No abstract

Surface frustrated Lewis pairs (SFLPs) have been implicated in the gas‐phase heterogeneous (photo)catalytic hydrogenation of CO2 to CO and CH3OH by In2O3−x(OH)y. A key step in the reaction pathway is envisioned to be the heterolysis of H2 on a proximal Lewis acid–Lewis base pair, the SFLP, the chemistry of which is described as In⋅⋅⋅In‐OH + H2 → In‐OH2+⋅⋅⋅In‐H−. The product of the heterolysis, thought to be a protonated hydroxide Lewis base In‐OH2+ and a hydride coordinated Lewis acid In‐H−, can react with CO2 to form either CO or CH3OH. While the experimental and theoretical evidence is compelling for heterolysis of H2 on the SFLP, all conclusions derive from indirect proof, and direct observation remains lacking. Unexpectedly, we have discovered rhombohedral In2O3−x(OH)y can enable dissociation of H2 at room temperature, which allows its direct observation by several analytical techniques. The collected analytical results lean towards the heterolysis rather than the homolysis reaction pathway.

Two-dimensional (2D) materials are of considerable interest for catalyzing the heterogeneous conversion of CO 2 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 CO 2 methanation. Significantly, a CO 2 methanation rate of 100 mmol g Ni −1 h −1 is achieved with over 90% selectivity when nickel resides specifically between the sheets of siloxene.

Catalytic reduction of carbon dioxide is a promising strategy for mitigating global carbon emissions. In particular, the abundant and nontoxic material hydroxyapatite demonstrates high activity at a low cost when its constituent cations are replaced with transition metals, which also enables its catalytic properties to be tailored. Using this method, the facile and scalable synthesis of a coppersubstituted hydroxyapatite catalyst is presented, demonstrating its high activity in the reverse water gas shift reaction. Thorough in situ characterization using X-ray absorption and Fourier transform infrared spectroscopic methods provides unrivaled insight into both the structure of the active catalyst and the speciation of reaction intermediates. It is thus shown that this copper-substituted hydroxyapatite catalyst is an exemplary candidate for use in large-scale carbon dioxide reduction systems.