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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 BixIn2-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 BixIn2-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. Surface frustrated Lewis pairs (SFLPs) provide a unique class of active sites that enable efficient gas-phase CO2 photocatalysis. How to tailor the reactivity of the SFLPs represents a major challenge, which the authors address here by single-site Bi3+ ion substitution of the SFLPs. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) materials are of considerable interest for catalyzing the heterogeneous conversion of CO2 to synthetic fuels. In this regard, 2D siloxene nanosheets, have escaped thorough exploration, despite being composed of earth-abundant elements. Herein we demonstrate the remarkable catalytic activity, selectivity, and stability of a nickel@siloxene nanocomposite; it is found that this promising catalytic performance is highly sensitive to the location of the nickel component, being on either the interior or the exterior of adjacent siloxene nanosheets. Control over the location of nickel is achieved by employing the terminal groups of siloxene and varying the solvent used during its nucleation and growth, which ultimately determines the distinct reaction intermediates and pathways for the catalytic CO2 methanation. Significantly, a CO2 methanation rate of 100 mmol gNi−1 h−1 is achieved with over 90% selectivity when nickel resides specifically between the sheets of siloxene. There is a strong push to develop new catalysts and supports to convert low-value CO2 into high-value CH4. Here, authors found that the internal or external confinement of Ni on multi-layered siloxene supports determined the reaction pathway, activity, selectivity, and stability in CO2 methanation. [ABSTRACT FROM AUTHOR]