No abstract

Initial quantum yields φ for the formation of DMPO-OH adducts in clear, aerated, unbuffered TiO2 sols irradiated at 295 nm were determined by kinetic electron paramagnetic resonance spectrometry as function of the 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin trap concentration, photon irradiance I o, and added dichlorobenzene DCB, at 298 K. φ steadily increases with [DMPO] in the range 0.3 mM to 0.3 M, extrapolating to φ [DMPO]→∞ = 0.54 ± 0.10, in contrast with the constant yields obtained for the homogeneous generation of OH radicals in the photodissociation of H2O2 at 254 nm under similar conditions. In TiO2 sols at [DMPO] = 0.6 mM, φ (≈0.002) remains constant over a 20-fold variation of Io , but decreases upon addition of comparable DCB concentrations. These observations prove that (1) DMPO reacts with photogenerated holes and/or OH radicals on the surface of TiO2 particles rather than in the solution bulk, (2) it is possible to approach quantitative carrier trapping, (3) DCB is as reactive as DMPO toward some of the photogenerated carriers, and (4) the recombination of a single carrier pairthe usual event in small particles at moderate photon fluxesis a pseudo-first-order process. Photocatalysis in semiconductor sols is a stochastic process not amenable to conventional kinetic analysis based on rate expressions involving continuous concentration variables. Quantum yields are largely controlled by the anodic (h + D → D+), rather than by the slower (e + O2 → O2 •-) cathodic charge transfer reaction.

Cr(VI) photocatalytic reduction experiments over TiO2 particles under near UV irradiation in the presence of excess oxalate were performed at acid pH (2 and 3) and under air and N2 bubbling. Initial photonic efficiencies for Cr(VI) reduction are nearly the same under aerobic and anaerobic conditions, but show a significant increase at the lowest pH. At pH 2, the addition of oxalate facilitates Cr(VI) reduction, hindering the electron-shuttle mechanism taking place in pure water. The oxalate synergistic effect at pH 2 is lower than that previously found for EDTA and negligible at pH 3. Chromium(V) oxalate concentration profiles were obtained by EPR spectroscopy in the presence of excess oxalate at pH 1.5. Coordinated Cr(V) complexes [Cr(V)(O)(Ox)2]-, [Cr(V)(OH2)(Ox)2]-, and [Cr(V)(O)(OH)2(Ox)]- were identified, on the basis of the comparison of their corresponding g values with recent literature data. The kinetic analysis of the temporal evolution of the paramagnetic Cr(V) species indicates also an effective photocatalytic degradation of chromium(V) oxalate complexes. This new evidence reinforces previous findings regarding sequential one-electron-transfer processes in Cr(VI) photocatalytic reduction, suggesting that this route may represent a general behavior for the Cr(VI) reduction over UV-irradiated TiO2 particles.