Photochemical reduction of CO2 using TiO2: effects of organic adsorbates on TiO2 and deposition of Pd onto TiO2.

Reduction of CO(2) using semiconductors as photocatalysts has recently attracted a great deal of attention again. The effects of organic adsorbates on semiconductors on the photocatalytic products are noteworthy. On untreated TiO(2) (P-25) particles a considerable number of organic molecules such as acetic acid were adsorbed. Although irradiation of an aqueous suspension of this TiO(2) resulted in the formation of a significant amount of CH(4) as a major product, it was strongly suggested that its formation mainly proceeded via the photo-Kolbe reaction of acetic acid. Using TiO(2) treated by calcination and washing procedures for removal of the organic adsorbates, CO was photocatalytically generated as a major product, along with a very small amount of CH(4), from an aqueous suspension under a CO(2) atmosphere. In contrast, by using Pd (>0.5 wt %) deposited on TiO(2) (Pd-TiO(2)) on which organic adsorbates were not detected, CH(4) was the main product, but CO formation was drastically reduced compared with that on the pretreated TiO(2). Experimental data, including isotope labeling, indicated that CO(2) and CO(3)(2-) are the main carbon sources of the CH(4) formation, which proceeds on the Pd site of Pd-TiO(2). Prolonged irradiation caused deactivation of the photocatalysis of Pd-TiO(2) because of the partial oxidation of the deposited Pd to PdO.

Decomposition of environmentally persistent perfluorooctanoic acid in water by photochemical approaches.

The decomposition of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water by UV-visible light irradiation, by H202 with UV-visible light irradiation, and by a tungstic heteropolyacid photocatalyst was examined to develop a technique to counteract stationary sources of PFOA. Direct photolysis proceeded slowly to produce CO2, F-, and short-chain perfluorocarboxylic acids. Compared to the direct photolysis, H2O2 was less effective in PFOA decomposition. On the other hand, the heteropolyacid photocatalyst led to efficient PFOA decomposition and the production of F- ions and CO2. The photocatalyst also suppressed the accumulation of short-chain perfluorocarboxylic acids in the reaction solution. PFOA in the concentrations of 0.34-3.35 mM, typical of those in wastewaters after an emulsifying process in fluoropolymer manufacture, was completely decomposed by the catalyst within 24 h of irradiation from a 200-W xenon-mercury lamp, with no accompanying catalyst degradation, permitting the catalyst to be reused in consecutive runs. Gas chromatography/mass spectrometry (GC/MS) measurements showed no trace of environmentally undesirable species such as CF4, which has a very high global-warming potential. When the (initial PFOA)/(initial catalyst) molar ratio was 10: 1, the turnover number for PFOA decomposition reached 4.33 over 24 h of irradiation.

Improvement of catalyst durability by deposition of Rh on TiO2 in photooxidation of aromatic compounds.

Gas-solid heterogeneous photocatalytic oxidation of aromatic compounds in air was carried out at room temperature with a fixed bed flow reactor. The deposition of Rh on TiO2 catalyst improved the catalyst durability in benzene photooxidation. The Rh deposition reduced the amounts of carbonaceous materials on the catalyst surface that were the cause of catalyst deactivation. The highest reaction rate was obtained at the Rh loading of 0.5-1.0 wt %. The Rh/TiO2 catalyst was gradually deactivated in prolonged benzene photooxidation, due to the increasing amount of carbonaceous materials on the catalyst surface. XPS studies showed that the gradual deactivation was related to the changes in the oxidation state of the surface Rh metals. The catalysts were regenerated by the treatment of hydrogen reduction after the photoirradiation in humidified air, indicating that Rh(0) was essential for the improvement of the catalyst durability. The catalyst was also regenerated by the heat treatment in N2 flow instead of the hydrogen reduction. Rh deposition was also effective for the improvement of catalyst durability in toluene photooxidation.

Heterogeneous decomposition of CHF2OCH2CF3 and CHF2OCH2C2F5 over various standard aluminosilica clay minerals in air at 313 K.

The heterogeneous decomposition of CHF2OCH2C2F5, a potential substitute for hydrofluorocarbons, over aluminosilica clay minerals in air, was confirmed to occur at 313 K in a closed-circulation reactor. HC(O)OCH2C2F5, the gaseous main product was produced through hydrolytic elimination of F atoms from the CHF2OCH2- group. CHF2OCH2CF3 also decomposed to HC(O)OCH2CF3 over the clay minerals. The pseudo-first-order rate constants were determined for the decompositions over eight types of clay minerals (19 samples). The various clay minerals had different abilities to decompose these hydrofluoroethers. The decomposition rates per Brunauer-Emmett-Teller surface area and the conversion ratios to HC(O)OCH2C2F5 or HC(O)OCH2CF3 for the reactions over kaolinite, halloysite, and illite were high in comparison to those for the same reactions over montmorillonite, hectorite, and nontronite. The dependence of this heterogeneous reaction on temperature and relative humidity indicates that, in the environment, the reaction could be important only in hot, dry regions. The results did not suggest that sunlight would directly accelerate the decay of CHF2OCH2CF3 or CHF2OCH2C2F5. In the presence of clay-containing soils in arid areas, this hydrolytic oxidation reaction may significantly affect both the lifetime and the degradation products of CHF2OCH2CF3 and CHF2OCH2C2F5 in the troposphere.