Promoting water photooxidation on transparent WO3 thin films using an alumina overlayer

Abstract

Tungsten trioxide (WO3) is being investigated as one of the most promising materials for water oxidation using solar light. Its inherent surface-related drawbacks (e. g., fast charge recombination caused by surface defect sites, the formation of surface peroxo-species, etc.) are nowadays being progressively overcome by different methods, such as surface passivation and the deposition of co-catalysts. Among them, the role of surface passivation is still poorly understood. Herein, transparent WO3 (electrodeposited) and Al2O3/WO3 (prepared by atomic layer deposition, ALD) thin film electrodes were employed to investigate the role of an alumina overlayer by using both photoelectrochemical and laser flash photolysis measurements. Films with a 5 nm-alumina overlayer (30 ALD cycles) showed an optimum photoelectrochemical performance, portraying a 3-fold photocurrent and Faradaic efficiency enhancement under voltage biases. Moreover, IPCE measurements revealed that alumina effect was only significant with an applied potential ca. 1 V (vs. Ag/AgCl), matching the thermodynamic potential for water oxidation at pH 1 (0.97 V vs. Ag/AgCl). According to the investigation of electron accumulation through optical absorption measurements, the alumina overlayer dominantly decreased the number of electron trapping sites on the WO3