Isolating Clusters of Light Elements in Molecular Sieves with Atom Probe Tomography
Abstract
Understanding the 3-D distribution and nature of active sites in heterogeneous catalysts is critical to developing structure–function relationships. However, this is difficult to achieve in microporous materials as there is little relative z-contrast between active and inactive framework elements (e.g., Al, O, P, and Si), making them difficult to differentiate with electron microscopies. We have applied atom probe tomography (APT), currently the only nanometer-scale 3-D microscopy to offer routine light element contrast, to the methanol-to-hydrocarbons (MTH) catalyst SAPO-34, with Si as the active site, which may be present in the framework as either isolated Si species or clusters (islands) of Si atoms. 29Si solid-state NMR data on isotopically enriched and natural abundance materials are consistent with the presence of Si islands, and the APT results have been complemented with simulations to show the smallest detectable cluster size as a function of instrument spatial resolution and detector efficiency. We have identified significant Si–Si affinity in the materials, as well as clustering of coke deposited by the MTH reaction (13CH3OH used) and an affinity between Brønsted acid sites and coke. A comparison with simulations shows that the ultimate spatial resolution that can be attained by APT applied to molecular sieves is 0.5–1more »
- Authors:
-
[3];
[1];
[1]
- Univ. of Utrecht (Netherlands)
- Grinnell College, IA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1474493
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 29; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Schmidt, Joel E., Peng, Linqing, Paioni, Alessandra Lucini, Ehren, Helena Leona, Guo, Wei, Mazumder, Baishakhi, Matthijs de Winter, D. A., Attila, Özgün, Fu, Donglong, Chowdhury, Abhishek Dutta, Houben, Klaartje, Baldus, Marc, Poplawsky, Jonathan D., and Weckhuysen, Bert M. Isolating Clusters of Light Elements in Molecular Sieves with Atom Probe Tomography. United States: N. p., 2018.
Web. doi:10.1021/jacs.8b04494.
Schmidt, Joel E., Peng, Linqing, Paioni, Alessandra Lucini, Ehren, Helena Leona, Guo, Wei, Mazumder, Baishakhi, Matthijs de Winter, D. A., Attila, Özgün, Fu, Donglong, Chowdhury, Abhishek Dutta, Houben, Klaartje, Baldus, Marc, Poplawsky, Jonathan D., & Weckhuysen, Bert M. Isolating Clusters of Light Elements in Molecular Sieves with Atom Probe Tomography. United States. https://doi.org/10.1021/jacs.8b04494
Schmidt, Joel E., Peng, Linqing, Paioni, Alessandra Lucini, Ehren, Helena Leona, Guo, Wei, Mazumder, Baishakhi, Matthijs de Winter, D. A., Attila, Özgün, Fu, Donglong, Chowdhury, Abhishek Dutta, Houben, Klaartje, Baldus, Marc, Poplawsky, Jonathan D., and Weckhuysen, Bert M. Fri .
"Isolating Clusters of Light Elements in Molecular Sieves with Atom Probe Tomography". United States. https://doi.org/10.1021/jacs.8b04494. https://www.osti.gov/servlets/purl/1474493.
