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The photocatalytic activity of nanostructured In2O3-x(OH)y for the ReverseWater Gas Shift (RWGS) Reaction CO2 + H2 -> CO + H2O can be greatly enhanced bysubstitution of Bi(III) for In(III) in the lattice of BizIn2-zO3-xOHy. Thisbehavior was hypothesized as the effect of the population and location ofBi(III) on the Lewis acidity and Lewis basicity of proximal hydroxide andcoordinately unsaturated metal surface sites in BizIn2-zO3-xOHy actingsynergistically as a Frustrated Lewis Acid-Base Pair reaction. Reported herein,XPS interrogates this photochemical RWGS reaction transiting from vacuum stateto similar conditions in a photocatalytic reactor, under dark and ambienttemperature, 150 degC, and 150 degC with photoillumination. Binding energyshifts were used to correlate the material system's Lewis basicity response tothese acidic probe gases. In-situ gas electronic sensitivity and in-situ UV-Visderived band gap trends confirm the trends shown in the XPS results. Theenhanced photo-catalytic reduction rate of CO2 with H2 with low doped 0.05% a.tBi system is thus associated with an increased gas sensitivity in H2+CO2, agreater increase in the OH shoulder than that of the undoped system under heatand light conditions. The photo-induced expansion of the OH shoulder and theincreased positive binding energy shifts shows the important role ofphotoillumination over that of thermal conditions. The poor catalyticperformance of the high doped system can be attributed to a competing H2reduction of In3+. The results provide new insight into how methodical tuningof the Lewis acidity and Lewis basicity of surface Frustrated Lewis Acid BasePair sites by varying z amount in BizIn2O3-xOHy enables optimization of therate of the photochemical RWGS.

Reactor based XPS and other in-situ studies on the Effect of  Substitution of Bismuth for Indium in Defect Laden Indium Oxide Hydroxide  BizIn2-zO3-x(OH)y on the Photocatalytic Hydrogenation of Carbon Dioxide