skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Nanoscale Chemical Imaging of Zeolites Using Atom Probe Tomography

Abstract

Understanding structure–composition–property relationships in zeolite-based materials is critical to engineering improved solid catalysts. However, this can be difficult to realize as even single zeolite crystals can exhibit heterogeneities spanning several orders of magnitude, with consequences for, for example, reactivity, diffusion as well as stability. Great progress has been made in characterizing these porous solids using tomographic techniques, though each method has an ultimate spatial resolution limitation. Atom probe tomography (APT) is the only technique so far capable of producing 3D compositional reconstructions with sub-nanometer-scale resolution, and has only recently been applied to zeolite-based catalysts. Herein, we discuss the use of APT to study zeolites, including the critical aspects of sample preparation, data collection, assignment of mass spectral peaks including the predominant CO peak, the limitations of spatial resolution for the recovery of crystallographic information, and proper data analysis. All sections are illustrated with examples from recent literature, as well as previously unpublished data and analyses to demonstrate practical strategies to overcome potential pitfalls in applying APT to zeolites, thereby highlighting new insights gained from the APT method.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Utrecht (Netherlands)
  2. Grinnell College, IA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1474492
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 33; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Schmidt, Joel E., Peng, Linqing, Poplawsky, Jonathan D., and Weckhuysen, Bert M. Nanoscale Chemical Imaging of Zeolites Using Atom Probe Tomography. United States: N. p., 2018. Web. doi:10.1002/anie.201712952.
Schmidt, Joel E., Peng, Linqing, Poplawsky, Jonathan D., & Weckhuysen, Bert M. Nanoscale Chemical Imaging of Zeolites Using Atom Probe Tomography. United States. doi:10.1002/anie.201712952.
Schmidt, Joel E., Peng, Linqing, Poplawsky, Jonathan D., and Weckhuysen, Bert M. Wed . "Nanoscale Chemical Imaging of Zeolites Using Atom Probe Tomography". United States. doi:10.1002/anie.201712952. https://www.osti.gov/servlets/purl/1474492.
@article{osti_1474492,
title = {Nanoscale Chemical Imaging of Zeolites Using Atom Probe Tomography},
author = {Schmidt, Joel E. and Peng, Linqing and Poplawsky, Jonathan D. and Weckhuysen, Bert M.},
abstractNote = {Understanding structure–composition–property relationships in zeolite-based materials is critical to engineering improved solid catalysts. However, this can be difficult to realize as even single zeolite crystals can exhibit heterogeneities spanning several orders of magnitude, with consequences for, for example, reactivity, diffusion as well as stability. Great progress has been made in characterizing these porous solids using tomographic techniques, though each method has an ultimate spatial resolution limitation. Atom probe tomography (APT) is the only technique so far capable of producing 3D compositional reconstructions with sub-nanometer-scale resolution, and has only recently been applied to zeolite-based catalysts. Herein, we discuss the use of APT to study zeolites, including the critical aspects of sample preparation, data collection, assignment of mass spectral peaks including the predominant CO peak, the limitations of spatial resolution for the recovery of crystallographic information, and proper data analysis. All sections are illustrated with examples from recent literature, as well as previously unpublished data and analyses to demonstrate practical strategies to overcome potential pitfalls in applying APT to zeolites, thereby highlighting new insights gained from the APT method.},
doi = {10.1002/anie.201712952},
journal = {Angewandte Chemie (International Edition)},
number = 33,
volume = 57,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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, Vol. 128, Issue 37
  • DOI: 10.1002/ange.201606099

Some aspects of atom probe specimen preparation and analysis of thin film materials
journal, July 2004


Evidence for Anisotropic Mechanical Behavior and Nanoscale Chemical Heterogeneity in Cycled LiCoO 2
journal, January 2014

  • Diercks, David R.; Musselman, Matthew; Morgenstern, Amanda
  • Journal of The Electrochemical Society, Vol. 161, Issue 11
  • DOI: 10.1149/2.0071411jes

The second revolution in atom probe tomography
journal, February 2012

  • Kelly, Thomas F.; Larson, David J.
  • MRS Bulletin, Vol. 37, Issue 2
  • DOI: 10.1557/mrs.2012.3

Tailoring and visualizing the pore architecture of hierarchical zeolites
journal, January 2015

  • Wei, Ying; Parmentier, Tanja E.; de Jong, Krijn P.
  • Chemical Society Reviews, Vol. 44, Issue 20
  • DOI: 10.1039/C5CS00155B

The Problem with Determining Atomic Structure at the Nanoscale
journal, April 2007


