The surface frustrated Lewis pairs (SFLPs) on defect-laden metal oxides provide catalytic sites to activate H₂ and CO₂ molecules and enable efficient gas-phase CO₂ photocatalysis. Lattice engineering of metal oxides provides a useful strategy to tailor the reactivity of SFLPs. Herein, a one-step solvothermal synthesis is developed that enables isomorphic replacement of Lewis acidic site In³⁺ ions in In₂O₃ by single-site Bi³⁺ ions, thereby enhancing the propensity to activate CO₂ molecules. The so-formed Bi_xIn_2-xO₃ materials prove to be three orders of magnitude more photoactive for the reverse water gas shift reaction than In₂O₃ itself, while also exhibiting notable photoactivity towards methanol production. The increased solar absorption efficiency and efficient charge-separation and transfer of Bi_xIn_2-xO₃ also contribute to the improved photocatalytic performance. These traits exemplify the opportunities that exist for atom-scale engineering in heterogeneous CO₂ photocatalysis, another step towards the vision of the solar CO₂ refinery.

Photoelectrochemical (PEC) water splitting that functions in pH-neutral electrolyte attracts increasing attention to energy demand sustainability. Here, we propose a strategy to in situ form a NiB layer by tuning the composition of the neutral electrolyte with the additions of nickel and borate species, which improves the PEC performance of the BiVO ₄ photoanode. The NiB/BiVO ₄ exhibits a photocurrent density of 6.0 mA cm ⁻² at 1.23 V _RHE with an onset potential of 0.2 V _RHE under 1 sun illumination. The photoanode displays a photostability of over 600 hours in a neutral electrolyte. The additive of Ni ²⁺ in the electrolyte, which efficiently inhibits the dissolution of NiB, can accelerate the photogenerated charge transfer and enhance the water oxidation kinetics. The borate species with B─O bonds act as a promoter of catalyst activity by accelerating proton-coupled electron transfer. The synergy effect of both species suppresses the surface charge recombination and inhibits the photocorrosion of BiVO ₄ .