The anaerobic photocatalytic decomposition of methanol in aqueous solution
has been investigated using a Pd/TiO2 catalyst. The rate is near zero order
in methanol over most of the range of reaction, but has a complicated depe
ndence on the loading of Pd on the photoactive support. This dependence is
explained by assigning the active site for the rate determining step to be
at the interface between the Pd and the TiO2. In the absence of light, the
methanol does not decompose at steady state on the catalyst, probably due t
o poisoning of the Pd surface with adsorbed CO. Light of greater energy tha
n the TiO2 band gap (similar to 3.2 eV) causes photoexcitation of electrons
into the conduction band; this produces an oxidant which reacts with adsor
bed CO to produce CO2 and hence maintains a steady state rate of methanol d
ecomposition. The overall oxidant is water. A detailed model for the reacti
on is proposed. (C) 1999 Elsevier Science B.V. All rights reserved.