CuFeO2 Integrated with Orderly Stacked Multilamellar ZSM-5 Nanosheets for Highly Active and Selective Synthesis of Aromatics from CO2 Hydrogenation

Direct conversion of CO2 to value-added aromatics using renewable hydrogen is gaining significant attention. However, achieving a high aromatic selectivity at high CO2 conversion remains challenging. Herein, we report a high-performance bifunctional catalyst for CO2 hydrogenation to aromatics, integrating CuFeO2 with orderly stacked multilamellar ZSM-5 nanosheets (ML-ZSM-5), synthesized via a facile and low-cost hydrothermal route. This catalyst achieves a high aromatic selectivity of 68.4 and 31.4% light aromatics (BTX: benzene, toluene, and xylene) selectivity at high CO2 conversion of 59.9%, while minimizing CH4 and CO selectivity to 2.8 and 5.4%, respectively. In situ XRD and DRIFTS analyses reveal that CuFeO2 exhibits a high carburization rate, generating abundant iron carbides and active surface CHx species, leading to the production of abundant long-chain olefin intermediates. The ML-ZSM-5 component, with its orderly multilayered nanosheet structure, exhibits great mass transfer and limited external surface acidity. This facilitates rapid diffusion of both olefin intermediates and aromatics, favorably shifting the equilibrium of CO2 hydrogenation and subsequent aromatization, thereby enhancing CO2 conversion and aromatics selectivity. Meanwhile, the efficient diffusion of hydrogen species away from ML-ZSM-5, coupled with their consumption by CuFeO2 in the CO2-FTS reactions, further enhances hydrogenation activity. Hence, a synergistic, “dual-gear conveyor belt” mechanism between the bifunctional components facilitates highly active and selective hydrogenation of CO2 to aromatics. Furthermore, the limited external surface acidity of ML-ZSM-5 also improves the selectivity of BTX. This work offers a promising route to high-performance bifunctional catalysts for the selective hydrogenation of CO2 to aromatics.