@article{osti_1474493,
title = {Isolating Clusters of Light Elements in Molecular Sieves with Atom Probe Tomography},
author = {Schmidt, Joel E. and Peng, Linqing and Paioni, Alessandra Lucini and Ehren, Helena Leona and Guo, Wei and Mazumder, Baishakhi and Matthijs de Winter, D. A. and Attila, Özgün and Fu, Donglong and Chowdhury, Abhishek Dutta and Houben, Klaartje and Baldus, Marc and Poplawsky, Jonathan D. and Weckhuysen, Bert M.},
abstractNote = {Understanding the 3-D distribution and nature of active sites in heterogeneous catalysts is critical to developing structure–function relationships. However, this is difficult to achieve in microporous materials as there is little relative z-contrast between active and inactive framework elements (e.g., Al, O, P, and Si), making them difficult to differentiate with electron microscopies. We have applied atom probe tomography (APT), currently the only nanometer-scale 3-D microscopy to offer routine light element contrast, to the methanol-to-hydrocarbons (MTH) catalyst SAPO-34, with Si as the active site, which may be present in the framework as either isolated Si species or clusters (islands) of Si atoms. 29Si solid-state NMR data on isotopically enriched and natural abundance materials are consistent with the presence of Si islands, and the APT results have been complemented with simulations to show the smallest detectable cluster size as a function of instrument spatial resolution and detector efficiency. We have identified significant Si–Si affinity in the materials, as well as clustering of coke deposited by the MTH reaction (13CH3OH used) and an affinity between Brønsted acid sites and coke. A comparison with simulations shows that the ultimate spatial resolution that can be attained by APT applied to molecular sieves is 0.5–1 nm. Finally, the observed 13C clusters are consistent with hydrocarbon pool mechanism intermediates that are preferentially located in regions of increased Brønsted acidity.},
doi = {10.1021/jacs.8b04494},
journal = {Journal of the American Chemical Society},
number = 29,
volume = 140,
place = {United States},
year = {Fri Jul 13 00:00:00 EDT 2018},
month = {Fri Jul 13 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 21 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Zeolites as catalysts in oil refining
journal, January 2014
- Primo, Ana; Garcia, Hermenegildo
- Chem. Soc. Rev., Vol. 43, Issue 22
Impact of Zeolites on the Petroleum and Petrochemical Industry
journal, May 2009
- Vermeiren, W.; Gilson, J. -P.
- Topics in Catalysis, Vol. 52, Issue 9
Heterogeneous Catalysis: Understanding for Designing, and Designing for Applications
journal, April 2016
- Corma, Avelino
- Angewandte Chemie International Edition, Vol. 55, Issue 21
The Merits of Static and Dynamic High-Resolution Electron Microscopy (HREM) for the Study of Solid Catalysts
journal, July 2010
- Thomas, John Meurig; Midgley, Paul A.
- ChemCatChem, Vol. 2, Issue 7
Methanol to Olefins (MTO): From Fundamentals to Commercialization
journal, February 2015
- Tian, Peng; Wei, Yingxu; Ye, Mao
- ACS Catalysis, Vol. 5, Issue 3
Conversion of Methanol to Hydrocarbons: How Zeolite Cavity and Pore Size Controls Product Selectivity
journal, April 2012
- Olsbye, Unni; Svelle, Stian; Bjørgen, Morten
- Angewandte Chemie International Edition, Vol. 51, Issue 24, p. 5810-5831
Charge compensation dominates the distribution of silica in SAPO-34
journal, February 2016
- Zhao, Huiru; Shi, Shumei; Wu, Jinxiong
- Chinese Journal of Catalysis, Vol. 37, Issue 2
The Effect of Acid Strength on the Conversion of Methanol to Olefins Over Acidic Microporous Catalysts with the CHA Topology
journal, January 2009
- Bleken, Francesca; Bjørgen, Morten; Palumbo, Luisa
- Topics in Catalysis, Vol. 52, Issue 3
Product shape selectivity dominates the Methanol-to-Olefins (MTO) reaction over H-SAPO-34 catalysts
journal, May 2009
- Hereijgers, Bart P. C.; Bleken, Francesca; Nilsen, Merete H.
- Journal of Catalysis, Vol. 264, Issue 1
Small-Pore Molecular Sieves SAPO-34 and SAPO-44 with Chabazite Structure: A Study of Silicon Incorporation
journal, May 1994
- Ashtekar, Sunil; Chilukuri, Satyanarayana V. V.; Chakrabarty, Dipak K.
