Selectivity descriptors for the direct hydrogenation of CO2 to hydrocarbons during zeolite-mediated bifunctional catalysis

• Published in: Nature communications Vol. 12; no. 1; pp. 5914 - 13
• Main Authors: Ramirez, Adrian, Gong, Xuan, Caglayan, Mustafa, Nastase, Stefan-Adrian F., Abou-Hamad, Edy, Gevers, Lieven, Cavallo, Luigi, Dutta Chowdhury, Abhishek, Gascon, Jorge
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 08.10.2021; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/133; 639/638/298; 639/638/77/887; Alkenes; Aromatic compounds; Carbon dioxide; Catalysis; Catalysts; Computer applications; Humanities and Social Sciences; Hydrocarbons; Hydrogenation; Intermediates; Magnetic resonance spectroscopy; multidisciplinary; Multivariate analysis; NMR; NMR spectroscopy; Nuclear magnetic resonance; Paraffins; Reaction mechanisms; Science; Science (multidisciplinary); Selectivity; Topology; Vapor phases; Zeolites
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-021-26090-5

Cascade processes are gaining momentum in heterogeneous catalysis. The combination of several catalytic solids within one reactor has shown great promise for the one-step valorization of C1-feedstocks. The combination of metal-based catalysts and zeolites in the gas phase hydrogenation of CO 2 leads to a large degree of product selectivity control, defined mainly by zeolites. However, a great deal of mechanistic understanding remains unclear: metal-based catalysts usually lead to complex product compositions that may result in unexpected zeolite reactivity. Here we present an in-depth multivariate analysis of the chemistry involved in eight different zeolite topologies when combined with a highly active Fe-based catalyst in the hydrogenation of CO 2 to olefins, aromatics, and paraffins. Solid-state NMR spectroscopy and computational analysis demonstrate that the hybrid nature of the active zeolite catalyst and its preferred CO 2 -derived reaction intermediates (CO/ester/ketone/hydrocarbons, i.e., inorganic-organic supramolecular reactive centers), along with 10 MR-zeolite topology, act as descriptors governing the ultimate product selectivity. The reaction mechanism of carbon dioxide to high-value hydrocarbons over metal-zeolite bifunctional catalysts remains ambiguous. Here, the authors demonstrate that active zeolite catalysts’ topology and hybrid nature are descriptors; regulating the reaction mechanism and ultimate product selectivity.