CO 2 Photoreduction Activity Enhancement and Unexpected Observation of Carbon Monoxide Adsorbates on the Surface of TiO 2 Nanotube Arrays Synthesized in Formamide Electrolytes.

TiO 2 nanotube arrays grown through electrochemical anodization in a formamide-based electrolyte (TNTA-FA) exhibited a whole host of unusual properties compared to nanotubes grown in the conventional ethylene glycol-based electrolyte (TNTA-EG). TNTA-FA exhibited shorter phonon lifetimes, lower lattice strain, more visible light absorption, lower work function, and a highly unusual adsorbate structure consisting of physisorbed and chemisorbed CO along with linearly adsorbed CO 2 and various monodentate and bidentate carbonate species. The observation of adsorbed CO in the dark is highly unusual and indicates spontaneous deoxygenation of CO 2 on the surface of TNTA-FA. The significance of this finding is that the formation of CO 2 •- is no longer the rate-limiting bottleneck for the reduction of CO 2 on TNTA-FA surfaces as it is for all TiO 2 surfaces. TNTA-FA samples are strongly colored (inclusive of a fluorescent green color) and consist of rounded, vertically oriented hollow cylinders as opposed to the honeycomb-like morphology of TNTA-EG arranged in an approximate triangular lattice. The photocatalytic activity was tested through the CO 2 photoreduction and dye degradation tests. Formamide-based nanotubes outperformed the EG-based nanotubes by almost 1.7 and 2 times, respectively, in CO 2 reduction and dye degradation tests done on methylene blue, brilliant green, and rhodamine B dyes. These results are attributed to stronger surface band bending in TNTA-FA which facilitates more efficient separation of photogenerated electron-hole pairs.