A framework to determine the quantum efficiency eta of a photoreaction in a
porous layer of a photocatalyst is presented, The procedure relies on a mo
del of the photoproduct diffusion in the porous structure of the photocatal
yst. The model incorporates a position-dependent source term mirroring the
Light intensity profile in the layer and an effective diffusion coefficient
D-eff It allows for a simultaneous determination of eta as well as of D-ef
f. The method is applied to the photosynthesis of CH4 from gaseous H2O and
CO2 at the solid/gas interface of a porous layer of TiO2 (Degussa P25). A v
alue of eta = (8.79 +/- 0.79) x 10(-4) is found for the formation of CH4. T
he effective diffusion coefficient for the photoproduct CHS is D-eff = (5.6
4 +/- 2.51) x 10(-10) cm(2) s(-1). This value is much too low to be explain
ed by classical Knudsen diffusion in the layers with an experimentally dete
rmined porosity phi = 0.58. We suggest that the TiO2 layers contain a large
number of unconnected pores separated by walls of densely packed microcrys
tals almost impenetrable for gases such as CH4 Whether processes other than
diffusion are also responsible for the small value of D-eff is not clear a
t present.