Investigating Deposition Sequence During Synthesis of Pd/Al2O3 Catalysts Modified with Organic Monolayers

Blanchette, Zachary; Zhang, Jing; Yazdi, Sadegh; Griffin, Michael B.; Schwartz, Daniel K.; Medlin, J. Will

doi:10.1039/D1CY02131A

Investigating Deposition Sequence During Synthesis of Pd/Al2O3 Catalysts Modified with Organic Monolayers

Journal Article · 21 February 2022 · Catalysis Science and Technology

DOI:https://doi.org/10.1039/D1CY02131A· OSTI ID:1866766

Blanchette, Zachary; Zhang, Jing; Yazdi, Sadegh; Griffin, Michael B.; Schwartz, Daniel K.; Medlin, J. Will

Modification of supported metal catalysts with self-assembled monolayers (SAMs) has been shown to improve selectivity and turnover frequencies (TOFs) for many catalytic reactions. However, these benefits are often accompanied by a decrease in overall mass activity due to partial blocking of active sites by the monolayers. Therefore, a potential method for increasing site accessibility is to deposit the active metal (e.g., Pd) after deposition of a SAM modifier on the support material. In this work, Pd/Al2O3 catalysts were synthesized using both a conventional, "metal-first" sequence in which the phosphonic acid (PA) SAM was deposited on Pd/Al2O3 and a "SAM-first" technique in which the ligands were deposited onto the support prior to deposition of the metal. Although metal-first catalysts showed a significant increase in TOF during benzyl alcohol HDO, they exhibited only a modest increase in overall mass activity due to a decrease in the number of active sites. Meanwhile, SAM-first catalysts showed similar improvements in TOF and toluene selectivity but exhibited significantly improved HDO rates compared to metal-first catalysts. The rate increase was attributed to reduced site blocking as evidenced by CO chemisorption measurements. Additionally, analysis of catalysts having high Pd loadings using transmission electron microscopy (TEM) showed that SAM-first catalysts generally resulted in lower average particle sizes than traditionally modified and unmodified catalysts, suggesting that precoating the support surface with PAs changes the way that Pd is deposited during incipient wetness, leading here to improved activity.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences, and Biosciences Division

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 1866766

Report Number(s):: NREL/JA-5100-82844; MainId:83617; UUID:7271afee-c5eb-49d5-8eaa-271cbea564c1; MainAdminID:64457

Journal Information:: Catalysis Science and Technology, Vol. 12, Issue 7

Country of Publication:: United States

Language:: English

References (52)

Recent Developments in the Synthesis of Supported Catalysts Munnik, Peter; de Jongh, Petra E.; de Jong, Krijn P. Chemical Reviews, Vol. 115, Issue 14 https://doi.org/10.1021/cr500486u	journal	June 2015
Heterogeneous Catalysis: A Central Science for a Sustainable Future Friend, Cynthia M.; Xu, Bingjun Accounts of Chemical Research, Vol. 50, Issue 3 https://doi.org/10.1021/acs.accounts.6b00510	journal	March 2017
Review of fast pyrolysis of biomass and product upgrading Bridgwater, A. V. Biomass and Bioenergy, Vol. 38, p. 68-94 https://doi.org/10.1016/j.biombioe.2011.01.048	journal	March 2012
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
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
Catalytic hydrodeoxygenation Furimsky, Edward Applied Catalysis A: General, Vol. 199, Issue 2, p. 147-190 https://doi.org/10.1016/S0926-860X(99)00555-4	journal	June 2000
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
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
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
In Situ Generation of Brønsted Acidity in the Pd-I Bifunctional Catalysts for Selective Reductive Etherification of Carbonyl Compounds under Mild Conditions Wu, Dan; Hernández, Willinton Y.; Zhang, Songwei ACS Catalysis, Vol. 9, Issue 4 https://doi.org/10.1021/acscatal.8b04925	journal	February 2019
A review of catalytic upgrading of bio-oil to engine fuels Mortensen, P. M.; Grunwaldt, J.-D.; Jensen, P. A. Applied Catalysis A: General, Vol. 407, Issue 1-2, p. 1-19 https://doi.org/10.1016/j.apcata.2011.08.046	journal	November 2011
Scalable synthesis of selective hydrodeoxygenation inverted Pd@TiO2 nanocatalysts Ranadive, Pinaki; Blanchette, Zachary; Spanos, Alexander Journal of Flow Chemistry, Vol. 11, Issue 3 https://doi.org/10.1007/s41981-021-00171-4	journal	May 2021
Bimetallic effects in the hydrodeoxygenation of meta-cresol on γ-Al2O3 supported Pt–Ni and Pt–Co catalysts Do, Phuong T. M.; Foster, Andrew J.; Chen, Jingguang Green Chemistry, Vol. 14, Issue 5 https://doi.org/10.1039/c2gc16544a	journal	January 2012
Effects of support identity and metal dispersion in supported ruthenium hydrodeoxygenation catalysts Newman, Cody; Zhou, Xiaobo; Goundie, Ben Applied Catalysis A: General, Vol. 477 https://doi.org/10.1016/j.apcata.2014.02.030	journal	May 2014
Interfacial electronic effects control the reaction selectivity of platinum catalysts Chen, Guangxu; Xu, Chaofa; Huang, Xiaoqing Nature Materials, Vol. 15, Issue 5 https://doi.org/10.1038/nmat4555	journal	January 2016
Cross-Linked “Poisonous” Polymer: Thermochemically Stable Catalyst Support for Tuning Chemoselectivity Yun, Seongho; Lee, Songhyun; Yook, Sunwoo ACS Catalysis, Vol. 6, Issue 4 https://doi.org/10.1021/acscatal.5b02613	journal	March 2016
Controlling surface crowding on a Pd catalyst with thiolate self-assembled monolayers Schoenbaum, Carolyn A.; Schwartz, Daniel K.; Medlin, J. Will Journal of Catalysis, Vol. 303 https://doi.org/10.1016/j.jcat.2013.03.012	journal	July 2013
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
Surface molecular imprinting over supported metal catalysts for size-dependent selective hydrogenation reactions Wu, Dan; Baaziz, Walid; Gu, Bang Nature Catalysis, Vol. 4, Issue 7 https://doi.org/10.1038/s41929-021-00649-3	journal	July 2021
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
Phosphonic acid modifiers for enhancing selective hydrodeoxygenation over Pt catalysts: The role of the catalyst support Coan, Patrick D.; Griffin, Michael B.; Ciesielski, Peter N. Journal of Catalysis, Vol. 372 https://doi.org/10.1016/j.jcat.2019.03.011	journal	April 2019
Phosphonic acid promotion of supported Pd catalysts for low temperature vanillin hydrodeoxygenation in ethanol Hao, Pengxiao; Schwartz, Daniel K.; Medlin, J. Will Applied Catalysis A: General, Vol. 561 https://doi.org/10.1016/j.apcata.2018.05.008	journal	July 2018
