Toward the Rational Design of More Efficient Mo 2 C Catalysts for Hydrodeoxygenation-Mechanism and Descriptor Identification.

Viable alternatives to scarce and expensive noble-metal-based catalysts are transition-metal carbides such as Mo and W carbides. It has been shown that these are active and selective catalysts in the hydrodeoxygenation of renewable lipid-based feedstocks. However, the reaction mechanism and the structure-activity relationship of these transition-metal carbides have not yet been fully clarified. In this work, the reaction mechanism of butyric acid hydrodeoxygenation (HDO) over molybdenum carbide (Mo 2 C) has been studied comprehensively by means of density functional theory coupled with microkinetic modeling. We identified the rate-determining step to be butanol dissociation: C 4 H 9 *OH + * → C 4 H 9 * + *OH. Then we further explored the possibility to facilitate this step upon heteroatom doping and found that Zr- and Nb-doped Mo 2 C are the most promising catalysts with enhanced HDO catalytic activity. Linear-scaling relationships were established between the electronic and geometrical descriptors of the dopants and the catalytic performance of various doped Mo 2 C catalysts. It was demonstrated that descriptors such as dopants' d-band filling and atomic radius play key roles in governing the catalytic activity. This fundamental understanding delivers practical strategies for the rational design of Mo 2 C-based transition-metal carbide catalysts with improved HDO performance.