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The photochemical reduction of CO2 to chemicals, such as CO and CH4, is a promising carbon management approach that can generate revenue from chemical sales to help offset the costs associated with the use of carbon-management technologies. Delafossite materials of the general stoichiometry ABO2 are a new class of photocatalysts being considered for this application. Symmetry breaking in these materials, by chemical substitution, modifies the band structure of the solid, which enhances optical transitions at the fundamental gap and can therefore be used to engineer the photocatalytic performance of delafossites by adjusting the alignment of band edges with chemical redox potentials and enhancing the optical activity associated with the production of photoexcited charge carriers. The photochemical activity of CuGaO2 and CuGa1–x Fe x O2 (x = 0.05, 0.10, 0.15, 0.20) for the reduction of CO2 has been studied. Our results show that the CuGaO2 materials investigated have an optical gap at ∼3.7 eV in agreement with previous literature reports. An optical feature is also observed at ∼2.6 eV, which is not as commonly reported due to a weak absorption cross section. Alloying at the B-site with Fe to form CuGa1–x Fe x O2 (x = 0.05, 0.10, 0.15, 0.20) creates new features in the visible and near-infrared region of the optical spectra for the substituted materials. Electronic density of states calculations indicate that B-site alloying with Fe creates new midgap states caused by O atoms associated with Fe substitution sites; increased Fe concentration contributes to broadening of these midgap states. The strain caused by Fe incorporation breaks the symmetry of the crystal structure giving rise to the new optical transitions noted experimentally. The photoreduction of CO2 in the presence of H2O vapor using CuGaO2 and CuGa1–x Fe x O2 produces CO with little evidence for other products such as H2 or hydrocarbons. The impact of Fe alloying with Ga on the band structure and photochemical activity of this delafossite system is discussed.

NMR spectrum of compound 4 (Figure SI), a Pluto plot of the ground-state conformation of compound 3 (Figure S2), and a stereoview of the X-ray structure of compound 5 (Figure S3) and X-ray crystallographic data (39 pages). Ordering information is given on any current masthead page.

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