The photocatalytic activity of nanostructured In2O3–x
(OH)y for
the reverse
water gas shift (RWGS) reaction CO2 + H2 →
CO + H2O can be greatly enhanced by substitution of Bi(III)
for In(III) in the lattice of Bi
z
In2–z
O3–x
(OH)
y
. This behavior was hypothesized
as the effect of the population and location of Bi(III) on the Lewis
acidity and Lewis basicity of proximal hydroxide and coordinately
unsaturated metal surface sites in Bi
z
In2–z
O3–x
(OH)
y
acting synergistically as
a frustrated Lewis acid–base pair reaction. Nonetheless, such
photocatalytic activity is usually optimized in a specific batch reactor
setup sequence, with H2 as an initial gas input under photo
and thermal conditions before introducing CO2. Hence, the
chemical interplay between environment parameters such as photoillumination,
thermal input, and gas reactant components with the effects of Bi
substitution is unclear. Reported herein, glovebox-protected X-ray
photoelectron spectroscopy (XPS) interrogates this photochemical RWGS
reaction transiting from vacuum state to similar conditions in a photocatalytic
reactor, under dark and ambient temperatures, 150°C in dark and
150 °C under photoillumination. Binding energy shifts were used
to correlate the material system’s Lewis basicity response
to these acidic probe gases. In-situ gas electronic sensitivity and
in-situ UV–vis-derived band-gap trends confirm the trends shown
in the XPS results, hence showing its equivalency with in situ methods.
The enhanced photocatalytic reduction rate of CO2 with
H2 with a low doped 0.05% a.t Bi system is thus associated
with an increased gas sensitivity in H2 + CO2, a greater expansion in the OH shoulder than that of the undoped
system under heat and light conditions, as well as a greater thermal
stability of dissociated H adatoms. The photoinduced expansion of
the OH shoulder and the increased positive binding energy shifts show
the important role of photoillumination over that of thermal conditions.
The poor catalytic performance of the high doped system can be attributed
to a competing H2 reduction of In3+. The results
provide new insight into how pairing photo and thermal conditions
with the methodical tuning of the Lewis acidity and Lewis basicity
of surface frustrated Lewis acid–base pair sites by varying
z amount in Bi
z
In2–z
O3–x
(OH)
y
enables optimization of the rate of the photochemical
RWGS.