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

Coan, Patrick D.; Ellis, Lucas D.; Griffin, Michael B.; Schwartz, Daniel K.; Medlin, J. Will

doi:10.1021/acs.jpcc.7b12442

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

Journal Article · Mon Mar 05 00:00:00 EST 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b12442· OSTI ID:1433482

Coan, Patrick D. ^[1]; Ellis, Lucas D. ^[1]; Griffin, Michael B. ^[2]; Schwartz, Daniel K. ^[1];

^[1]

Univ. of Colorado, Boulder, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

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.

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Research Organization:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1433482

Report Number(s):: NREL/JA-5100-71319; TRN: US1802537

Journal Information:: Journal of Physical Chemistry. C, Vol. 122, Issue 12; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 20 works

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References (58)

Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates Huber, George W.; Chheda, Juben N.; Barrett, Christopher J. Science, Vol. 308, Issue 5727, p. 1446-1450 https://doi.org/10.1126/science.1111166	journal	June 2005
Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals Chheda, Juben N.; Huber, George W.; Dumesic, James A. Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7164-7183 https://doi.org/10.1002/anie.200604274	journal	September 2007
Role of the Support and Reaction Conditions on the Vapor-Phase Deoxygenation of m -Cresol over Pt/C and Pt/TiO ₂ Catalysts Griffin, Michael B.; Ferguson, Glen A.; Ruddy, Daniel A. ACS Catalysis, Vol. 6, Issue 4 https://doi.org/10.1021/acscatal.5b02868	journal	March 2016
Bifunctional Catalysts for Upgrading of Biomass-Derived Oxygenates: A Review Robinson, Allison M.; Hensley, Jesse E.; Medlin, J. Will ACS Catalysis, Vol. 6, Issue 8 https://doi.org/10.1021/acscatal.6b00923	journal	July 2016
Cooperative catalysis by silica-supported organic functional groups Margelefsky, Eric L.; Zeidan, Ryan K.; Davis, Mark E. Chemical Society Reviews, Vol. 37, Issue 6 https://doi.org/10.1039/b710334b	journal	January 2008
Multifunctional Heterogeneous Catalysts: SBA-15-Containing Primary Amines and Sulfonic Acids Zeidan, Ryan K.; Hwang, Son-Jong; Davis, Mark E. Angewandte Chemie International Edition, Vol. 45, Issue 38 https://doi.org/10.1002/anie.200602243	journal	September 2006
Enhancing Heterogeneous Catalysis through Cooperative Hybrid Organic–Inorganic Interfaces Notestein, Justin M.; Katz, Alexander Chemistry - A European Journal, Vol. 12, Issue 15 https://doi.org/10.1002/chem.200501152	journal	May 2006
The effect of acid–base pairing on catalysis: An efficient acid–base functionalized catalyst for aldol condensation Zeidan, R.; Davis, M. Journal of Catalysis, Vol. 247, Issue 2 https://doi.org/10.1016/j.jcat.2007.02.005	journal	April 2007
DFT Study of Furfural Conversion to Furan, Furfuryl Alcohol, and 2-Methylfuran on Pd(111) Vorotnikov, Vassili; Mpourmpakis, Giannis; Vlachos, Dionisios G. ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs300395a	journal	October 2012
Adsorption and Reaction of Furfural and Furfuryl Alcohol on Pd(111): Unique Reaction Pathways for Multifunctional Reagents Pang, Simon H.; Medlin, J. Will ACS Catalysis, Vol. 1, Issue 10 https://doi.org/10.1021/cs200226h	journal	August 2011
Hydrodeoxygenation of Furfural Over Supported Metal Catalysts: A Comparative Study of Cu, Pd and Ni Sitthisa, Surapas; Resasco, Daniel E. Catalysis Letters, Vol. 141, Issue 6 https://doi.org/10.1007/s10562-011-0581-7	journal	March 2011
