Role of Catalyst Support's Physicochemical Properties on Catalytic Transfer Hydrogenation over Palladium Catalysts

Abstract Catalytic transfer hydrogenation (CTH) is a promising reaction for valorisation of bio‐based feedstocks via hydrogenation without needing to use H 2 . Unlike standard hydrogenation, CTH occurs via dehydrogenation (DHD) of a hydrogen donor (H‐donor) and hydrogenation (HYD) of a substrate. Therefore, the “ideal” CTH catalyst must balance the catalysis of both reactions to maximize the hydrogen transfer between H‐donor and substrate with minimal H 2 loss to gas (high atom efficiency). Additionally, the H‐donor must be highly stable to prevent secondary reactions with the substrate. Herein we study the impact of the catalyst's properties on CTH of guaiacol using bicyclohexyl, a liquid organic hydrogen carrier, as a H‐donor. The reaction was promoted by palladium dispersed on three typical support materials (γ‐Al 2 O 3 , MgO, and SiO 2 ). The performance of these catalysts in the conversion of bicyclohexyl and guaiacol was evaluated, allowing to estimate the H‐transfer efficiency, as well as the potential for recycling the spent H‐donor (bicyclohexyl). The apparent activation energies for DHD of bicyclohexyl and HYD of guaiacol revealed that slow DHD combined with fast HYD, as is the case with Pd/MgO, favours hydrogen transfer efficiency and selectivity towards hydrogenated products. In addition, an investigation of the DHD of bicyclohexyl and HYD of guaiacol independently showed that the affinity between the organic molecules and the support significantly impacts CTH. Indeed, Pd/SiO 2 was highly active for both reactions individually and almost inactive for CTH. Consequently, these findings highlight the importance of the interaction between solvent‐substrate‐support in designing catalysts for transfer hydrogenation.