Transformation of atomically dispersed platinum in SAPO-37 into platinum clusters: catalyst for ethylene hydrogenation
Abstract
Atomically dispersed supported platinum catalysts were synthesized by the reaction of Pt(acac)2 (acac = acetylacetonato) with the silicoaluminophosphate molecular sieve SAPO-37, with infrared spectra showing that the reaction involved SAPO OH groups. Extended X-ray absorption fine structure (EXAFS) spectra show that, after heating in air to 623 K, each platinum atom on average was bonded to approximately two oxygen atoms of the SAPO support, with no evidence of platinum clusters. X-ray absorption near edge spectra (XANES) indicate a platinum formal oxidation state of approximately +2. Here, these supported mononuclear species lacked catalytic activity for ethylene hydrogenation at 1 bar and room temperature, but activity arose during catalysis in a once-through flow reactor/X-ray absorption spectroscopy cell, as the XANES white line intensity decreased, indicating reduction of the platinum, and the EXAFS-determined Pt–Pt coordination number (CN) increased from essentially zero to 2.7 ± 0.5 after 2 h, indicating the formation of platinum clusters of only a few atoms each. The data indicate the almost instantaneous formation of the clusters and identify them as the catalytically active species. Subsequent exposure of the catalyst to ethylene as in situ EXAFS and XANES data were recorded led to a decrease in the Pt–Pt coordination numbermore »
- Authors:
-
- University of California, Davis, CA (United States)
- Zeolyst International, Conshohocken, PA (United States)
- University of California, Davis, CA (United States); Chevron Technical Center, Richmond, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of California, Davis, CA (United States); Stanford Univ., CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE
- OSTI Identifier:
- 1978773
- Alternate Identifier(s):
- OSTI ID: 1812825
- Grant/Contract Number:
- FG02-04ER15513; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysis Science and Technology
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 20; Journal ID: ISSN 2044-4753
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; SAPO-37; ethylene hydrogenation; platinum complex catalyst; platinum clusters; molecular sieve
Citation Formats
Perez-Aguilar, Jorge E., Hughes, James T., Chen, Cong-Yan, and Gates, Bruce C. Transformation of atomically dispersed platinum in SAPO-37 into platinum clusters: catalyst for ethylene hydrogenation. United States: N. p., 2021.
Web. doi:10.1039/d1cy01216a.
Perez-Aguilar, Jorge E., Hughes, James T., Chen, Cong-Yan, & Gates, Bruce C. Transformation of atomically dispersed platinum in SAPO-37 into platinum clusters: catalyst for ethylene hydrogenation. United States. https://doi.org/10.1039/d1cy01216a
Perez-Aguilar, Jorge E., Hughes, James T., Chen, Cong-Yan, and Gates, Bruce C. Tue .
"Transformation of atomically dispersed platinum in SAPO-37 into platinum clusters: catalyst for ethylene hydrogenation". United States. https://doi.org/10.1039/d1cy01216a. https://www.osti.gov/servlets/purl/1978773.
@article{osti_1978773,
title = {Transformation of atomically dispersed platinum in SAPO-37 into platinum clusters: catalyst for ethylene hydrogenation},
author = {Perez-Aguilar, Jorge E. and Hughes, James T. and Chen, Cong-Yan and Gates, Bruce C.},
abstractNote = {Atomically dispersed supported platinum catalysts were synthesized by the reaction of Pt(acac)2 (acac = acetylacetonato) with the silicoaluminophosphate molecular sieve SAPO-37, with infrared spectra showing that the reaction involved SAPO OH groups. Extended X-ray absorption fine structure (EXAFS) spectra show that, after heating in air to 623 K, each platinum atom on average was bonded to approximately two oxygen atoms of the SAPO support, with no evidence of platinum clusters. X-ray absorption near edge spectra (XANES) indicate a platinum formal oxidation state of approximately +2. Here, these supported mononuclear species lacked catalytic activity for ethylene hydrogenation at 1 bar and room temperature, but activity arose during catalysis in a once-through flow reactor/X-ray absorption spectroscopy cell, as the XANES white line intensity decreased, indicating reduction of the platinum, and the EXAFS-determined Pt–Pt coordination number (CN) increased from essentially zero to 2.7 ± 0.5 after 2 h, indicating the formation of platinum clusters of only a few atoms each. The data indicate the almost instantaneous formation of the clusters and identify them as the catalytically active species. Subsequent exposure of the catalyst to ethylene as in situ EXAFS and XANES data were recorded led to a decrease in the Pt–Pt coordination number to 1.6 ± 0.3 and an increase in the white line intensity, indicating partial oxidative fragmentation of the clusters by ethylene. Platinum clusters in SAPO-37 formed in separate experiments by exposure to H2 prior to catalysis were also catalytically active for ethylene hydrogenation. Here, the data thus show how to dial in the catalytic activity by forming platinum clusters by exposure of mononuclear platinum to H2 and how to dial back the activity by oxidative fragmentation of the clusters by reaction with ethylene, all under mild conditions; the ethylene : H2 ratio of the reactant gas determines the average platinum nuclearity and thus the catalytic activity.},
doi = {10.1039/d1cy01216a},
journal = {Catalysis Science and Technology},
number = 20,
volume = 11,
place = {United States},
year = {Tue Aug 03 00:00:00 EDT 2021},
month = {Tue Aug 03 00:00:00 EDT 2021}
}
Works referenced in this record:
Regioselective Generation of Single‐Site Iridium Atoms and Their Evolution into Stabilized Subnanometric Iridium Clusters in MWW Zeolite
journal, August 2020
- Liu, Lichen; Lopez‐Haro, Miguel; Meira, Debora M.
- Angewandte Chemie International Edition, Vol. 59, Issue 36
Preparation of Highly Dispersed Pt Particles in Zeolite Y with a Narrow Particle Size Distribution: Characterization by Hydrogen Chemisorption, TEM, EXAFS Spectroscopy, and Particle Modeling
journal, October 2001
- de Graaf, J.; van Dillen, A. J.; de Jong, K. P.
- Journal of Catalysis, Vol. 203, Issue 2
Uniformity Is Key in Defining Structure–Function Relationships for Atomically Dispersed Metal Catalysts: The Case of Pt/CeO 2
journal, December 2019
- Resasco, Joaquin; DeRita, Leo; Dai, Sheng
- Journal of the American Chemical Society, Vol. 142, Issue 1
Delicate Distinction between OH Groups on Proton-Exchanged H-Chabazite and H-SAPO-34 Molecular Sieves
journal, October 2015
- Halasz, Istvan; Moden, Bjorn; Petushkov, Anton
- The Journal of Physical Chemistry C, Vol. 119, Issue 42
A Bifunctional Mechanism for Ethene Dimerization: Catalysis by Rhodium Complexes on Zeolite HY in the Absence of Halides
journal, April 2011
- Serna, Pedro; Gates, B. C.
- Angewandte Chemie International Edition, Vol. 50, Issue 24
Real-Time Characterization of Formation and Breakup of Iridium Clusters in Highly Dealuminated Zeolite Y
journal, August 2008
- Uzun, Alper; Gates, Bruce C.
- Angewandte Chemie International Edition, Vol. 47, Issue 48
Effect of the Preparation of Pt-Modified Zeolite Beta-Bentonite Extrudates on Their Catalytic Behavior in n -Hexane Hydroisomerization
journal, June 2019
- Vajglová, Zuzana; Kumar, Narendra; Peurla, Markus
- Industrial & Engineering Chemistry Research, Vol. 58, Issue 25
High-Surface-Area Catalyst Design: Synthesis, Characterization, and Reaction Studies of Platinum Nanoparticles in Mesoporous SBA-15 Silica †
journal, February 2005
- Rioux, R. M.; Song, H.; Hoefelmeyer, J. D.
- The Journal of Physical Chemistry B, Vol. 109, Issue 6
SAPO-37: the implications of structure flexibility on acidity
journal, January 1993
- Corma, Avelino; Fornes, Vicente; Pérez-Pariente, Joaquin
- J. Chem. Soc., Chem. Commun., Issue 8
Zeolite- and MgO-supported rhodium complexes and rhodium clusters: Tuning catalytic properties to control carbon–carbon vs. carbon–hydrogen bond formation reactions of ethene in the presence of H2
journal, December 2013
- Serna, Pedro; Gates, Bruce C.
- Journal of Catalysis, Vol. 308
Tracking Rh Atoms in Zeolite HY: First Steps of Metal Cluster Formation and Influence of Metal Nuclearity on Catalysis of Ethylene Hydrogenation and Ethylene Dimerization
journal, June 2016
- Yang, Dong; Xu, Pinghong; Browning, Nigel D.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 13
Determination of the Evolution of Heterogeneous Single Metal Atoms and Nanoclusters under Reaction Conditions: Which Are the Working Catalytic Sites?
journal, October 2019
- Liu, Lichen; Meira, Debora M.; Arenal, Raul
- ACS Catalysis, Vol. 9, Issue 12
Operando Dual Beam FTIR Study of Hydroxyl Groups and Zn Species over Defective HZSM-5 Zeolite Supported Zinc Catalysts
journal, January 2019
- Lin, Long; Zhang, Xiaotong; He, Ning
- Catalysts, Vol. 9, Issue 1
Structure of Ethene Adsorption Sites on Supported Metal Catalysts from in Situ XANES Analysis
journal, July 2007
- Bus, Eveline; Ramaker, David E.; van Bokhoven, Jeroen A.
- Journal of the American Chemical Society, Vol. 129, Issue 26
Catalytic N2O decomposition and reduction by NH3 over Fe/Beta and Fe/SSZ-13 catalysts
journal, February 2018
- Wang, Aiyong; Wang, Yilin; Walter, Eric D.
- Journal of Catalysis, Vol. 358
Highly dispersed and stable Pt clusters encapsulated within ZSM-5 with aid of sodium ion for partial oxidation of methane
journal, April 2021
- Guo, Jing; Ding, Chuanmin; Ma, Zili
- Fuel, Vol. 289
A Single-Site Platinum CO Oxidation Catalyst in Zeolite KLTL: Microscopic and Spectroscopic Determination of the Locations of the Platinum Atoms
journal, July 2014
- Kistler, Joseph D.; Chotigkrai, Nutchapon; Xu, Pinghong
- Angewandte Chemie International Edition, Vol. 53, Issue 34
Investigations into the nature of a silicoaluminophosphate with the faujasite structure
journal, April 1987
- Sierra de Saldarriaga, Ligia; Saldarriaga, Carlos; Davis, Mark E.
- Journal of the American Chemical Society, Vol. 109, Issue 9
Dynamics of Single Pt Atoms on Alumina during CO Oxidation Monitored by Operando X-ray and Infrared Spectroscopies
journal, May 2019
- Dessal, Caroline; Len, Thomas; Morfin, Franck
- ACS Catalysis, Vol. 9, Issue 6
Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts
journal, September 2015
- Ding, K.; Gulec, A.; Johnson, A. M.
- Science, Vol. 350, Issue 6257
Isostructural Zeolite-Supported Rhodium and Iridium Complexes: Tuning Catalytic Activity and Selectivity by Ligand Modification
journal, August 2015
- Martinez-Macias, Claudia; Serna, Pedro; Gates, Bruce C.
- ACS Catalysis, Vol. 5, Issue 10
A General Strategy for Fabricating Isolated Single Metal Atomic Site Catalysts in Y Zeolite
journal, May 2019
- Liu, Yiwei; Li, Zhi; Yu, Qiuying
- Journal of the American Chemical Society, Vol. 141, Issue 23
Elucidation of the zeolite role on the hydrogenating activity of Pt-catalysts
journal, January 2017
- Mendes, Pedro S. F.; Gregório, André F. C.; Daudin, Antoine
- Catalysis Communications, Vol. 89
Single‐Site vs. Cluster Catalysis in High Temperature Oxidations
journal, June 2021
- Serna, Pedro; Rodríguez‐Fernández, Aida; Yacob, Sara
- Angewandte Chemie, Vol. 133, Issue 29
The hydrogen spillover effect. A misunderstanding story
journal, July 2020
- Bettahar, Mohammed M.
- Catalysis Reviews
Rhodium Complex with Ethylene Ligands Supported on Highly Dehydroxylated MgO: Synthesis, Characterization, and Reactivity
journal, January 2006
- Bhirud, Vinesh A.; Ehresmann, Justin O.; Kletnieks, Philip W.
- Langmuir, Vol. 22, Issue 1
Impact of Zeolites on the Petroleum and Petrochemical Industry
journal, May 2009
- Vermeiren, W.; Gilson, J. -P.
- Topics in Catalysis, Vol. 52, Issue 9
In situ observation of phase changes of a silica-supported cobalt catalyst for the Fischer–Tropsch process by the development of a synchrotron-compatible in situ/operando powder X-ray diffraction cell
journal, October 2018
- Hoffman, Adam S.; Singh, Joseph A.; Bent, Stacey F.
