Photocatalytic Oxidation of Aromatic Hydrocarbons

In acidic aqueous solutions UO(2)(2+) serves as a photocatalyst (lambda(irr) >/= 425 nm) for the oxidation of benzene by H(2)O(2). Under conditions where 50% of the excited state UO(2)(2+) is quenched by H(2)O(2) (k = 5.4 x 10(6) M(-)(1) s(-)(1)) and 50% by benzene (k = 2.9 x 10(8) M(-)(1) s(-)(1)), the quantum yield for the formation of phenol is 0.70. The yield does not change when benzene is replaced by benzene-d(6), but decreases by a factor of approximately 4 upon the change of solvent from H(2)O to D(2)O. Photocatalytic oxidation of toluene by UO(2)(2+)/H(2)O(2) produces PhCHO, PhCH(2)OH, and a mixture of cresols with a total quantum yield of 0.28 under conditions where 50% of UO(2)(2+) is quenched by H(2)O(2). The quenching of UO(2)(2+) by benzene and substituted benzenes takes place with k > 10(8) M(-)(1) s(-)(1). The system UO(2)(2+)/t-BuOOH/C(6)H(6)/hnu does not result in the oxidation of benzene, but instead yields methane and ethane.