Efficient CO ₂ Hydrogenation to Aviation Kerosene over Oxide-Zeolite Tandem Catalysts through <i>p-p</i> Orbital Overlap Manipulation

CO 2 hydrogenation to kerosene-range aviation fuels over oxide-zeolite (OX-ZEO) tandem catalysts is a promising route. Improving CO 2 hydrogenation performance requires precise tuning of the oxide electronic structure because it governs the adsorption strength of key reactants and intermediates. In this work, we propose a p-p orbital overlap manipulation strategy to promote CO 2 hydrogenation over the OX-ZEO tandem catalyst. As a proof of concept, we construct a p-block In-incorporated tetragonal solid solution oxide (InZnZrO x ) and couple it with HZSM-5 to obtain the InZnZrO x /HZSM-5 tandem catalyst, employing the asymmetric In-O-M motifs (M = Zn, Zr) as the model system to clarify the role of p-p (In 5p -O 2p ) orbital overlap in enhancing the catalytic activity of CO 2 hydrogenation. The optimized tandem catalyst delivers 81.7% selectivity to C 8 -C 15 hydrocarbons, a space-time yield of 16.4 g·kg cat −1 h −1, and stable operation for more than 100 h. Theoretical calculation reveals that such an enhanced p-p orbital overlap manipulation strategy can reduce the Zr−O bond covalency and elevate the d -band center of InZnZrO x, thus boosting oxygen vacancy formation and CO 2 /H 2 activation. This work opens avenues for rational design of OX-ZEO tandem catalysts and in-depth structure−activity relationship analysis of CO 2 hydrogenation to kerosene-range fuels.