Transformation of Active Sites in Fe/SSZ-13 SCR Catalysts during Hydrothermal Aging: A Spectroscopic, Microscopic, and Kinetics Study
journal, March 2017


Atom probe tomography
journal, March 2007

  • Kelly, Thomas F.; Miller, Michael K.
  • Review of Scientific Instruments, Vol. 78, Issue 3
  • DOI: 10.1063/1.2709758

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
  • DOI: 10.1038/srep37586

Heterogeneities of individual catalyst particles in space and time as monitored by spectroscopy
journal, October 2012

  • Buurmans, Inge L. C.; Weckhuysen, Bert M.
  • Nature Chemistry, Vol. 4, Issue 11
  • DOI: 10.1038/nchem.1478

Chemical Imaging of Spatial Heterogeneities in Catalytic Solids at Different Length and Time Scales
journal, June 2009

  • Weckhuysen, Bert M.
  • Angewandte Chemie International Edition, Vol. 48, Issue 27
  • DOI: 10.1002/anie.200900339

Toward atom probe tomography of microelectronic devices
journal, November 2011


Single molecule methods for the study of catalysis: from enzymes to heterogeneous catalysts
journal, January 2014

  • Janssen, Kris P. F.; De Cremer, Gert; Neely, Robert K.
  • Chem. Soc. Rev., Vol. 43, Issue 4
  • DOI: 10.1039/C3CS60245A

Advances in atom probe tomography instrumentation: Implications for materials research
journal, January 2016

  • Moody, Michael P.; Vella, Angela; Gerstl, Stephan S. A.
  • MRS Bulletin, Vol. 41, Issue 1
  • DOI: 10.1557/mrs.2015.311

Atom probe tomography of metallic nanostructures
journal, January 2016

  • Hono, Kazuhiro; Raabe, Dierk; Ringer, Simon P.
  • MRS Bulletin, Vol. 41, Issue 1
  • DOI: 10.1557/mrs.2015.314

UV-VIS-NIR spectroscopy and microscopy of heterogeneous catalysts
journal, January 2010

  • Schoonheydt, Robert A.
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00080a

Preface: recent advances in the in-situ characterization of heterogeneous catalysts
journal, January 2010


Spectroscopic electron tomography
journal, September 2003


Strategies for fabricating atom probe specimens with a dual beam FIB
journal, March 2005


Direct observations of nucleation in a nondilute multicomponent alloy
journal, June 2006


Probing the surfaces of heterogeneous catalysts by in situ IR spectroscopy
journal, January 2010

  • Lamberti, Carlo; Zecchina, Adriano; Groppo, Elena
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00117a

Atom Probe Tomography Characterization of Thin Copper Layers on Aluminum Deposited by Galvanic Displacement
journal, January 2012

  • Zhang, Yi; Ai, Jiahe; Hillier, Andrew C.
  • Langmuir, Vol. 28, Issue 3
  • DOI: 10.1021/la204156d

Clustering and nearest neighbour distances in atom-probe tomography
journal, September 2009


Behavior of molecules and molecular ions near a field emitter
journal, March 2016


Nanoscale tomography in materials science
journal, December 2007


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
  • DOI: 10.1038/ncomms8589

Colossal injection of catalyst atoms into silicon nanowires
journal, April 2013

  • Moutanabbir, Oussama; Isheim, Dieter; Blumtritt, Horst
  • Nature, Vol. 496, Issue 7443
  • DOI: 10.1038/nature11999

Atom probe tomography today
journal, December 2007


Nanoscale Chemical Imaging of Coking Mechanisms in a Zeolite ZSM-5 Crystal by Atom Probe Tomography
journal, July 2017

  • Poplawsky, Jonathan D.; Schmidt, Joel E.; Mazumder, Baishakhi
  • Microscopy and Microanalysis, Vol. 23, Issue S1
  • DOI: 10.1017/S1431927617004032

Hard and soft X-ray microscopy and tomography in catalysis: bridging the different time and length scales
journal, January 2010

  • Grunwaldt, Jan-Dierk; Schroer, Christian G.
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00036a

Interpreting atom probe data from chromium oxide scales
journal, December 2015


Quantitative analysis of doped/undoped ZnO nanomaterials using laser assisted atom probe tomography: Influence of the analysis parameters
journal, December 2015

  • Amirifar, Nooshin; Lardé, Rodrigue; Talbot, Etienne
  • Journal of Applied Physics, Vol. 118, Issue 21
  • DOI: 10.1063/1.4936167

