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article
Photoelectrochemical water oxidation using a Bi2MoO6/MoO3 heterojunction photoanode synthesised by hydrothermal treatment of an anodised MoO3 thin film
Abstract
An effective Mo-based ternary oxide Bi<sub>2</sub>MoO<sub>6</sub>/MoO<sub>3</sub> thin film for photoelectrochemical (PEC) water oxidation was prepared via a simple and direct thin film synthesis route. The synthesis strategy involved subjecting a MoO<sub>3</sub> thin film, prepared by anodising a Mo foil, to hydrothermal treatment in the presence of a bismuth salt solution. The new approach removes the need for preformed particles to prepare the film, in turn providing a robust and stable anode for PEC water splitting. X-ray diffraction of the Bi<sub>2</sub>MoO<sub>6</sub>/MoO<sub>3</sub> thin film revealed the film possessed two photocatalytically active phases of Bi<sub>2</sub>MoO<sub>6</sub>: (i) a low temperature phase (γ(L)-Bi<sub>2</sub>MoO<sub>6</sub>), and (ii) a high temperature phase (γ(H)-Bi<sub>2</sub>MoO<sub>6</sub>). UV-vis spectroscopy showed the optical band gaps of γ(L)-Bi<sub>2</sub>MoO<sub>6</sub> and γ(H)-Bi<sub>2</sub>MoO<sub>6</sub> were 2.75 eV and 3.1 eV, respectively. In contrast, the neat MoO<sub>3</sub> thin film had a wider band gap of 3.4 eV. Transforming the surface MoO<sub>3</sub> into Bi<sub>2</sub>MoO<sub>6</sub> to construct the Bi<sub>2</sub>MoO<sub>6</sub>/MoO<sub>3</sub> composite electrode leads to an improvement in photoelectrochemical (PEC) performance. The Bi<sub>2</sub>MoO<sub>6</sub>/MoO<sub>3</sub> electrode exhibited a 79% enhancement in anodic photocurrent density compared to the unmodified MoO<sub>3</sub> thin film under a positive bias of 0.4 V vs. Ag/AgCl. The better performance was attributed to: (i) the narrow optical band gap of Bi<sub>2</sub>MoO<sub>6</sub>, which extended the absorption of light by the film into the visible range and (ii) the well-aligned band structure of MoO<sub>3</sub> and Bi<sub>2</sub>MoO<sub>6</sub>. The Bi<sub>2</sub>MoO<sub>6</sub>/MoO<sub>3</sub> thin film electrode was subsequently utilised as a photoanode for PEC water splitting. The Bi<sub>2</sub>MoO<sub>6</sub>/MoO<sub>3</sub> thin film electrode provided close to 100% faradic photocurrent-to-O<sub>2</sub> conversion efficiency for PEC water splitting under UV illumination and, importantly, exhibited excellent photostability as a consequence of the unique synthesis method.