- Journal of Synchrotron Radiation, Vol. 25, Issue 6
Structural Characterization of Supported Platinum Carbonyl Clusters by X-ray Absorption Spectroscopy
journal, August 2000
- Torigoe, Kanjiro; Remita, Hynd; Picq, Georgette
- The Journal of Physical Chemistry B, Vol. 104, Issue 30
Identification of isolated Pt atoms in H-mordenite
journal, January 1994
- Zholobenko, Vladimir L.; Lei, Guan-Dao; Carvill, Brian T.
- Journal of the Chemical Society, Faraday Transactions, Vol. 90, Issue 1
Platinum Nanoparticles Encapsulated in MFI Zeolite Crystals by a Two-Step Dry Gel Conversion Method as a Highly Selective Hydrogenation Catalyst
journal, October 2015
- Gu, Jing; Zhang, Zhiyang; Hu, Pei
- ACS Catalysis, Vol. 5, Issue 11
Platinum species in the pores of NaX, NaY and NaA zeolites studied using EPR, XAS and FTIR spectroscopies
journal, January 2008
- Akdogan, Yasar; Vogt, Christina; Bauer, Matthias
- Physical Chemistry Chemical Physics, Vol. 10, Issue 20
Catalysis by Gold: Isolated Surface Au3+ Ions are Active Sites for Selective Hydrogenation of 1,3-Butadiene over Au/ZrO2 Catalysts
journal, November 2005
- Zhang, Xin; Shi, Hui; Xu, Bo-Qing
- Angewandte Chemie International Edition, Vol. 44, Issue 43
Reversible Transformation of Pt Nanoparticles into Single Atoms inside High-Silica Chabazite Zeolite
journal, November 2016
- Moliner, Manuel; Gabay, Jadeene E.; Kliewer, Chris E.
- Journal of the American Chemical Society, Vol. 138, Issue 48
Aromatization of ethane on platinum containing ZSM-5 zeolites
journal, November 1990
- Steinberg, Karl-Hermann; Mroczek, Uwe; Roessner, Frank
- Applied Catalysis, Vol. 66, Issue 1
FTIR study of weak hydrogen bonding of Broensted hydroxyls in zeolites and aluminophosphates
journal, April 1994
- Makarova, Marina A.; Ojo, Adeola F.; Karim, Khalid
- The Journal of Physical Chemistry, Vol. 98, Issue 14
A new method for parameterization of phase shift and backscattering amplitude
journal, March 1995
- Vaarkamp, Marius; Linders, Johannes C.; Koningsberger, Diek C.
- Physica B: Condensed Matter, Vol. 208-209
Single-Atom Catalysts: Synthetic Strategies and Electrochemical Applications
journal, July 2018
- Chen, Yuanjun; Ji, Shufang; Chen, Chen
- Joule, Vol. 2, Issue 7
Isostructural Atomically Dispersed Rhodium Catalysts Supported on SAPO-37 and on HY Zeolite
journal, June 2020
- Perez-Aguilar, Jorge E.; Chen, Cong-Yan; Hughes, James T.
- Journal of the American Chemical Society, Vol. 142, Issue 26
Spillover in Heterogeneous Catalysis
journal, May 1995
- Conner, W. Curtis.; Falconer, John L.
- Chemical Reviews, Vol. 95, Issue 3
Structure and Reactivity of a Mononuclear Gold-Complex Catalyst Supported on Magnesium Oxide
journal, February 2003
- Guzman, Javier; Gates, Bruce C.
- Angewandte Chemie International Edition, Vol. 42, Issue 6
Supported Molecular Iridium Catalysts: Resolving Effects of Metal Nuclearity and Supports as Ligands
journal, October 2011
- Lu, Jing; Serna, Pedro; Aydin, Ceren
- Journal of the American Chemical Society, Vol. 133, Issue 40
Influence of preparation variables on the dispersion of platinum on zeolite KL
journal, August 1997
- M'Kombe, C. M.; Dry, M. E.; O'Connor, C. T.
- Zeolites, Vol. 19, Issue 2-3
FTIR spectroscopic study of CO adsorption on Pt–H–ZSM-5
journal, June 2005
- Chakarova, Kristina; Mihaylov, Mihail; Hadjiivanov, Konstantin
- Microporous and Mesoporous Materials, Vol. 81, Issue 1-3
Hydrogen Activation and Metal Hydride Formation Trigger Cluster Formation from Supported Iridium Complexes
journal, March 2012
- Lu, Jing; Aydin, Ceren; Browning, Nigel D.