Effect of Surface Hydrophobicity of Pd/Al ₂ O ₃ on Vanillin Hydrodeoxygenation in a Water/Oil System Hao, Pengxiao; Schwartz, Daniel K.; Medlin, J. Will ACS Catalysis, Vol. 8, Issue 12 https://doi.org/10.1021/acscatal.8b03141	journal	October 2018
Alkylphosphonate Modified Aluminum Oxide Surfaces Hoque, E.; DeRose, J. A.; Kulik, G. The Journal of Physical Chemistry B, Vol. 110, Issue 22 https://doi.org/10.1021/jp061327a	journal	June 2006
Study of the Self-Assembling of n -Octylphosphonic Acid Layers on Aluminum Oxide Hauffman, Tom; Blajiev, Orlin; Snauwaert, Johan Langmuir, Vol. 24, Issue 23 https://doi.org/10.1021/la801978a	journal	December 2008
Control of Molecular Bonding Strength on Metal Catalysts with Organic Monolayers for CO ₂ Reduction Zhang, Jing; Deo, Shyam; Janik, Michael J. Journal of the American Chemical Society, Vol. 142, Issue 11 https://doi.org/10.1021/jacs.9b12980	journal	February 2020
Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers Coan, Patrick D.; Ellis, Lucas D.; Griffin, Michael B. The Journal of Physical Chemistry C, Vol. 122, Issue 12 https://doi.org/10.1021/acs.jpcc.7b12442	journal	March 2018
Organic Modifiers Promote Furfuryl Alcohol Ring Hydrogenation via Surface Hydrogen-Bonding Interactions Coan, Patrick D.; Farberow, Carrie A.; Griffin, Michael B. ACS Catalysis, Vol. 11, Issue 6 https://doi.org/10.1021/acscatal.0c04138	journal	March 2021
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
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
Covalent Surface Modification of Calcium Hydroxyapatite Using n -Alkyl- and n -Fluoroalkylphosphonic Acids D'Andre, Susan C.; Fadeev, Alexander Y. Langmuir, Vol. 19, Issue 19 https://doi.org/10.1021/la027000s	journal	August 2003
Self-Assembled Monolayers Supported on TiO ₂ : Comparison of C ₁₈ H ₃₇ SiX ₃ (X = H, Cl, OCH ₃ ), C ₁₈ H ₃₇ Si(CH ₃ ) ₂ Cl, and C ₁₈ H ₃₇ PO(OH) ₂ Helmy, Roy; Fadeev, Alexander Y. Langmuir, Vol. 18, Issue 23 https://doi.org/10.1021/la0262506	journal	October 2002
Nanostructural Features of Pd/C Catalysts Investigated by Physical Methods: A Reference for Chemisorption Analysis Fagherazzi, Giuliano; Canton, Patrizia; Riello, Pietro Langmuir, Vol. 16, Issue 10 https://doi.org/10.1021/la991463p	journal	May 2000
Pd/CO Average Chemisorption Stoichiometry in Highly Dispersed Supported Pd/γ-Al ₂ O ₃ Catalysts Canton, Patrizia; Fagherazzi, Giuliano; Battagliarin, Marino Langmuir, Vol. 18, Issue 17 https://doi.org/10.1021/la015650a	journal	August 2002
Promotion of Activity and Selectivity by Alkanethiol Monolayers for Pd-Catalyzed Benzyl Alcohol Hydrodeoxygenation Lien, Chih-Heng; Medlin, J. Will The Journal of Physical Chemistry C, Vol. 118, Issue 41 https://doi.org/10.1021/jp507114g	journal	October 2014
Fundamental studies of microscopic wetting on organic surfaces. 1. Formation and structural characterization of a self-consistent series of polyfunctional organic monolayers Nuzzo, Ralph G.; Dubois, Lawrence H.; Allara, David L. Journal of the American Chemical Society, Vol. 112, Issue 2 https://doi.org/10.1021/ja00158a012	journal	January 1990
Carbon-Hydrogen Stretching Frequencies Wiberley, S. E.; Bunce, S. C.; Bauer, W. H. Analytical Chemistry, Vol. 32, Issue 2 https://doi.org/10.1021/ac60158a025	journal	February 1960
Vibrational spectra in the CH stretching region and the structure of the polymethylene chain Snyder, R. G.; Hsu, S. L.; Krimm, S. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 34, Issue 4 https://doi.org/10.1016/0584-8539(78)80167-6	journal	January 1978
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
Systematic Control of the Packing Density of Self-Assembled Monolayers Using Bidentate and Tridentate Chelating Alkanethiols Park, Joon-Seo; Vo, Andy Nguyen; Barriet, David Langmuir, Vol. 21, Issue 7 https://doi.org/10.1021/la0475573	journal	March 2005
