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Title: Deoxygenation of Palmitic Acid on Unsupported Transition-Metal Phosphides

Abstract

Abstract Highly active bulk transition metal phosphides (WP, MoP, and Ni2P) were synthesized for the catalytic hydrodeoxygenation of palmitic acid, hexadecanol, hexadecanal, and microalgae oil. The specific activities positively correlated with the concentration of exposed metal sites, although the relative rates changed with temperature due to activation energies varying from 57 kJ·mol-1 for MoP to 142 kJ·mol-1 for WP. The reduction of the fatty acid to the aldehyde occurs through a Langmuir-Hinshelwood mechanism, where the rate-determining step is the addition of the second H to the hydrocarbon. On WP, the conversion of palmitic acid proceeds via R-CH2COOH R-CH2CHO R-CH2CH2OH R-CHCH2 R-CH2CH3 (hydrodeoxygenation). Decarbonylation of the intermittently formed aldehyde (R-CH2COOH R-CH2CHO R-CH3) was an important pathway on MoP and Ni2P. Conversion via dehydration to a ketene, followed by its decarbonylation occurred only on Ni2P. The rates of alcohol dehydration (R-CH2CH2OH R-CHCH2) correlate with the concentration of Lewis acid sites of the phosphides. Acknowledgements The authors would like to thank Roel Prins for the critical discussion of the results. We are also grateful to Xaver Hecht for technical support. Funding by the German Federal Ministry of Food and Agriculture in the framework of the Advanced Biomass Value project (03SF0446A) is gratefully acknowledged.more » J.A.L. acknowledges support for his contribution by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for exploring non-oxidic supports for deoxygenation reactions.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [2]
  1. Technische Universität München, Department of Chemistry, Catalysis Research Center, Lichtenbergstraße 4, 85748 Garching, Germany
  2. Technische Universität München, Department of Chemistry, Catalysis Research Center, Lichtenbergstraße 4, 85748 Garching, Germany; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352 (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1398207
Report Number(s):
PNNL-SA-125374
Journal ID: ISSN 2155-5435; KC0302010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Catalysis; Journal Volume: 7; Journal Issue: 9
Country of Publication:
United States
Language:
English
Subject:
Hydrodeoxygenation; Ni2P; MoP; Transition metal phosphides; Bio-oil; Unsupported catalysts

Citation Formats

Peroni, Marco, Lee, Insu, Huang, Xiaoyang, Baráth, Eszter, Gutiérrez, Oliver Y., and Lercher, Johannes A.. Deoxygenation of Palmitic Acid on Unsupported Transition-Metal Phosphides. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b01294.
Peroni, Marco, Lee, Insu, Huang, Xiaoyang, Baráth, Eszter, Gutiérrez, Oliver Y., & Lercher, Johannes A.. Deoxygenation of Palmitic Acid on Unsupported Transition-Metal Phosphides. United States. doi:10.1021/acscatal.7b01294.
Peroni, Marco, Lee, Insu, Huang, Xiaoyang, Baráth, Eszter, Gutiérrez, Oliver Y., and Lercher, Johannes A.. Fri . "Deoxygenation of Palmitic Acid on Unsupported Transition-Metal Phosphides". United States. doi:10.1021/acscatal.7b01294.
@article{osti_1398207,
title = {Deoxygenation of Palmitic Acid on Unsupported Transition-Metal Phosphides},
author = {Peroni, Marco and Lee, Insu and Huang, Xiaoyang and Baráth, Eszter and Gutiérrez, Oliver Y. and Lercher, Johannes A.},
abstractNote = {Abstract Highly active bulk transition metal phosphides (WP, MoP, and Ni2P) were synthesized for the catalytic hydrodeoxygenation of palmitic acid, hexadecanol, hexadecanal, and microalgae oil. The specific activities positively correlated with the concentration of exposed metal sites, although the relative rates changed with temperature due to activation energies varying from 57 kJ·mol-1 for MoP to 142 kJ·mol-1 for WP. The reduction of the fatty acid to the aldehyde occurs through a Langmuir-Hinshelwood mechanism, where the rate-determining step is the addition of the second H to the hydrocarbon. On WP, the conversion of palmitic acid proceeds via R-CH2COOH R-CH2CHO R-CH2CH2OH R-CHCH2 R-CH2CH3 (hydrodeoxygenation). Decarbonylation of the intermittently formed aldehyde (R-CH2COOH R-CH2CHO R-CH3) was an important pathway on MoP and Ni2P. Conversion via dehydration to a ketene, followed by its decarbonylation occurred only on Ni2P. The rates of alcohol dehydration (R-CH2CH2OH R-CHCH2) correlate with the concentration of Lewis acid sites of the phosphides. Acknowledgements The authors would like to thank Roel Prins for the critical discussion of the results. We are also grateful to Xaver Hecht for technical support. Funding by the German Federal Ministry of Food and Agriculture in the framework of the Advanced Biomass Value project (03SF0446A) is gratefully acknowledged. J.A.L. acknowledges support for his contribution by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for exploring non-oxidic supports for deoxygenation reactions.},
doi = {10.1021/acscatal.7b01294},
journal = {ACS Catalysis},
number = 9,
volume = 7,
place = {United States},
year = {Fri Aug 18 00:00:00 EDT 2017},
month = {Fri Aug 18 00:00:00 EDT 2017}
}