Rebalancing Hydrogenation and Dehydration Performances for Efficient Hydrodeoxygenation of Biomass Derivatives to Match Reaction Temperature-Induced Rate-Determining Step Switch

For reactions with multielementary steps, typically hydrodeoxygenation (HDO), balancing the reaction rate of each step (hydrogenation and dehydration) is crucial to speed up the overall process. However, reaction-condition-induced rate-determining step switch has long been overlooked and misleads our configuration of active sites. In this work, a relay catalysis of PtFe5/WOx and Pt/WOx is applied to facilitate the whole HDO process, in which bimetallic PtFe5/WOx catalyst boosts the hydrogenation step by promoting the adsorption of oxygen-containing intermediates at high temperatures via the oxophilic Fe species and Pt/WOx with more W–OH–W Brønsted acid sites (BAS) facilitates the deoxygenation activity. By balancing hydrogenation and dehydration performances, the relay catalysis system achieves a turnover frequency of 671.5 h–1 in the HDO of m-cresol, 3–18 times higher than that of most reported catalysts. This finding offers caution to the catalyst design based on reaction conditions for reactions with multielementary steps.