- The Journal of Physical Chemistry, Vol. 98, Issue 18
Unraveling the non-classic crystallization of SAPO-34 in a dry gel system towards controlling meso-structure with the assistance of growth inhibitor: Growth mechanism, hierarchical structure control and catalytic properties
journal, May 2016
- Zheng, Jingwei; Zhang, Weiping; Liu, Zhiting
- Microporous and Mesoporous Materials, Vol. 225
Effect of different TEAOH/DEA combinations on SAPO-34’s synthesis and catalytic performance
journal, March 2010
- Ye, Liping; Cao, Fahai; Ying, Weiyong
- Journal of Porous Materials, Vol. 18, Issue 2
A study of the acidity of SAPO-34 by solid-state NMR spectroscopy
journal, August 2012
- Shen, Wanling; Li, Xin; Wei, Yingxu
- Microporous and Mesoporous Materials, Vol. 158
Influence of the Choice of the Template on the Short- and Long-Term Stability of SAPO-34 Zeolite
journal, May 1995
- Briend, M.; Vomscheid, R.; Peltre, M. J.
- The Journal of Physical Chemistry, Vol. 99, Issue 20
Complex relationship between SAPO framework topology, content and distribution of Si and catalytic behaviour in the MTO reaction
journal, January 2017
- Pinilla-Herrero, I.; Márquez-Álvarez, C.; Sastre, E.
- Catalysis Science & Technology, Vol. 7, Issue 17
Methanol to olefins: activity and stability of nanosized SAPO-34 molecular sieves and control of selectivity by silicon distribution
journal, January 2013
- Li, Zhibin; Martínez-Triguero, Joaquín; Concepción, Patricia
- Physical Chemistry Chemical Physics, Vol. 15, Issue 35
Mechanisms of the Deactivation of SAPO-34 Materials with Different Crystal Sizes Applied as MTO Catalysts
journal, February 2013
- Dai, Weili; Wu, Guangjun; Li, Landong
- ACS Catalysis, Vol. 3, Issue 4
Coke Formation in a Zeolite Crystal During the Methanol-to-Hydrocarbons Reaction as Studied with Atom Probe Tomography
journal, August 2016
- Schmidt, Joel E.; Poplawsky, Jonathan D.; Mazumder, Baishakhi
- Angewandte Chemie International Edition, Vol. 55, Issue 37
Determining the location and nearest neighbours of aluminium in zeolites with atom probe tomography
journal, July 2015
- Perea, Daniel E.; Arslan, Ilke; Liu, Jia
- Nature Communications, Vol. 6, Issue 1
Discerning the Location and Nature of Coke Deposition from Surface to Bulk of Spent Zeolite Catalysts
journal, November 2016
- Devaraj, Arun; Vijayakumar, Murugesan; Bao, Jie
- Scientific Reports, Vol. 6, Issue 1
Iron Loading Effects in Fe/SSZ-13 NH 3 -SCR Catalysts: Nature of the Fe Ions and Structure–Function Relationships
journal, April 2016
- Gao, Feng; Zheng, Yang; Kukkadapu, Ravi K.
- ACS Catalysis, Vol. 6, Issue 5
Nanoscale Chemical Imaging of Zeolites Using Atom Probe Tomography
journal, July 2018
- Schmidt, Joel E.; Peng, Linqing; Poplawsky, Jonathan D.
- Angewandte Chemie International Edition, Vol. 57, Issue 33
Transformation of Active Sites in Fe/SSZ-13 SCR Catalysts during Hydrothermal Aging: A Spectroscopic, Microscopic, and Kinetics Study
journal, March 2017
- Kovarik, Libor; Washton, Nancy M.; Kukkadapu, Ravi
- ACS Catalysis, Vol. 7, Issue 4
Nanoscale tomography reveals the deactivation of automotive copper-exchanged zeolite catalysts
journal, November 2017
- Schmidt, Joel E.; Oord, Ramon; Guo, Wei
- Nature Communications, Vol. 8, Issue 1
The Role of the Template in Directing the Si Distribution in SAPO Zeolites
journal, September 1994
- Vomscheid, R.; Briend, M.; Peltre, M. J.