Understanding and Controlling Reactivity of Unsaturated Oxygenates and Polyols on Metal Catalysts Medlin, J. Will ACS Catalysis, Vol. 1, Issue 10 https://doi.org/10.1021/cs200336r	journal	August 2011
Experimental and Theoretical Insights into the Hydrogen-Efficient Direct Hydrodeoxygenation Mechanism of Phenol over Ru/TiO ₂ Nelson, Ryan C.; Baek, Byeongjin; Ruiz, Pamela ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01554	journal	October 2015
Hydrodeoxygenation of Phenol over Zirconia-Supported Catalysts: The Effect of Metal Type on Reaction Mechanism and Catalyst Deactivation Teles, Camila A.; Rabelo-Neto, Raimundo C.; Jacobs, Gary ChemCatChem, Vol. 9, Issue 14 https://doi.org/10.1002/cctc.201700047	journal	June 2017
Control of interfacial acid–metal catalysis with organic monolayers Zhang, Jing; Ellis, Lucas D.; Wang, Bingwen Nature Catalysis, Vol. 1, Issue 2 https://doi.org/10.1038/s41929-017-0019-8	journal	January 2018
Renewable Alkanes by Aqueous-Phase Reforming of Biomass-Derived Oxygenates Huber, George W.; Cortright, Randy D.; Dumesic, James A. Angewandte Chemie International Edition, Vol. 43, Issue 12, p. 1549-1551 https://doi.org/10.1002/anie.200353050	journal	March 2004
Inorganic Solid Acids and Their Use in Acid-Catalyzed Hydrocarbon Reactions Corma, A. Chemical Reviews, Vol. 95, Issue 3 https://doi.org/10.1021/cr00035a006	journal	May 1995
Selective Hydrogenolysis of Polyols and Cyclic Ethers over Bifunctional Surface Sites on Rhodium–Rhenium Catalysts Chia, Mei; Pagán-Torres, Yomaira J.; Hibbitts, David Journal of the American Chemical Society, Vol. 133, Issue 32 https://doi.org/10.1021/ja2038358	journal	August 2011
The critical role of water at the gold-titania interface in catalytic CO oxidation Saavedra, J.; Doan, H. A.; Pursell, C. J. Science, Vol. 345, Issue 6204 https://doi.org/10.1126/science.1256018	journal	September 2014
Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis Zope, B. N.; Hibbitts, D. D.; Neurock, M. Science, Vol. 330, Issue 6000 https://doi.org/10.1126/science.1195055	journal	September 2010
Introducing structural sensitivity into adsorption–energy scaling relations by means of coordination numbers Calle-Vallejo, Federico; Loffreda, David; Koper, Marc T. M. Nature Chemistry, Vol. 7, Issue 5 https://doi.org/10.1038/nchem.2226	journal	April 2015
Scaling the rough heights Medlin, J. Will; Montemore, Matthew M. Nature Chemistry, Vol. 7, Issue 5 https://doi.org/10.1038/nchem.2245	journal	April 2015
Recent Advances in Breaking Scaling Relations for Effective Electrochemical Conversion of CO ₂ Li, Yawei; Sun, Qiang Advanced Energy Materials, Vol. 6, Issue 17 https://doi.org/10.1002/aenm.201600463	journal	April 2016
Catalytic upgrading of biomass pyrolysis vapors using transition metal-modified ZSM-5 zeolite Iliopoulou, E. F.; Stefanidis, S. D.; Kalogiannis, K. G. Applied Catalysis B: Environmental, Vol. 127 https://doi.org/10.1016/j.apcatb.2012.08.030	journal	October 2012
Upgrading Pyrolysis Oil over Ni/HZSM-5 by Cascade Reactions Zhao, Chen; Lercher, Johannes A. Angewandte Chemie, Vol. 124, Issue 24 https://doi.org/10.1002/ange.201108306	journal	January 2012
Bifunctional transalkylation and hydrodeoxygenation of anisole over a Pt/HBeta catalyst Zhu, Xinli; Lobban, Lance L.; Mallinson, Richard G. Journal of Catalysis, Vol. 281, Issue 1 https://doi.org/10.1016/j.jcat.2011.03.030	journal	July 2011
Controlled selectivity for palladium catalysts using self-assembled monolayers Marshall, Stephen T.; O’Brien, Marykate; Oetter, Brittany Nature Materials, Vol. 9, Issue 10 https://doi.org/10.1038/nmat2849	journal	September 2010
Asymmetric Catalysis at Chiral Metal Surfaces Mallat, T.; Orglmeister, E.; Baiker, A. Chemical Reviews, Vol. 107, Issue 11 https://doi.org/10.1021/cr0683663	journal	November 2007
Functionalization of Platinum Nanoparticles with l -Proline: Simultaneous Enhancements of Catalytic Activity and Selectivity Schrader, Imke; Warneke, Jonas; Backenköhler, Jana Journal of the American Chemical Society, Vol. 137, Issue 2 https://doi.org/10.1021/ja511349p	journal	January 2015
Control of Metal Catalyst Selectivity through Specific Noncovalent Molecular Interactions Kahsar, Karl R.; Schwartz, Daniel K.; Medlin, J. Will Journal of the American Chemical Society, Vol. 136, Issue 1 https://doi.org/10.1021/ja411973p	journal	December 2013
Controlling the Surface Environment of Heterogeneous Catalysts Using Self-Assembled Monolayers Schoenbaum, Carolyn A.; Schwartz, Daniel K.; Medlin, J. Will Accounts of Chemical Research, Vol. 47, Issue 4 https://doi.org/10.1021/ar500029y	journal	February 2014
Trimethylsilyl functionalization of alumina (γ-Al ₂ O ₃ ) increases activity for 1,2-propanediol dehydration Ellis, L. D.; Pylypenko, S.; Ayotte, S. R. Catalysis Science & Technology, Vol. 6, Issue 14 https://doi.org/10.1039/c6cy00574h	journal	January 2016
Selective Hydrogenation of α,β-Unsaturated Aldehydes Catalyzed by Amine-Capped Platinum-Cobalt Nanocrystals Wu, Binghui; Huang, Huaqi; Yang, Jing Angewandte Chemie International Edition, Vol. 51, Issue 14 https://doi.org/10.1002/anie.201108593	journal	February 2012
Controlling the Surface Reactivity of Titania via Electronic Tuning of Self-Assembled Monolayers Ellis, Lucas D.; Trottier, Ryan M.; Musgrave, Charles B. ACS Catalysis, Vol. 7, Issue 12 https://doi.org/10.1021/acscatal.7b02789	journal	November 2017
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
Performance of B3LYP Density Functional Methods for a Large Set of Organic Molecules Tirado-Rives, Julian; Jorgensen, William L. Journal of Chemical Theory and Computation, Vol. 4, Issue 2 https://doi.org/10.1021/ct700248k	journal	January 2008
6-31G* basis set for third-row atoms Rassolov, Vitaly A.; Ratner, Mark A.; Pople, John A. Journal of Computational Chemistry, Vol. 22, Issue 9 https://doi.org/10.1002/jcc.1058	journal	January 2001
Formation and Structure of Self-Assembled Monolayers Ulman, Abraham Chemical Reviews, Vol. 96, Issue 4, p. 1533-1554 https://doi.org/10.1021/cr9502357	journal	January 1996
Self-Assembly of Carboxyalkylphosphonic Acids on Metal Oxide Powders Pawsey, Shane; Yach, Kimberly; Reven, Linda Langmuir, Vol. 18, Issue 13 https://doi.org/10.1021/la015749h	journal	June 2002
Phosphonate- and Carboxylate-Based Self-Assembled Monolayers for Organic Devices: A Theoretical Study of Surface Binding on Aluminum Oxide with Experimental Support Bauer, Thilo; Schmaltz, Thomas; Lenz, Thomas ACS Applied Materials & Interfaces, Vol. 5, Issue 13 https://doi.org/10.1021/am4008374	journal	June 2013
Self-assembled Monolayers of Alkylphosphonic Acids on Aluminum Oxide Surfaces - A Theoretical Study Luschtinetz, Regina; Oliveira, Augusto F.; Duarte, Hélio A. Zeitschrift für anorganische und allgemeine Chemie, Vol. 636, Issue 8 https://doi.org/10.1002/zaac.201000016	journal	May 2010
An infrared study of pyridine adsorbed on acidic solids. Characterization of surface acidity Parry, E. Journal of Catalysis, Vol. 2, Issue 5 https://doi.org/10.1016/0021-9517(63)90102-7	journal	October 1963
Determination of Integrated Molar Extinction Coefficients for Infrared Absorption Bands of Pyridine Adsorbed on Solid Acid Catalysts Emeis, C. A. Journal of Catalysis, Vol. 141, Issue 2 https://doi.org/10.1006/jcat.1993.1145	journal	June 1993
