanodes premodified with TiO2 coatings for better stability. SEM, TEM, and ICP-MS analysis of the Co deposits and electrochemical techniques were used to demonstrate the advantages provided by the photoassisted CoOx electrodeposition method. Specifically, this method allows the selective and facile functionalization of the TiO2-TaON surface with a uniform layer of near-(hemi)spherical CoOx particles having a diameter of 5–15 nm. In comparison to the TiO2-TaON photoanodes, the optimized CoOx/TiO2-TaON configuration provides an enhancement in the photocurrent densities of up to 2 orders of magnitude and a substantial improvement in the long-term stability on testing in borate buffer solutions (pH 9.2). The highest oxidative photocurrent density of 0.7 mA cm–2 was achieved with CoOx/TiO2-TaON under visible light irradiation (λ >400 nm; 100 mW cm–2) at 1.2 V vs reversible hydrogen electrode, and the system remained stable for at least 24 h. The Co loading in the best-performing photoanode is ca. 0.1 wt % with respect to TaON; higher and lower loadings result in poorer photocatalytic activity and stability. Comparisons of the performance of CoOx/TiO2-TaON with other representative inorganic water photoelectrooxidation systems are provided and discussed.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.6b00629.

  • Optimization data for CoOx electrodeposition under different conditions and their effect on photoactivity measured voltammetrically and chronoamperometrically, transients for the electrodeposition of CoOx, SEM images (before and/or after stability test), EIS data, chronoamperometric data under various conditions, comparison of Faradaic efficiency and amount of H2 and O2 gases evolved from water splitting in three- and two-electrode configurations, and AB-SHE data (PDF)

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