The effect of illumination with visual and near-UV light on the isomer
ization and cracking of n-pentane and formation of radical cations fro
m benzene and its derivatives over sulfated zirconia has been studied.
Sulfated zirconia proved to have very strong acceptor sites capable o
f ionizing benzene and methylbenzenes to corresponding radical cations
. The ionization of aromatic molecules could be initiated with visual
light. The presence of oxygen in the gas phase appeared to strengthen
the acceptor sites and shift the photoreaction red edge to longer wave
lengths. Electron donor-acceptor complexes are shown to be key interme
diates in the ionization of aromatic molecules on sulfated zirconia. A
qualitative correlation between the presence of the strongest accepto
r sites and the isomerization activity was observed. Illumination with
visual light significantly increased the pentane cracking selectivity
with little effect on the isomerization activity. Pentane cracking is
proposed to proceed via dimerization initiated by the charge transfer
with the formation of unstable radical cations. (C) 1998 Academic Pre
ss.