Title: Identification of Active Metal Carbide and Nitride Catalytic Facets for Hydrodeoxygenation Reactions

Abstract

The catalytic hydrodeoxygenation (HDO) reaction is of considerable interest for biomass conversion to valuable chemicals and fuels, where one of the critical bottlenecks is the lack of cost-effective and efficient catalysts. To discover cost-efficient catalysts for the HDO reaction, we employed a density functional theory-based hierarchical catalyst design strategy based on catalytic descriptors, reaction energy profiles, and microkinetic modeling (MKM). We focused on the carbide and nitride catalyst space, for which we calculated 121 catalyst surfaces of Mo₂C, MoC, Mo₂N, W₂C, NbC, VC, VN, and NbN catalysts. Based on the computed surface energies, reaction energies of oxygen removal, carbon binding strength, and the surface area of nanoparticles, the likely active facets are the Mo₂C(111), MoC(011), VN(100), Mo₂N(001), Mo₂N(011), and Mo₂N(100) surfaces. Further, detailed energy profiles were obtained, and MKM was performed for a model reaction (glycolaldehyde + 2H₂. ethylene + 2H₂O) on the Mo₂C(111), VN(100), and MoC(100) surfaces. Based on the computed volcano map obtained from MKM, the predicted active facets for this HDO reaction are the Mo₂C(111), MoC(011), VN(011), Mo₂N(001), Mo₂N(011), and Mo₂N(100) surfaces. Additionally, none of the carbide and nitride catalyst surfaces are located in the optimal catalytic activity part. Therefore, it is essential to modify the catalystmore » via adding dopants or alloying to improve the catalytic activity. Catalytic modifications that can destabilize the surface adsorption of O*/H₂O* and decrease the energy barriers of O-H bond formation are recommended to facilitate the HDO on the carbide and nitride catalysts. These a priori investigations provide guidelines for future low-cost HDO catalyst development.« less

Authors:

Zhou, Mingxia  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-1896-1024"

Doan, Hieu A. ^[1]; Curtiss, Larry A.  ^[1];

• Search DOE PAGES for author "Curtiss, Larry A."
• Search DOE PAGES for ORCID "0000-0001-8855-8006"

Assary, Rajeev S.  ^[1]

• Search DOE PAGES for author "Assary, Rajeev S."
• Search DOE PAGES for ORCID "0000-0002-9571-3307"

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+ Show Author Affiliations

1. Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:

Tue Apr 20 00:00:00 EDT 2021

Research Org.:

Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE)

OSTI Identifier:

1797905

Grant/Contract Number:  

AC02-06CH11357

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Physical Chemistry. C

Additional Journal Information:

Journal Volume: 125; Journal Issue: 16; Journal ID: ISSN 1932-7447

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; density functional theory; glycolaldehyde; hydrodeoxygenation; metal carbides; metal nitrides; microkinetic modeling