The thermocatalytic conversion of carbon dioxide (CO2) into valuable hydrocarbons presents a promising solution for mitigating anthropogenic CO2 emissions while producing drop‐in replacements for fossil‐derived products. Among the two tandem mechanisms for the direct hydrogenation of CO2, the methanol synthesis coupled with the methanol to hydrocarbon (MTH) reaction offers an improvement over the reverse water‐gas shift coupled with Fischer‐Tropsch synthesis reaction (RWGS‐FTS), as it is not limited Anderson‐Schulz‐Flory distribution and yields higher selectivity towards specific products (e.g., olefins, aromatics, higher hydrocarbons). Herein, we focus on the recent progress achieved through this pathway and outline the existing knowledge gaps. We discuss the challenges involved in the process and highlight the key descriptors in the selection of catalyst components. Finally, we present several potential solutions to circumvent the current challenges, aiming to expedite the advancement of this route toward an efficient CO2 hydrogenation process.
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