Thermal Characterization of Self-Assembled Monolayers of Dialkyl Disulfides Containing the Urea Moiety Shin, Hyeon Suk; Kim, Jang Hoon; Kim, Seung Bin Langmuir, Vol. 23, Issue 21 https://doi.org/10.1021/la7015947	journal	September 2007
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
Stability of Pd nanoparticles on carbon-coated supports under hydrothermal conditions Huo, Jiajie; Johnson, Robert L.; Duan, Pu Catalysis Science & Technology, Vol. 8, Issue 4 https://doi.org/10.1039/C7CY02098H	journal	January 2018
Hydrogenation on Palladium Nanoparticles Supported by Graphene Nanoplatelets Dobrezberger, Klaus; Bosters, Johannes; Moser, Nico The Journal of Physical Chemistry C, Vol. 124, Issue 43 https://doi.org/10.1021/acs.jpcc.0c06636	journal	October 2020
Enhancing Au/TiO ₂ Catalyst Thermostability and Coking Resistance with Alkyl Phosphonic-Acid Self-Assembled Monolayers Jenkins, Alexander H.; Musgrave, Charles B.; Medlin, J. Will ACS Applied Materials & Interfaces, Vol. 11, Issue 44 https://doi.org/10.1021/acsami.9b13170	journal	October 2019
Enhancing sintering resistance of atomically dispersed catalysts in reducing environments with organic monolayers Zhang, Jing; Asokan, Chithra; Zakem, Gregory Green Energy & Environment https://doi.org/10.1016/j.gee.2021.01.022	journal	February 2021
Operando and Kinetic Study of Low-Temperature, Lean-Burn Methane Combustion over a Pd/γ-Al ₂ O ₃ Catalyst Xu, Jing; Ouyang, Like; Mao, Wei ACS Catalysis, Vol. 2, Issue 2 https://doi.org/10.1021/cs200694k	journal	January 2012
Infrared Study of CO Adsorbed on Pd/Al ₂ O ₃ −ZrO ₂ . Effect of Zirconia Added by Impregnation Tiznado, Hugo; Fuentes, Sergio; Zaera, Francisco Langmuir, Vol. 20, Issue 24 https://doi.org/10.1021/la049606h	journal	November 2004
Spectroscopic study of the interaction of carbon monoxide with cationic and metallic palladium in palladium–alumina catalysts Tessier, Didier; Rakai, Ahmed; Bozon-Verduraz, François J. Chem. Soc., Faraday Trans., Vol. 88, Issue 5 https://doi.org/10.1039/FT9928800741	journal	January 1992
Characterization of well faceted palladium nanoparticles supported on alumina by transmission electron microscopy and FT-IR spectroscopy of CO adsorption Di Gregorio, F.; Bisson, L.; Armaroli, T. Applied Catalysis A: General, Vol. 352, Issue 1-2 https://doi.org/10.1016/j.apcata.2008.09.034	journal	January 2009
Synthesis of highly dispersed palladium alumina supported particles: Influence of the particle surface density on physico-chemical properties Benkhaled, M.; Morin, S.; Pichon, C. Applied Catalysis A: General, Vol. 312 https://doi.org/10.1016/j.apcata.2006.06.011	journal	September 2006
CH ₄ Oxidation Activity in Pd and Pt–Pd Bimetallic Catalysts: Correlation with Surface PdO _x Quantified from the DRIFTS Study Jang, Eun Jeong; Lee, Jaekyoung; Oh, Dong Gun ACS Catalysis, Vol. 11, Issue 10 https://doi.org/10.1021/acscatal.1c00156	journal	April 2021

Similar Records

Investigating deposition sequence during synthesis of Pd/Al₂O₃ catalysts modified with organic monolayers

Journal Article · 2022 · Catalysis Science and Technology · OSTI ID:1866621

Blanchette, Zachary; Zhang, Jing; Yazdi, Sadegh; +3 more

Organic Modifiers Promote Furfuryl Alcohol Ring Hydrogenation via Surface Hydrogen-Bonding Interactions

Journal Article · 2021 · ACS Catalysis · OSTI ID:1785252

Coan, Patrick D.; Farberow, Carrie A.; Griffin, Michael B.; +1 more

Controlling Heterogeneous Catalysis with Organic Monolayers on Metal Oxides

Journal Article · 2021 · Accounts of Chemical Research · OSTI ID:1866623

Jenkins, Alexander H.; Medlin, J. Will

Related Subjects

INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalytic reactions
deposition
self-assembled monolayers
turnover frequencies

Investigating Deposition Sequence During Synthesis of Pd/Al2O3 Catalysts Modified with Organic Monolayers

Citation Formats

References (52)

Similar Records

Related Subjects