Single-molecule nanocatalysis reveals heterogeneous reaction pathways and catalytic dynamics
journal, November 2008

  • Xu, Weilin; Kong, Jason S.; Yeh, Yun-Ting E.
  • Nature Materials, Vol. 7, Issue 12
  • DOI: 10.1038/nmat2319

Identifying reaction intermediates and catalytic active sites through in situ characterization techniques
journal, January 2010

  • Foster, Andrew J.; Lobo, Raul F.
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00016g

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
  • DOI: 10.1002/anie.201606099

The first direct observation of hydrogen trapping sites in TiC precipitation-hardening steel through atom probe tomography
journal, August 2010


Atom probe specimen preparation with a dual beam SEM/FIB miller
journal, September 2007


In situ study on molecular diffusion phenomena in nanoporous catalytic solids
journal, January 2010

  • Chmelik, Christian; Kärger, Jörg
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00100g

Quantitative binomial distribution analyses of nanoscale like‐solute atom clustering and segregation in atom probe tomography data
journal, July 2008

  • Moody, Michael P.; Stephenson, Leigh T.; Ceguerra, Anna V.
  • Microscopy Research and Technique, Vol. 71, Issue 7
  • DOI: 10.1002/jemt.20582

Nanoscale chemical tomography of buried organic–inorganic interfaces in the chiton tooth
journal, January 2011


Atomically Resolved Tissue Integration
journal, July 2014

  • Karlsson, Johan; Sundell, Gustav; Thuvander, Mattias
  • Nano Letters, Vol. 14, Issue 8
  • DOI: 10.1021/nl501564f

Structural analyses in three-dimensional atom probe: a Fourier transform approach
journal, September 2001


Atom probe tomography of interfaces in ceramic films and oxide scales
journal, January 2016

  • Stiller, K.; Thuvander, M.; Povstugar, I.
  • MRS Bulletin, Vol. 41, Issue 1
  • DOI: 10.1557/mrs.2015.307

Nanometer-scale isotope analysis of bulk diamond by atom probe tomography
journal, November 2015


Atom probe tomography
journal, June 2009


Atom probe tomography spatial reconstruction: Status and directions
journal, October 2013

  • Larson, D. J.; Gault, B.; Geiser, B. P.
  • Current Opinion in Solid State and Materials Science, Vol. 17, Issue 5
  • DOI: 10.1016/j.cossms.2013.09.002

Recent advances in zeolite science based on advance characterization techniques
journal, May 2014


A review of fine structures of nanoporous materials as evidenced by microscopic methods
journal, January 2013

  • Liu, Zheng; Fujita, Nobuhisa; Miyasaka, Keiichi
  • Microscopy, Vol. 62, Issue 1
  • DOI: 10.1093/jmicro/dfs098

The future of atom probe tomography
journal, April 2012


Zeolites are no longer a challenge: Atomic resolution data by Aberration-corrected STEM
journal, January 2015


Dynamic multinuclear sites formed by mobilized copper ions in NO x selective catalytic reduction
journal, August 2017

  • Paolucci, Christopher; Khurana, Ishant; Parekh, Atish A.
  • Science, Vol. 357, Issue 6354
  • DOI: 10.1126/science.aan5630

Oxidation and Surface Segregation Behavior of a Pt–Pd–Rh Alloy Catalyst
journal, October 2014

  • Bagot, Paul A. J.; Kruska, Karen; Haley, Daniel
  • The Journal of Physical Chemistry C, Vol. 118, Issue 45
  • DOI: 10.1021/jp508144z

Advanced visualization strategies bridge the multidimensional complexity of technical catalysts
journal, August 2013

  • Mitchell, Sharon; Michels, Nina-Luisa; Majano, Gerardo
  • Current Opinion in Chemical Engineering, Vol. 2, Issue 3
  • DOI: 10.1016/j.coche.2013.04.005

Trends and advances in Operando methodology
journal, May 2016


Fluorescence micro(spectro)scopy as a tool to study catalytic materials in action
journal, January 2010

  • De Cremer, Gert; Sels, Bert F.; De Vos, Dirk E.
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00047g

Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions
journal, November 2016


Single-molecule fluorescence imaging of nanocatalytic processes
journal, January 2010

  • Chen, Peng; Zhou, Xiaochun; Shen, Hao
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/b909052p

Encapsulation method for atom probe tomography analysis of nanoparticles
journal, December 2015


Organic Materials and Organic/Inorganic Heterostructures in Atom Probe Tomography
journal, May 2012


Structural and compositional dependence of the CdTexSe1−x alloy layer photoactivity in CdTe-based solar cells
journal, July 2016

