Late-Transition-Metal-Modified β-Mo2C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation

Baddour, Frederick G.; Witte, Vanessa A.; Nash, Connor P.; Griffin, Michael B.; Ruddy, Daniel A.; Schaidle, Joshua A.

doi:10.1021/acssuschemeng.7b02544

Title: Late-Transition-Metal-Modified β-Mo₂C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation

Journal Article · Thu Oct 26 00:00:00 EDT 2017 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.7b02544· OSTI ID:1408685

Baddour, Frederick G. ^[1]; Witte, Vanessa A. ^[1]; Nash, Connor P. ^[1]; Griffin, Michael B. ^[1];

^[1]; Schaidle, Joshua A. ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center

Molybdenum carbide has been identified as a promising bifunctional catalyst in the deoxygenation of a variety of pyrolysis vapor model compounds. Although high deoxygenation activity has been demonstrated, complementary hydrogenation activity has been limited, especially for lignin-derived, aromatic model compounds. The ability to control the relative site densities of acidic and hydrogenation functionalities represents a catalyst design challenge for these materials with the goal to improve hydrogenation activity under ex situ catalytic fast pyrolysis (CFP) conditions. Here in this paper, we demonstrate that the addition of Pt and Ni to Mo₂C resulted in an increase in the H*-site density with only a minor decrease in the acid-site density. In contrast, the addition of Pd did not significantly alter the H* or acid site densities. High conversions (>94%) and high selectivities to 0-oxygen products (>80%) were observed in guaiacol deoxygenation under ex situ CFP conditions (350 °C and 0.44 MPa H₂) for all catalysts. Pt addition resulted in the greatest deoxygenation, and site-time yields to hydrogenated products over the Pt/Mo₂C catalyst were increased to 0.048 s^-1 compared to 0.015-0.019 s^-1 for all other catalysts. The Pt/Mo₂C catalyst demonstrated the highest hydrogenation performance, but modification with Ni also significantly enhanced hydrogenation performance, representing a promising lower-cost alternative.

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Research Organization:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1408685

Report Number(s):: NREL/JA-5100-68710

Journal Information:: ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 12; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 33 works

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Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation Murugappan, Karthick; Anderson, Eric M.; Teschner, Detre Nature Catalysis, Vol. 1, Issue 12 https://doi.org/10.1038/s41929-018-0171-9	journal	November 2018
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09 BIOMASS FUELS
catalytic fast pyrolysis
vapor phase upgrading
deoxygenation
hydrogenation
molybdenum carbide
guaiacol

Title: Late-Transition-Metal-Modified β-Mo2C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation

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Title: Late-Transition-Metal-Modified β-Mo₂C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation