Upgrading CO2 to sustainable aromatics via perovskite-mediated tandem catalysis

Abstract

Abstract The directional transformation of carbon dioxide (CO 2 ) with renewable hydrogen into specific carbon-heavy products (C 6+ ) of high value presents a sustainable route for net-zero chemical manufacture. However, it is still challenging to simultaneously achieve high activity and selectivity due to the unbalanced CO 2 hydrogenation and C–C coupling rates on complementary active sites in a bifunctional catalyst, thus causing unexpected secondary reaction. Here we report LaFeO 3 perovskite-mediated directional tandem conversion of CO 2 towards heavy aromatics with high CO 2 conversion (> 60%), exceptional aromatics selectivity among hydrocarbons (> 85%), and no obvious deactivation for 1000 hours. This is enabled by disentangling the CO 2 hydrogenation domain from the C-C coupling domain in the tandem system for Iron-based catalyst. Unlike other active Fe oxides showing wide hydrocarbon product distribution due to carbide formation, LaFeO 3 by design is endowed with superior resistance to carburization, therefore inhibiting uncontrolled C–C coupling on oxide and isolating aromatics formation in the zeolite. In-situ spectroscopic evidence and theoretical calculations reveal an oxygenate-rich surface chemistry of LaFeO 3 , that easily escape from the oxide surface for further precise C–C coupling inside zeolites, thus steering CO 2 -HCOOH/H 2 CO-Aromatics reaction pathway to enable a high yield of aromatics.