- Journal of the American Chemical Society, Vol. 134, Issue 11
Isomerization of hydrocarbons over Pt supported on micro-mesoporous ZSM-5
journal, November 2018
- Tamizhdurai, P.; Krishnan, P. Santhana; Ramesh, A.
- Polyhedron, Vol. 154
Confining isolated atoms and clusters in crystalline porous materials for catalysis
journal, October 2020
- Liu, Lichen; Corma, Avelino
- Nature Reviews Materials, Vol. 6, Issue 3
Evolution and stabilization of subnanometric metal species in confined space by in situ TEM
journal, February 2018
- Liu, Lichen; Zakharov, Dmitri N.; Arenal, Raul
- Nature Communications, Vol. 9, Issue 1
Infrared study of the adsorption of acetone, acrolein, ethanoic acid and propene–NO mixtures on Rh/Al2O3 catalysts
journal, January 1989
- Anderson, James A.; Rochester, Colin H.
- Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 5
Transmission and fluorescence X-ray absorption spectroscopy cell/flow reactor for powder samples under vacuum or in reactive atmospheres
journal, July 2016
- Hoffman, A. S.; Debefve, L. M.; Bendjeriou-Sedjerari, A.
- Review of Scientific Instruments, Vol. 87, Issue 7
Stable complete methane oxidation over palladium based zeolite catalysts
journal, June 2018
- Petrov, Andrey W.; Ferri, Davide; Krumeich, Frank
- Nature Communications, Vol. 9, Issue 1
Structural evolution of atomically dispersed Pt catalysts dictates reactivity
journal, April 2019
- DeRita, Leo; Resasco, Joaquin; Dai, Sheng
- Nature Materials, Vol. 18, Issue 7
Silicoaluminophosphate molecular sieves: another new class of microporous crystalline inorganic solids
journal, October 1984
- Lok, Brent M.; Messina, Celeste A.; Patton, R. Lyle
- Journal of the American Chemical Society, Vol. 106, Issue 20
Hydroisomerization and Hydrocracking of Alkanes
journal, September 1996
- Alvarez, F.; Ribeiro, F. R.; Perot, G.
- Journal of Catalysis, Vol. 162, Issue 2
Can the state of platinum species be unambiguously determined by the stretching frequency of an adsorbed CO probe molecule?
journal, January 2016
- Aleksandrov, Hristiyan A.; Neyman, Konstantin M.; Hadjiivanov, Konstantin I.
- Physical Chemistry Chemical Physics, Vol. 18, Issue 32
The State and Catalytic Properties of Platinum and Palladium in Faujasite-type Zeolites
journal, January 1979
- Gallezot, Pierre
- Catalysis Reviews, Vol. 20, Issue 1
Characterization of the morphology of Pt clusters incorporated in a KL zeolite by vapor phase and incipient wetness impregnation. Influence of Pt particle morphology on aromatization activity and deactivation
journal, November 1999
- Jacobs, Gary; Ghadiali, Firoz; Pisanu, Adriana
- Applied Catalysis A: General, Vol. 188, Issue 1-2
Aromatization of n-hexane by platinum-containing molecular sieves I. Catalyst preparation by the vapor phase impregnation method
journal, March 1992
- Hong, S.
- Journal of Catalysis, Vol. 134, Issue 1
Dynamic Structural Changes in a Molecular Zeolite-Supported Iridium Catalyst for Ethene Hydrogenation
journal, November 2009
- Uzun, Alper; Gates, Bruce C.
- Journal of the American Chemical Society, Vol. 131, Issue 43
Time-Resolved Structural Characterization of Formation and Break-up of Rhodium Clusters Supported in Highly Dealuminated Y Zeolite
journal, October 2008
- Liang, Ann J.; Gates, Bruce C.
- The Journal of Physical Chemistry C, Vol. 112, Issue 46
Hydroisomerization of long-chain paraffins: Mechanism and catalysts. Part I
journal, April 2015
- Gerasimov, D. N.; Fadeev, V. V.; Loginova, A. N.
- Catalysis in Industry, Vol. 7, Issue 2
Hydroisomerization and hydrocracking of linear and multibranched long model alkanes on hierarchical Pt/ZSM-22 zeolite
journal, December 2013
- Martens, Johan A.; Verboekend, Danny; Thomas, Karine
- Catalysis Today, Vol. 218-219
The acidic properties of SAPO-37 compared to faujasites and SAPO-5
journal, March 1990
- Dzwigaj, S.; Briend, M.; Shikholeslami, A.
- Zeolites, Vol. 10, Issue 3