The photochemical fixation of CO2 to energy rich products for solar energy storage or feedstock chemicals is an attractive, albeit daunting, challenge. The overall feasibility of CO2 conversion is limited by the availability of efficient photo-active materials that meet the energetic requirements for CO2 reduction and are optically matched to the solar spectrum. Surface modification of TiO2 with earth abundant metal oxides presents one approach to develop visible active photocatalysts through band gap narrowing, while providing catalytic sites to lower the activation energy for CO2 reduction. In this work density functional theory was used to model the effect of surface modification of rutile and anatase using MnOx nanoclusters. The results indicate the formation of inter-band gap states following surface modification with MnOx, but surface water can change this. Oxygen vacancies are predicted to form in supported MnOx and the interaction with CO2 was investigated. MnOx-TiO2 was synthesized and characterised using surface analytical methods and photoelectrochemistry. The interaction of CO2 with the materials under irradiation was probed using in-situ FTIR to interrogate the role of oxygen vacancies in CO2 binding and reaction. These results provide insights into the requirements of a multifunctional catalyst for CO2 conversion

The phase junction of nanocomposite materials is key to enhanced performance but is largely ignored in recent theoretical examinations of photocatalytic interactions in titania-based composites. Computational advances now allow more precise modeling of the electronic and optical properties of composites, and focusing on mixed-phase TiO2 as a model, we use density functional theory (DFT) to interrogate the essential structural feature, namely, the rutile–anatase interface, and its relationship to photogenerated charge localization, bulk band alignments, and defect formation. The interfacial region is disordered and distinct from rutile and anatase and contains low coordinated Ti sites and oxygen vacancies, both drivers of charge localization. The relaxations of the interface upon formation of excited electrons and holes determine the final location of charges which cannot always be predicted from bulk band alignments. A detailed understanding of the interfacial phase junction lays the foundation for directed synthesis of highly active and efficient composite photocatalysts.

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Titania nanotubes (TiNT) combine unique nanotubular morphology with the desirable electronic, optical, and chemical properties of nanostructured titania. This perspective provides an overview of the three major synthesis methods for TiNT and the corresponding physical and chemical characteristics of the material. Promising applications in photocatalysis are explored with special emphasis on recent insights in the photooxidative and photoreductive activity of TiNT materials. The major challenge for future work is to connect observed improvements in catalytic activity with an understanding of the fundamental processes in photocatalysis in order to tailor the structure of TiNT composites to targeted functions.

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