The directional transformation of carbon dioxide (CO₂) with renewable hydrogen into specific carbon-heavy products (C₆₊) 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 CO₂ hydrogenation and C–C coupling rates on complementary active sites in a bifunctional catalyst, thus causing unexpected secondary reaction. Here we report LaFeO₃ perovskite-mediated directional tandem conversion of CO₂ towards heavy aromatics with high CO₂ conversion (> 60%), exceptional aromatics selectivity among hydrocarbons (> 85%), and no obvious deactivation for 1000 hours. This is enabled by disentangling the CO₂ 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, LaFeO₃ 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 LaFeO₃, that easily escape from the oxide surface for further precise C–C coupling inside zeolites, thus steering CO₂-HCOOH/H₂CO-Aromatics reaction pathway to enable a high yield of aromatics.

The crystallographic pore sizes of zeolites are substantially smaller than those inferred from catalytic transformation and molecular sieving capabilities, which reflects flexible variation in zeolite opening pores. Using in situ electron microscopy, we imaged the straight channels of ZSM-5 zeolite with benzene as a probe molecule and observed subcell flexibility of the framework. The opening pores stretched along the longest direction of confined benzene molecules with a maximum aspect change of 15%, and thePnmaspace group symmetry of the MFI framework caused adjacent channels to deform. This compensation maintained the stability and rigidity of the overall unit cell within 0.5% deformation. The subcell flexibility originates mainly from the topologically soft silicon-oxygen-silicon hinges between rigid tetrahedral SiO₄units, with inner angles varying from 135° to 153°, as confirmed by ab initio molecular dynamics simulations.

Spontaneous monodispersion of reducible active species (e.g., Fe, Co) and their stabilization in reductive atmospheres remain a key challenge in catalytic syngas chemistry. In this study, we present a series of catalysts including spontaneously monodispersed and enriched Fe on ZnCr₂O₄. Deep investigation shows remarkable performance in the syngas-to-aromatic reaction only when monodispersed Fe coupled with a H-ZSM-5 zeolite. Monodispersed Fe increases the turnover frequency from 0.14 to 0.48 s⁻¹ without sacrificing the record high selectivity of total aromatics (80–90%) at a single pass. The increased activity is ascribed to more efficient activation of CO and H₂ at oxygen vacancy nearest to the isolated Fe site and the prevention of carbide formation. Atomic precise characterization and theoretical calculations shed light on the origin and implications of spontaneous Fe monodispersion, which provide guidance to the design of next-generation catalyst for upgrading small molecules to synthetic fuels and chemicals.