Molecular dynamics simulations of phosphonic acid–aluminum oxide self-organization and their evolution into ordered monolayers Dietrich, H.; Schmaltz, T.; Halik, M. Physical Chemistry Chemical Physics, Vol. 19, Issue 7 https://doi.org/10.1039/c6cp08681k	journal	January 2017
An evaluation of the performance of density functional theory, MP2, MP4, F4, G2(MP2) and G2 procedures in predicting gas-phase proton affinities Smith, Brian J.; Radom, Leo Chemical Physics Letters, Vol. 231, Issue 4-6 https://doi.org/10.1016/0009-2614(94)01273-3	journal	December 1994
Gas-phase acidities: a comparison of density functional, MP2, MP4, F4, G2(MP2, SVP), G2(MP2) and G2 procedures Smith, Brian J.; Radom, Leo Chemical Physics Letters, Vol. 245, Issue 1 https://doi.org/10.1016/0009-2614(95)00988-g	journal	October 1995
Acid Catalysts in Industrial Hydrocarbon Chemistry Busca, Guido Chemical Reviews, Vol. 107, Issue 11, p. 5366-5410 https://doi.org/10.1021/cr068042e	journal	November 2007
Intramolecular Hydrogen Bonding as a Factor in Determining the K1/K2 Ratios of Dicarboxylic Acids. Eberson, Lennart; Wadsö, Ingemar; Lindberg, Bengt Acta Chemica Scandinavica, Vol. 17 https://doi.org/10.3891/acta.chem.scand.17-1552	journal	January 1963
The Geometry of Intramolecular Hydrogen Bonding in 1,2-Dicarboxylic Acids McCoy, Layton L. Journal of the American Chemical Society, Vol. 89, Issue 7 https://doi.org/10.1021/ja00983a024	journal	March 1967
Intramolecular hydrogen bonding in monoanions of o-phthalic acid and the homologous oxalic acid series in acetonitrile Kolthoff, I. M.; Chantooni, M. K. Journal of the American Chemical Society, Vol. 97, Issue 6 https://doi.org/10.1021/ja00839a015	journal	March 1975
Phosphonic acid adsorption at the TiO2 anatase (101) surface investigated by periodic hybrid HF-DFT computations Nilsing, Mattias; Lunell, Sten; Persson, Petter Surface Science, Vol. 582, Issue 1-3 https://doi.org/10.1016/j.susc.2005.02.044	journal	May 2005
Investigation of vinyl phosphonic acid/hydroxylated α-Al2O3() reaction enthalpies Hector Jr, L. G.; Opalka, S. M.; Nitowski, G. A. Surface Science, Vol. 494, Issue 1 https://doi.org/10.1016/s0039-6028(01)01387-5	journal	November 2001
Infrared Spectra of Alkylphosphonic Acid Bound to Aluminium Surfaces Luschtinetz, Regina; Seifert, Gotthard; Jaehne, Evelin Macromolecular Symposia, Vol. 254, Issue 1 https://doi.org/10.1002/masy.200790068	journal	August 2007
Adsorption of phosphonic and ethylphosphonic acid on aluminum oxide surfaces Luschtinetz, Regina; Oliveira, Augusto F.; Frenzel, Johannes Surface Science, Vol. 602, Issue 7 https://doi.org/10.1016/j.susc.2008.01.035	journal	April 2008
Effects of Thiol Modifiers on the Kinetics of Furfural Hydrogenation over Pd Catalysts Pang, Simon H.; Schoenbaum, Carolyn A.; Schwartz, Daniel K. ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs500598y	journal	August 2014
Directing reaction pathways by catalyst active-site selection using self-assembled monolayers Pang, Simon H.; Schoenbaum, Carolyn A.; Schwartz, Daniel K. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3448	journal	September 2013
Hydrodeoxygenation of Phenol over Pd Catalysts. Effect of Support on Reaction Mechanism and Catalyst Deactivation de Souza, Priscilla M.; Rabelo-Neto, Raimundo C.; Borges, Luiz E. P. ACS Catalysis, Vol. 7, Issue 3 https://doi.org/10.1021/acscatal.6b02022	journal	February 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
bi-functional catalysts
catalyst performance
catalytic chemistry
cyclic structures
improved activities
methylene groups
organic monolayers