Catalytic Confinement Engineering for CO ₂ Conversion: From Catalytic Microenvironments to Sustainable Aviation Fuels

The efficient conversion of CO 2 into sustainable fuels remains one of the most demanding challenges in catalysis and energy research. Beyond the discovery of new materials, recent progress reveals that the decisive factor governing activity and selectivity pertains to the microenvironment of the reaction, how space, charge, and molecular motion are confined and regulated. This work integrates mechanistic understanding from electrochemical CO 2 reduction and thermocatalytic hydrogenation to establish a unified perspective on confinement engineering. By manipulating spatial confinement, local electric fields, and electronic structures, catalytic interfaces evolve from passive surfaces into dynamic microreactors capable of stabilizing intermediates and directing multi‐electron reactions. Experimental and theoretical studies on Cu‐, Fe‐, and Na‐promoted systems demonstrate that hierarchical confinement enhances C–C coupling, regulates proton–electron transfer (ET), and maintains structural integrity over long‐term operation. These effects collectively enable direct CO 2 hydrogenation to jet‐fuel‐range hydrocarbons (C 8 –C 16 ) with balanced olefin–paraffin distributions under mild conditions. The emerging picture reframes catalyst design as an environmental control problem wherein one can achieve programmable selectivity and stability by engineering active sites rather than solely relying on material composition optimization. This confinement‐driven strategy offers a blueprint for constructing adaptive catalytic ecosystems that transform CO 2 into high‐energy fuels, bridging molecular‐scale reactivity with global carbon neutrality.