Photochemical and Photo Electrochemical Conversion of Carbon Dioxide to Methanol Using Nanotubular TiO2

"Ordered arrays of TiO2 nanotubular photocatalysts were prepared by a simple anodization process. Band gap states of the TiO2 were altered by controlling the anodization electrolyte composition and thermal annealing conditions that resulted in enhanced photo activity. These nanotubes were used for reducing CO2 to methanol either by photochemical or photo electrochemical routes. Pd nano-particle loaded TiO2 nanotubes were employed for photochemical reduction of CO2 to methanol that showed a conversion rate of 12 x 10-3 mol m- 2h-1. Carbon modified TiO2-xCx type nanotubes were used as photo anode and Ti as cathode for photo electrochemical reduction of CO2. The potential of Ti cathode was maintained at -0.5 V SCE. The formation rate of methanol was determined as 13 x 10-3 mol.m-2h-1.1. IntroductionGlobal warming due to emission of carbon dioxide is a serious environmental concern. The atmospheric concentration of CO2 is about 384 ppm by volume and about 3 x 1012 tonnes by weight. Burning of fossil fuels and deforestation are the leading causes for increase in the anthropogenic CO2. More than 32 x 109 tonnes of CO2 are released per year (based on 2006 data) worldwide from the fossil fuel. Pumping CO2 from the fossil fuel power plants into deep ocean basin is one of the most discussed disposal options. The other potential option is converting this green house gas into valuable fuels.Carbon dioxide feed stock can be converted into fuels of solid, liquid or gas phase by chemical, electrolytic, photocatalytic and photo-electrocatalytic methods. Reduction of CO2 to fuel form of any phase requires energy. The reduction process should be energy efficient so that we do not spend more energy and emit more (indirect) CO2 in the process of converting CO2. From this point of view, conversion processes occurring at room temperature look attractive.Electrolytic conversion of CO2 into various forms such as methane1, ethane2, ethylene3, methanol4,5, ethanol6, n-propanol, formic acid7, and formaldehyde has been widely reported. The standard equilibrium potential (at pH: 0) for reduction of CO2 to methanol is 0.14 VSHE and to methane is 0.2 VSHE which is thermodynamically more favorable than hydrogen reduction. However, the gas phase reduction is kinetically complex requiring effective electrocatalyst. The major issues with electrolytic conversion of CO2 to useful products are:"