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article
Durable electrooxidation of acidic water catalysed by a cobalt-bismuth-based oxide composite: an unexpected role of the F‑doped SnO2 substrate
Abstract
Aiming to design a catalyst for stable electrooxidation of water at low pH, the present work explores the electrocatalytic properties and structural features of electrodeposited composite oxides based on bismuth and cobalt, which were anticipated to provide stability and catalytically activity, respectively. Materials deposited as very thin (ca 50 nm) films on F-doped SnO2 (FTO) substrate do not initially exhibit high performance during water oxidation in 0.1 M H2SO4, but are activated during operation through the electrooxidatively-induced enrichment of the catalytic surface with cobalt and tin oxides. The latter originate from the FTO support and are identified as an important component of the catalyst through control experiments with a Sn-free substrate and with Sn2+ intentionally added at the electrodeposition stage. A unique feature of the Co-Bi-Sn-based electrocatalyst is the slow but persistent improvement in the activity during operation in 0.1 M H2SO4 at both ambient and elevated (60 °C) temperatures, which contrasts the continuously degrading behaviour of state-of-the-art water oxidation catalysts at low pH. This is demonstrated by 9-day-long galvanostatic tests at 10 mA cm-2, during which the Co-Bi-Sn-based thin film catalyst shows no degradation and sustains stable water oxidation at ca 1.9 V vs. reversible hydrogen electrode. The effects of tin leaching from the support detected herein might have implications to other acidic water oxidation catalysts supported on different types of doped SnO2 materials.