- The Journal of Physical Chemistry, Vol. 98, Issue 38
Space- and Time-Resolved In-situ Spectroscopy on the Coke Formation in Molecular Sieves: Methanol-to-Olefin Conversion over H-ZSM-5 and H-SAPO-34
journal, November 2008
- Mores, Davide; Stavitski, Eli; Kox, Marianne H. F.
- Chemistry - A European Journal, Vol. 14, Issue 36
Single-Particle Spectroscopy on Large SAPO-34 Crystals at Work: Methanol-to-Olefin versus Ethanol-to-Olefin Processes
journal, July 2013
- Qian, Qingyun; Ruiz-Martínez, Javier; Mokhtar, Mohamed
- Chemistry - A European Journal, Vol. 19, Issue 34
Morphology-dependent zeolite intergrowth structures leading to distinct internal and outer-surface molecular diffusion barriers
journal, September 2009
- Karwacki, Lukasz; Kox, Marianne H. F.; Matthijs de Winter, D. A.
- Nature Materials, Vol. 8, Issue 12
Structural changes in SAPO-34 due to hydrothermal treatment. A NMR, XRD, and DRIFTS study
journal, May 2016
- Arstad, Bjørnar; Lind, Anna; Cavka, Jasmina H.
- Microporous and Mesoporous Materials, Vol. 225
Coke Formation in a Zeolite Crystal During the Methanol-to-Hydrocarbons Reaction as Studied with Atom Probe Tomography
journal, August 2016
- Schmidt, Joel E.; Poplawsky, Jonathan D.; Mazumder, Baishakhi
- Angewandte Chemie International Edition, Vol. 55, Issue 37
Nanoscale Chemical Imaging of Zeolites Using Atom Probe Tomography
journal, July 2018
- Schmidt, Joel E.; Peng, Linqing; Poplawsky, Jonathan D.
- Angewandte Chemie International Edition, Vol. 57, Issue 33
The Merits of Static and Dynamic High-Resolution Electron Microscopy (HREM) for the Study of Solid Catalysts
journal, July 2010
- Thomas, John Meurig; Midgley, Paul A.
- ChemCatChem, Vol. 2, Issue 7
Space- and Time-Resolved In-situ Spectroscopy on the Coke Formation in Molecular Sieves: Methanol-to-Olefin Conversion over H-ZSM-5 and H-SAPO-34
journal, November 2008
- Mores, Davide; Stavitski, Eli; Kox, Marianne H. F.
- Chemistry - A European Journal, Vol. 14, Issue 36
Single-Particle Spectroscopy on Large SAPO-34 Crystals at Work: Methanol-to-Olefin versus Ethanol-to-Olefin Processes
journal, July 2013
- Qian, Qingyun; Ruiz-Martínez, Javier; Mokhtar, Mohamed
- Chemistry - A European Journal, Vol. 19, Issue 34
Effect of different TEAOH/DEA combinations on SAPO-34’s synthesis and catalytic performance
journal, March 2010
- Ye, Liping; Cao, Fahai; Ying, Weiyong
- Journal of Porous Materials, Vol. 18, Issue 2
The Effect of Acid Strength on the Conversion of Methanol to Olefins Over Acidic Microporous Catalysts with the CHA Topology
journal, January 2009
- Bleken, Francesca; Bjørgen, Morten; Palumbo, Luisa
- Topics in Catalysis, Vol. 52, Issue 3
Impact of Zeolites on the Petroleum and Petrochemical Industry
journal, May 2009
- Vermeiren, W.; Gilson, J. -P.
- Topics in Catalysis, Vol. 52, Issue 9
A study of the acidity of SAPO-34 by solid-state NMR spectroscopy
journal, August 2012
- Shen, Wanling; Li, Xin; Wei, Yingxu
- Microporous and Mesoporous Materials, Vol. 158
Unraveling the non-classic crystallization of SAPO-34 in a dry gel system towards controlling meso-structure with the assistance of growth inhibitor: Growth mechanism, hierarchical structure control and catalytic properties
journal, May 2016
- Zheng, Jingwei; Zhang, Weiping; Liu, Zhiting
- Microporous and Mesoporous Materials, Vol. 225
Structural changes in SAPO-34 due to hydrothermal treatment. A NMR, XRD, and DRIFTS study
journal, May 2016
- Arstad, Bjørnar; Lind, Anna; Cavka, Jasmina H.
