Photoactivity of amorphous and crystalline TiO₂ nanotube arrays (TNA) films in gas phase CO₂ reduction to methane with simultaneous H₂ production

This study assessed the photoactivity of amorphous and crystalline TiO2 nanotube arrays (TNA) films in gas phase CO2 reduction. The TNA photocatalysts were fabricated by titanium anodization and submitted to an annealing treatment for crystallization and/or cathodic reduction to introduce Ti3+ and oxygen vacancies into the TiO2 structure. The cathodic reduction demonstrated a significant effect on the generated photocurrent. The photoactivity of the four TNA catalysts in CO2 reduction with water vapor was evaluated under UV irradiation for 3 h, where CH4 and H2 were detected as products. The annealed sample exhibited the best performance towards methane with a production rate of 78 μmol gcat−1 h−1, followed by the amorphous film, which also exhibited an impressive formation rate of 64 μmol gcat−1 h−1. The amorphous and reduced-amorphous films exhibited outstanding photoactivity regarding H2 production (142 and 144 μmol gcat−1 h−1, respectively). The annealed catalyst also revealed a good performance for H2 production (132 μmol gcat−1 h−1) and high stability up to five reaction cycles. Molecular dynamic simulations demonstrated the changes in the band structure by introducing oxygen vacancies. The topics covered in this study contribute to the Sustainable Development Goals (SDG), involving affordable and clean energy (SDG#7) and industry, innovation, and infrastructure (SDG#9).Green Open Access added to TU Delft Institutional Repository 'You share, we take care!' - Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.Micro and Nano Engineerin