The photocatalytic conversion of CO2 to CH4 on hybrid TiO2/CdS catalysts in water in the presence of isopropanol (IPA) was explored. As compared to TiO2, TiO2/CdS increased the production of CH4 by a factor of similar to 10, whereas the production of H-2 and CO remained comparable. The amount of CdS loaded on the TiO2 was not observed to significantly affect the yields and distributions of the products. An electron impact time-of-flight mass spectrometry (TOF-MS) study revealed (CH4)-C-13 to be a dominant product in the early stages of the photocatalysis under (CO2)-C-13 atmosphere, whereas only similar to 25% of the total observed methane accounted for (CH4)-C-13 resulting from (CO2)-C-13 in the prolonged photocatalytic reaction over 6 h. Although the remainder of the methane originated from unlabeled carbons (e.g., from C-12-IPA and C-12-organic contaminants), the use of deuterated IPA in the TOF-MS study did not provide evidence for the contribution of the methyl groups of IPA. Furthermore, the diffuse reflectance infrared Fourier transform analysis showed the adsorption of aquated CO2 species (e.g., (bi)carbonate via mono- and bi-dentate modes at pH similar to 4.5) to be enhanced by the coupling of CdS to TiO2, which was found to significantly weaken after the reactions. On the other hand, the IPA-associated IR bands were influenced to a lesser extent by the photoreaction. (C) 2015 Published by Elsevier B.V.