  • Poplawsky, Jonathan D.; Guo, Wei; Paudel, Naba
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12537

Zeolite molecular sieves: preparation and scale-up
journal, August 2005


Advanced X-ray absorption and emission spectroscopy: in situ catalytic studies
journal, January 2010

  • Singh, Jagdeep; Lamberti, Carlo; van Bokhoven, Jeroen A.
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/c0cs00054j

Recent advances in zeolite chemistry and catalysis
journal, January 2015

  • Weckhuysen, Bert M.; Yu, Jihong
  • Chemical Society Reviews, Vol. 44, Issue 20
  • DOI: 10.1039/C5CS90100F

Understanding Atom Probe Tomography of Oxide-Supported Metal Nanoparticles by Correlation with Atomic-Resolution Electron Microscopy and Field Evaporation Simulation
journal, March 2014

  • Devaraj, Arun; Colby, Robert; Vurpillot, François
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
  • DOI: 10.1021/jz500259c

Atomic-Scale Tomography: A 2020 Vision
journal, May 2013

  • Kelly, Thomas F.; Miller, Michael K.; Rajan, Krishna
  • Microscopy and Microanalysis, Vol. 19, Issue 3
  • DOI: 10.1017/S1431927613000494

Atom probe tomography analysis of poly(3-alkylthiophene)s
journal, February 2010


Application of Fourier transform and autocorrelation to cluster identification in the three-dimensional atom probe
journal, December 2004


Methods for in situ spectroscopic probing of the synthesis of a zeolite
journal, January 2010

  • Aerts, Alexander; Kirschhock, Christine E. A.; Martens, Johan A.
  • Chemical Society Reviews, Vol. 39, Issue 12
  • DOI: 10.1039/b919704b

Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes
journal, August 2015

  • Devaraj, A.; Gu, M.; Colby, R.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9014

In-situ Scanning Transmission X-Ray Microscopy of Catalytic Solids and Related Nanomaterials
journal, March 2010

  • de Groot, Frank M. F.; de Smit, Emiel; van Schooneveld, Matti M.
  • ChemPhysChem, Vol. 11, Issue 5
  • DOI: 10.1002/cphc.200901023

Influence of field evaporation on Radial Distribution Functions in Atom Probe Tomography
journal, April 2009


Translating new materials discoveries in zeolite research to commercial manufacture
journal, October 2011


Role of Photoexcitation and Field Ionization in the Measurement of Accurate Oxide Stoichiometry by Laser-Assisted Atom Probe Tomography
journal, March 2013

  • Devaraj, A.; Colby, R.; Hess, W. P.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 6
  • DOI: 10.1021/jz400015h

In situ site-specific specimen preparation for atom probe tomography
journal, February 2007


Point-by-point compositional analysis for atom probe tomography
journal, January 2014


Moving from discovery to real applications for your catalyst
journal, October 2016


New approaches to nanoparticle sample fabrication for atom probe tomography
journal, December 2015


Das Auflösungsvermögen des Feldionenmikroskopes
journal, January 1956


Mining information from atom probe data
journal, December 2015


Atomic Imaging of Carbon-Supported Pt, Pt/Co, and Ir@Pt Nanocatalysts by Atom-Probe Tomography
journal, December 2013

  • Li, Tong; Bagot, Paul A. J.; Christian, Elvis
  • ACS Catalysis, Vol. 4, Issue 2
  • DOI: 10.1021/cs401117e

Hydrogen production from formic acid decomposition at room temperature using a Ag–Pd core–shell nanocatalyst
journal, April 2011

  • Tedsree, Karaked; Li, Tong; Jones, Simon
  • Nature Nanotechnology, Vol. 6, Issue 5
  • DOI: 10.1038/nnano.2011.42

Three-dimensional nanoscale characterisation of materials by atom probe tomography
journal, November 2016


Detecting density variations and nanovoids
journal, May 2011


Atom Probe Tomography of Electronic Materials
journal, August 2007


Spatial Resolution in Atom Probe Tomography
journal, January 2010

  • Gault, Baptiste; Moody, Michael P.; De Geuser, Frederic
  • Microscopy and Microanalysis, Vol. 16, Issue 1
  • DOI: 10.1017/S1431927609991267

Atom probe crystallography
journal, September 2012


Nanoscale tomography reveals the deactivation of automotive copper-exchanged zeolite catalysts
journal, November 2017


    Works referencing / citing this record:

    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
    • DOI: 10.3390/app9132721

    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
    • DOI: 10.1002/cctc.201801378