- Microporous and Mesoporous Materials, Vol. 225
Mechanisms of silicon incorporation in aluminophosphate molecular sieves
journal, May 1997
- Sastre, G.; Lewis, D. W.; Catlow, C. R. A.
- Journal of Molecular Catalysis A: Chemical, Vol. 119, Issue 1-3
Methanol to Olefins (MTO): From Fundamentals to Commercialization
journal, February 2015
- Tian, Peng; Wei, Yingxu; Ye, Mao
- ACS Catalysis, Vol. 5, Issue 3
Mechanisms of the Deactivation of SAPO-34 Materials with Different Crystal Sizes Applied as MTO Catalysts
journal, February 2013
- Dai, Weili; Wu, Guangjun; Li, Landong
- ACS Catalysis, Vol. 3, Issue 4
The Role of the Template in Directing the Si Distribution in SAPO Zeolites
journal, September 1994
- Vomscheid, R.; Briend, M.; Peltre, M. J.
- The Journal of Physical Chemistry, Vol. 98, Issue 38
Determining the location and nearest neighbours of aluminium in zeolites with atom probe tomography
journal, July 2015
- Perea, Daniel E.; Arslan, Ilke; Liu, Jia
- Nature Communications, Vol. 6, Issue 1
Nanoscale tomography reveals the deactivation of automotive copper-exchanged zeolite catalysts
journal, November 2017
- Schmidt, Joel E.; Oord, Ramon; Guo, Wei
- Nature Communications, Vol. 8, Issue 1
Discerning the Location and Nature of Coke Deposition from Surface to Bulk of Spent Zeolite Catalysts
journal, November 2016
- Devaraj, Arun; Vijayakumar, Murugesan; Bao, Jie
- Scientific Reports, Vol. 6, Issue 1
Works referencing / citing this record:
Probing the Location and Speciation of Elements in Zeolites with Correlated Atom Probe Tomography and Scanning Transmission X‐Ray Microscopy
journal, October 2018
- Schmidt, Joel E.; Ye, Xinwei; van Ravenhorst, Ilse K.
- ChemCatChem, Vol. 11, Issue 1
Coated sulfated zirconia/SAPO-34 for the direct conversion of CO 2 to light olefins
journal, January 2020
- Ramirez, Adrian; Dutta Chowdhury, Abhishek; Caglayan, Mustafa
- Catalysis Science & Technology, Vol. 10, Issue 5
Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
journal, January 2020
- Wang, Zichun; Li, Tong; Jiang, Yijiao
- Nature Communications, Vol. 11, Issue 1
Atom Probe Tomography for Catalysis Applications: A Review
journal, July 2019
- Barroo, Cédric; Akey, Austin J.; Bell, David C.
- Applied Sciences, Vol. 9, Issue 13
Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks
text, January 2020
- Wang, Zichun; Li, Tong; Jiang, Yijiao
- ETH Zurich
Probing the Location and Speciation of Elements in Zeolites with Correlated Atom Probe Tomography and Scanning Transmission X‐Ray Microscopy
journal, October 2018
- Schmidt, Joel E.; Ye, Xinwei; van Ravenhorst, Ilse K.
- ChemCatChem, Vol. 11, Issue 1
Molecular elucidating of an unusual growth mechanism for polycyclic aromatic hydrocarbons in confined space
journal, February 2020
- Wang, Nan; Zhi, Yuchun; Wei, Yingxu
- Nature Communications, Vol. 11, Issue 1
Interpreting nanovoids in atom probe tomography data for accurate local compositional measurements
journal, February 2020
- Wang, Xing; Hatzoglou, Constantinos; Sneed, Brian
- Nature Communications, Vol. 11, Issue 1