Nanostructure of nickel-promoted indium oxide catalysts drives selectivity in CO<sub>2</sub> hydrogenation.

Frei, Matthias S; Mondelli, Cecilia; García-Muelas, Rodrigo; Morales-Vidal, Jordi; Philipp, Michelle; Safonova, Olga V; López, Núria; Stewart, Joseph A et al. · Nat Commun · 2021

basic_science · Level V

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Abstract

Metal promotion in heterogeneous catalysis requires nanoscale-precision architectures to attain maximized and durable benefits. Herein, we unravel the complex interplay between nanostructure and product selectivity of nickel-promoted In<sub>2</sub>O<sub>3</sub> in CO<sub>2</sub> hydrogenation to methanol through in-depth characterization, theoretical simulations, and kinetic analyses. Up to 10 wt.% nickel, InNi<sub>3</sub> patches are formed on the oxide surface, which cannot activate CO<sub>2</sub> but boost methanol production supplying neutral hydrogen species. Since protons and hydrides generated on In<sub>2</sub>O<sub>3</sub> drive methanol synthesis rather than the reverse water-gas shift but radicals foster both reactions, nickel-lean catalysts featuring nanometric alloy layers provide a favorable balance between charged and neutral hydrogen species. For nickel contents >10 wt.%, extended InNi<sub>3</sub> structures favor CO production and metallic nickel additionally present produces some methane. This study marks a step ahead towards green methanol synthesis and uncovers chemistry aspects of nickel that shall spark inspiration for other catalytic applications.