Photooxidation of M(CO)6 (M=Mo, W) adsorbed on TiO2
Abstract
Photooxidation of M(CO)
6
(M=Mo, W) adsorbed on
TiO
2
has been conducted from a viewpoint of the kinetics
and mechanism of the reaction and the photocatalytic effect of
TiO
2
. The reaction rate was first order with respect to the
surface concentration of M(CO)
6
and zero order with respect
to oxygen pressure. The photocatalytic effect of TiO
2
was
suggested by the fact that the reaction rate of the
W(CO)
6
/TiO
2
system was considerably greater than
that of W(CO)
6
/NaY zeolite. The rate constant strongly
depended on the TiO
2
employed and was delineated to a
direct-allowed band-gap of the TiO
2
. The photocatalytic
effects of TiO
2
are tentatively suggested to result from a
strongly enhanced decarbonylation of M(CO)
6
by photoinduced
valence band holes, followed by rapid reactions with anionic surface
oxygen species.
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