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Title: Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

Abstract

Here, cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al2O3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivity for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites onmore » the Al2O3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.« less

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [1]
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  1. Univ. of Colorado, Boulder, CO (United States)
  2. 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 Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1433482
Report Number(s):
NREL/JA-5100-71319
Journal ID: ISSN 1932-7447; TRN: US1802537
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 12; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; bi-functional catalysts; catalyst performance; catalytic chemistry; cyclic structures; improved activities; methylene groups; organic monolayers

Citation Formats

Coan, Patrick D., Ellis, Lucas D., Griffin, Michael B., Schwartz, Daniel K., and Medlin, J. Will. Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.7b12442.
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Coan, Patrick D., Ellis, Lucas D., Griffin, Michael B., Schwartz, Daniel K., & Medlin, J. Will. Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers. United States. https://doi.org/10.1021/acs.jpcc.7b12442
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Coan, Patrick D., Ellis, Lucas D., Griffin, Michael B., Schwartz, Daniel K., and Medlin, J. Will. Mon . "Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers". United States. https://doi.org/10.1021/acs.jpcc.7b12442. https://www.osti.gov/servlets/purl/1433482.
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@article{osti_1433482,
title = {Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers},
author = {Coan, Patrick D. and Ellis, Lucas D. and Griffin, Michael B. and Schwartz, Daniel K. and Medlin, J. Will},
abstractNote = {Here, cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al2O3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivity for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al2O3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.},
doi = {10.1021/acs.jpcc.7b12442},
journal = {Journal of Physical Chemistry. C},
number = 12,
volume = 122,
place = {United States},
year = {2018},
month = {3}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.7b12442
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Cited by: 12 works
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Figures / Tables:

Figure 1 Figure 1: (a) Dominant reaction pathways of furfuryl alcohol under hydrogenation conditions over supported Pd catalysts. (b) Bifunctional Brønsted acid−Pd interface prepared by the deposition of phosphonate SAMs having an alkyl tail (e.g., butylphosphonic acid) or CA tail (e.g., 2-phosphonoethanoic acid). Phosphonates are depicted in a monodentate binding configuration, althoughmore » other binding modes are also possible.« less
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    Role of tungsten modifiers in bimetallic catalysts for enhanced hydrodeoxygenation activity and selectivity
    journal, January 2020

    • Rasmussen, Mathew J.; Medlin, J. Will
    • Catalysis Science & Technology, Vol. 10, Issue 2
    • DOI: 10.1039/c9cy02240f
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