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Determining the Role of Synthesis and Reaction Conditions on the Exposed Surface and Shape of ..beta..-Mo2C Catalysts

Conference ·
OSTI ID:1870118
The production of drop-in quality biofuels typically can be achieved through catalytic fast pyrolysis (CFP) of biomass, followed by hydrodeoxygenation (HDO) of the vapor-phase product to reduce the oxygen content and stabilize the bio-oil product. To favor selectivity toward desired deoxygenation products, bifunctional catalysts with both acidic and hydrogenation sites are often employed. Due to both its oxophilicity and its ability to promote hydrogenation reactions, molybdenum carbide catalysts have shown promise for promoting the HDO of CFP vapors. However, the surface structure and composition of carbide catalyst particles are not well understood, precluding the establishment of fundamental structure-function relationships needed for the rational development of molybdedum carbide for HDO, as well as other reactions. For orthorhombic ..beta..-Mo2C, the (100) facet is largely studied for computational surface-reaction analyses, possibly due to its similarities with the close-packed (111) facet of noble-metal catalysts. However, it has previously been postulated through ab initio thermodynamic studies that the (111), (110), and (011) facets are most stable, though there is no consensus. Furthermore, while a majority of previous surface stability analyses of ..beta..-Mo2C focus on bulk terminations, the highly carburizing synthesis conditions and the use of ..beta..-Mo2C in carbon-containing reaction applications could introduce non-stoichiometric coverages of surface carbon. As such, this study uses ab initio thermodynamics calculations to assess the relative surface stability of the low-index facets of ..beta..-Mo2C, including consideration of varying the coverage of surface carbon. From this information, Wulff constructions are utilized to predict the synthesis and reaction condition-dependent shape and surface carbon composition of ..beta..-Mo2C catalyst particles.
Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
DOE Contract Number:
AC36-08GO28308;
OSTI ID:
1870118
Report Number(s):
NREL/PO-5100-80708; MainId:77492; UUID:dfeb4435-b7b1-4759-afae-c8b311f16313; MainAdminID:64578
Conference Information:
Presented at the ACS Fall 2021 Meeting, 22-26 August 2021, Atlanta, Georgia
Country of Publication:
United States
Language:
English