Origin of the High Performance of GaZrOx/SAPO‐34 Bifunctional OXZEO Catalyst for the Methanol‐Mediated CO Hydrogenation to Light Olefins

Abstract Gallium‐based catalysts have recently gained strong interest for (de)hydrogenation reactions. In this work, we evaluated GaZr mixed oxides associated with SAPO‐34 for the methanol‐mediated syngas conversion to light olefins and confirmed high performance of the mixture. A fundamental approach based on H 2 ‐TPD and in situ DRIFTS techniques were followed to decipher the origin of its high performance and provide insights on the still debated redox mechanism of CO hydrogenation to methanol. A pronounced lability and easy regeneration of OH groups on GaZr oxides were shown to facilitate CO conversion to HCOO* intermediate. Concomitantly, surface reduction under hydrogen leads to formation of oxygen vacancies favoring H 2 dissociation and formation of highly reactive Ga‐H hydrides which further readily hydrogenate HCOO* intermediate to CH 3 O*. The particular property of GaZr oxides making them an optimal component for OXZEO process is its low activity for olefins hydrogenation combined with high ability to generate methanol intermediate.