High rate CO2 photoreduction using flame annealed TiO2 nanotubes

The photocatalytic reduction of CO2 into light hydrocarbons using sunlight and water is a challenging reaction involving eight electron transfer steps; nevertheless, it has great potential to address the problem of rising anthropogenic carbon emissions and enable the use of fossil fuels in a sustainable way. Several decades after its first use, TiO2 remains one of the best performing and most durable photocatalysts for CO2 reduction albeit with a poor visible light absorption capacity. We have used flame annealing to improve the response of TiO2 to visible photons and engineered a nanotubular morphology with square-shaped cross-sections in flame-annealed nanotubes. An enhanced CH4 yield was achieved in the photoreduction of CO2 using flame annealed TiO2 nanotubes, and isotope labeled experiments confirmed the reaction products to originate from the CO2 reactant. Flame-annealed TiO2 nanotubes formed in aqueous electrolyte (FANT-aq) yielded 156.5 mu mol g(catalyst)(-1).hr(-1) of CH4, which is in the top tier of reported performance values achieved using TiO2 as a stand-alone photocatalyst. This performance resulted because appreciable amounts of CH4 were generated under visible light illumination as well. TiO2 nanotubes exhibited CO2 photoreduction activity up to a wavelength of 620 nm with visible light driven photocatalytic activity peaking at 450 nm for flame annealed TiO2 nanotubes. Isotope labelling studies, using GC-MS and gas-phase FTIR, indicated photoreduction of (CO2)-C-13 to (CH4)-C-13. The detection of (CO)-C-13 in the product mixture, and the absence of HCHO and HCOOH provides strong support for the photoreduction proceeding along a carbene pathway. The enhanced CO2 photoreduction performance of FANT-aq is attributed to increased visible light absorption, square morphology, and the presence of rutile as the only crystalline phase with (110) as the dominant plane.