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Title: Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

Abstract

Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo 2C) for the deoxygenation of acetic acid, an abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo 2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
OSTI Identifier:
1239059
Report Number(s):
NREL/JA-5100-64755
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 2; Related Information: ACS Catalysis; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANAYLYTICAL CHEMISTRY; molybdenum carbide; acetic acid; deoxygenation; bio-oil; vapor phase upgrading

Citation Formats

Schaidle, Joshua A., Blackburn, Jeffrey, Farberow, Carrie A., Nash, Connor, Steirer, K. Xerxes, Clark, Jared, Robichaud, David J., and Ruddy, Daniel A. Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity. United States: N. p., 2016. Web. doi:10.1021/acscatal.5b01930.
Schaidle, Joshua A., Blackburn, Jeffrey, Farberow, Carrie A., Nash, Connor, Steirer, K. Xerxes, Clark, Jared, Robichaud, David J., & Ruddy, Daniel A. Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity. United States. doi:10.1021/acscatal.5b01930.
Schaidle, Joshua A., Blackburn, Jeffrey, Farberow, Carrie A., Nash, Connor, Steirer, K. Xerxes, Clark, Jared, Robichaud, David J., and Ruddy, Daniel A. Thu . "Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity". United States. doi:10.1021/acscatal.5b01930. https://www.osti.gov/servlets/purl/1239059.
@article{osti_1239059,
title = {Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity},
author = {Schaidle, Joshua A. and Blackburn, Jeffrey and Farberow, Carrie A. and Nash, Connor and Steirer, K. Xerxes and Clark, Jared and Robichaud, David J. and Ruddy, Daniel A.},
abstractNote = {Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo2C) for the deoxygenation of acetic acid, an abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.},
doi = {10.1021/acscatal.5b01930},
journal = {ACS Catalysis},
number = 2,
volume = 6,
place = {United States},
year = {2016},
month = {1}
}

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