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Title: Composition-directed Fe X Mo 2-XP bimetallic catalysts for hydrodeoxygenation reactions

Abstract

The development of task-specific bimetallic phosphide catalysts can be accomplished by exploiting the electronic and bi-functional effects of multiple metal combinations, thus providing materials with tunable catalytic properties. Here, we present the modulation of metal compositions (i.e., Fe and Mo) in the synthesis of FeXMo 2-XP (0.88 ≤ X ≤ 1.55), leading to a series of iso-structural, orthorhombic Fe XMo2-XP catalysts via reduction at 750 °C. Hydrodeoxygenation of phenol was selected as a probe reaction to showcase the effect of metal composition on the catalytic performance. In particular, catalysts with Fe compositions between 0.99 and 1.14 (i.e., Fe0. 99Mo 1.01P and Fe 1.14Mo 0.86P) exhibited high selectivities to C–O bond cleavage of phenol with H2 to form benzene. The catalysts with the highest selectivities to C–O scission also exhibited the highest acidity as determined from NH 3 temperature programmed desorption experiments. Density functional theory (DFT) calculations indicate the high Lewis acidity for the ~1:1 Fe:Mo compositions resulted from a greater charge separation between metallic species and P species. These compositions led to greater selectivities to benzene due to desired coordination environment of the phenol on catalytic surface, as evidenced by both DFT calculations and a time on stream study usingmore » a benzonitrile poison. Enhanced TOFs were also observed with catalysts exhibiting greater Lewis acid character, which reduce the activation energy required to cleave the C–O bond of phenol, as evidenced by DFT calculations. This structure–property study highlights the effects of metal composition in bimetallic phosphides to enhance the activity and selectivity for C–O bond cleavage reactions.« less

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemical and Biomolecular Engineering; University of Notre Dame; 182 Fitzpatrick Hall; Indiana 46556; USA
  2. Dave C. Swalm School of Chemical Engineering and Center for Advanced Vehicular Systems; Mississippi State University; USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1492848
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 7; Journal Issue: 9; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Rensel, Dallas J., Kim, Jongsik, Jain, Varsha, Bonita, Yolanda, Rai, Neeraj, and Hicks, Jason C. Composition-directed Fe X Mo2-XP bimetallic catalysts for hydrodeoxygenation reactions. United States: N. p., 2017. Web. doi:10.1039/c7cy00324b.
Rensel, Dallas J., Kim, Jongsik, Jain, Varsha, Bonita, Yolanda, Rai, Neeraj, & Hicks, Jason C. Composition-directed Fe X Mo2-XP bimetallic catalysts for hydrodeoxygenation reactions. United States. doi:10.1039/c7cy00324b.
Rensel, Dallas J., Kim, Jongsik, Jain, Varsha, Bonita, Yolanda, Rai, Neeraj, and Hicks, Jason C. Sun . "Composition-directed Fe X Mo2-XP bimetallic catalysts for hydrodeoxygenation reactions". United States. doi:10.1039/c7cy00324b.
@article{osti_1492848,
title = {Composition-directed Fe X Mo2-XP bimetallic catalysts for hydrodeoxygenation reactions},
author = {Rensel, Dallas J. and Kim, Jongsik and Jain, Varsha and Bonita, Yolanda and Rai, Neeraj and Hicks, Jason C.},
abstractNote = {The development of task-specific bimetallic phosphide catalysts can be accomplished by exploiting the electronic and bi-functional effects of multiple metal combinations, thus providing materials with tunable catalytic properties. Here, we present the modulation of metal compositions (i.e., Fe and Mo) in the synthesis of FeXMo2-XP (0.88 ≤ X ≤ 1.55), leading to a series of iso-structural, orthorhombic FeXMo2-XP catalysts via reduction at 750 °C. Hydrodeoxygenation of phenol was selected as a probe reaction to showcase the effect of metal composition on the catalytic performance. In particular, catalysts with Fe compositions between 0.99 and 1.14 (i.e., Fe0.99Mo1.01P and Fe1.14Mo0.86P) exhibited high selectivities to C–O bond cleavage of phenol with H2 to form benzene. The catalysts with the highest selectivities to C–O scission also exhibited the highest acidity as determined from NH3 temperature programmed desorption experiments. Density functional theory (DFT) calculations indicate the high Lewis acidity for the ~1:1 Fe:Mo compositions resulted from a greater charge separation between metallic species and P species. These compositions led to greater selectivities to benzene due to desired coordination environment of the phenol on catalytic surface, as evidenced by both DFT calculations and a time on stream study using a benzonitrile poison. Enhanced TOFs were also observed with catalysts exhibiting greater Lewis acid character, which reduce the activation energy required to cleave the C–O bond of phenol, as evidenced by DFT calculations. This structure–property study highlights the effects of metal composition in bimetallic phosphides to enhance the activity and selectivity for C–O bond cleavage reactions.},
doi = {10.1039/c7cy00324b},
journal = {Catalysis Science and Technology},
issn = {2044-4753},
number = 9,
volume = 7,
place = {United States},
year = {2017},
month = {1}
}

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