Photocatalysis of chloroform decomposition by tetrachlorocuprate (II) on Dowex 2-X8.

Heterogenized on a polystyrene anion exchange resin and in the presence of oxygen, CuCl4(2-) catalyzes the photodecomposition of chloroform at wavelengths above 345 nm with greater efficiency than an equivalent amount in homogeneous solution. The reaction is proposed to proceed in two stages, the first stage yielding CCl4 and HO2(-) as products, the second consisting of a chain reaction resulting from the CuCl4(2-)-catalyzed photodissociation of CCl4, yielding phosgene with CCl3 radicals as chain carriers. Photodecomposition is retarded by added Cl(-), CH3CN, C6H12 or C2H5OH, which is ascribed to the displacement of CHCl3 molecules from the vicinity of the copper by attraction to the polystyrene matrix or to the alkylammonium cation sites.

Photodecomposition of chloroform catalyzed by unmodified MCM-41 mesoporous silica.

Unactivated MCM-41 mesoporous silica catalyzes the photodecomposition of chloroform to phosgene and hydrogen chloride under near-UV (λ > 360 nm) irradiation. The rate of photodecomposition increases toward an asymptotic limit as the O(2) partial pressure is increased. Deuterochloroform does not decompose under the same experimental conditions.

Photodecomposition of dichloromethane catalyzed by tetrachloroferrate(III) supported on a Dowex anion exchange resin.

The FeCl4(-) ion, heterogenized on a Dowex ion exchange resin, catalyzes the aerobic photodecomposition of neat CH2Cl2. Phosgene production was used to characterize the extent of decomposition, although it appears to be a secondary product from the decomposition of chloroform, which is suggested to arise from the reaction of dichloromethanol with hydrogen chloride. The yield of CHCl3 increases when the production of phosgene is suppressed by water or acetonitrile.

Photocatalysis of chloroform decomposition by the hexachlororuthenate(IV) ion.

Dissolved hexachlororuthenate(IV) effectively catalyzes the photodecomposition of chloroform to hydrogen chloride and phosgene under near-UV (λ > 345 nm) irradiation, whereby RuCl6(2-) is not itself photocatalytically active, but is photochemically transformed into a species that is active, possibly RuCl5 (CHCl3 )(-) . Conversion to a photoactive species during irradiation is consistent with the acceleration of the decomposition rate during the early stages and with the apparent inverse dependence of the decomposition rate on the initial concentration of RuCl6(2-) . The displacement of Cl(-) by CHCl3 in the coordination sphere to create the photoactive species is consistent with the retardation of photodecomposition by both Cl(-) and H2 O.