Exceptional CO ₂ Hydrogenation to Gasoline Enabled by GaZrO _x /Ga‐ZSM‐5 Tandem Catalyst

ABSTRACT CO ₂ hydrogenation to gasoline offers a promising route for addressing energy challenges and enabling the effective utilization of carbon resources. However, the efficient conversion of CO ₂ to gasoline remains a significant challenge due to insufficient hydrogen activation capacity on existing metal oxide/zeolite tandem catalysts, as well as low selectivity of gasoline among the reaction products. In this work, we develop a tandem catalytic system comprising GaZrO _x and Ga‐substituted ZSM‐5 (Ga‐ZSM‐5) that achieves high CO ₂ conversion and high gasoline yield in CO ₂ hydrogenation. The optimized tandem catalyst, GZO‐700/Ga‐Z5(50), achieves a CO ₂ conversion of 17.2% with a C ₅₊ selectivity of 83.2% at 320°C and 3 MPa, while maintaining low selectivities for CH ₄ (< 1%) and CO (11.7%). The catalyst shows no significant deactivation over 400 h of continuous operation. By tuning the calcination temperature, the GaZrO _x component is optimized to exhibit appropriate Ga‐H coverage and O‐vacancy concentration, which synergistically promotes H ₂ dissociation, H ₂ migration, and CO ₂ activation, leading to enhanced CO ₂ conversion and gasoline production. Furthermore, the incorporation of Ga into the ZSM‐5 framework in place of Al effectively reduces the acid strength and Brønsted/Lewis acid ratio while increasing the acid density, thereby significantly boosting the formation of C ₅₊ hydrocarbons. The decrease in the acid strength of the catalyst also suppresses carbon deposition and, thus results in more than a twofold increase in the catalyst lifetime.