Revealing the Potential of Bimetallic Carbide Catalysts for Upgrading Biomass‐Derived Bio‐Oil: A First Principles‐Based Investigation Using Representative Bio‐Oil Constituents

Abstract Bimetallic carbides, especially based on molybdenum carbide, proved to be a promising hydrodeoxygenation (HDO) catalyst, with enhanced selectivity towards C─O bonds cleavage. However, catalysts are generally investigated using limited model components derived from only one of the biopolymers in biomass (either lignin or carbohydrates), therefore, HDO of raw biomass‐derived bio‐oil still remains a challenge, as it contains molecules of different functionalities. This paper presents a systematic comparison of the monometallic carbide, Mo 2 C, with the novel bimetallic carbide incorporating W using representative bio‐oil components of different functionalities and derived from different bio‐polymers components of biomass. We employed quantum mechanical investigation to reveal that the W‐doped Mo 2 C carbide (MoWC) catalyst with increased oxophilicity, owing to tungsten incorporation, can perform HDO of real bio‐oil more effectively in comparison to its monometallic counterpart (Mo 2 C) using six substrates representing different components of bio‐oil. We showed MoWC can selectively cleave both single/double (C─O/C═O) bonds with similar barriers in comparison to Mo 2 C which can only selectively cleave single C─O bonds. This observation was consistent for 5‐HMF, Acetic acid, and Methyl Glyoxal. We also showed that MoWC outperforms its metallic counterpart Mo 2 C in the HDO for aromatic and carbohydrates components.