Extent of Radiolytic Damage from Liquid Cell TEM Experiments on Metal-Organic Frameworks via Post-Mortem 4D-STEM

Karthik Gnanasekaran; Nathan D. Rosenmann; Roberto dos Reis; Nathan C. Gianneschi

doi:10.1021/acs.nanolett.4c02242

Extent of Radiolytic Damage from Liquid Cell TEM Experiments on Metal-Organic Frameworks via Post-Mortem 4D-STEM

Karthik Gnanasekaran, Nathan D. Rosenmann, Roberto dos Reis, Nathan C. Gianneschi^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

We report a systematic analysis of electron beam damage of the zeolitic imidazolate framework (ZIF-8) during liquid cell transmission electron microscopy (LCTEM). Our analysis reveals ZIF-8 morphology is strongly affected by solvent used (water vs dimethylformamide), electron flux applied, and imaging mode (i.e., TEM vs STEM), while ZIF-8 crystallinity is primarily affected by accumulated electron fluence. Our observations indicate that the stability of ZIF-8 morphology is higher in dimethylformamide (DMF) than in water. However, in situ electron diffraction indicates that ZIF-8 nanocrystals lose crystallinity at critical fluence of ∼80 e^-Å^-2 independent of the presence of solvent. Furthermore, 4D-STEM analysis as a post-mortem method reveals the extent of electron beam damage beyond the imaging area and indicates that radiolytic reactions are more pronounced in TEM mode than in STEM mode. These results illustrate the significance of radiolysis occurring while imaging ZIF-8 and present a workflow for assessing damage in LCTEM experiments.

Original language	English (US)
Pages (from-to)	10161-10168
Number of pages	8
Journal	Nano letters
Volume	24
Issue number	33
DOIs	https://doi.org/10.1021/acs.nanolett.4c02242
State	Published - Aug 21 2024

Funding

K.G., N.D.R., and N.C.G. thank the National Science Foundation (NSF DMR-2207269) for supporting this work. This work made use of the EPIC facility of Northwestern University\u2019s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern\u2019s MRSEC program (NSF DMR-2308691). This research was supported in part through the computational resources and staff contributions provided for the Quest high performance computing facility at Northwestern University which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. This work was also supported by the Department of Energy, Basic Energy Science (BES) Office through awards no. DESC0022332. NDR would also like to acknowledge the support from the Ryan Fellowship and the IIN at Northwestern University. The authors would also like to thank Dr. Yu Chen, a post doctoral scholar in the Giannsechi group at Northwestern University, for designing the cover art associated with this manuscript.

Keywords

4D-STEM
ZIF-8
electron beam damage
liquid cell transmission electron microscopy
metal−organic frameworks

ASJC Scopus subject areas

Bioengineering
General Chemistry
General Materials Science
Condensed Matter Physics
Mechanical Engineering

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10.1021/acs.nanolett.4c02242

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title = "Extent of Radiolytic Damage from Liquid Cell TEM Experiments on Metal-Organic Frameworks via Post-Mortem 4D-STEM",

abstract = "We report a systematic analysis of electron beam damage of the zeolitic imidazolate framework (ZIF-8) during liquid cell transmission electron microscopy (LCTEM). Our analysis reveals ZIF-8 morphology is strongly affected by solvent used (water vs dimethylformamide), electron flux applied, and imaging mode (i.e., TEM vs STEM), while ZIF-8 crystallinity is primarily affected by accumulated electron fluence. Our observations indicate that the stability of ZIF-8 morphology is higher in dimethylformamide (DMF) than in water. However, in situ electron diffraction indicates that ZIF-8 nanocrystals lose crystallinity at critical fluence of ∼80 e-{\AA}-2 independent of the presence of solvent. Furthermore, 4D-STEM analysis as a post-mortem method reveals the extent of electron beam damage beyond the imaging area and indicates that radiolytic reactions are more pronounced in TEM mode than in STEM mode. These results illustrate the significance of radiolysis occurring while imaging ZIF-8 and present a workflow for assessing damage in LCTEM experiments.",

keywords = "4D-STEM, ZIF-8, electron beam damage, liquid cell transmission electron microscopy, metal−organic frameworks",

author = "Karthik Gnanasekaran and Rosenmann, {Nathan D.} and {dos Reis}, Roberto and Gianneschi, {Nathan C.}",

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AU - dos Reis, Roberto

AU - Gianneschi, Nathan C.

PY - 2024/8/21

Y1 - 2024/8/21

N2 - We report a systematic analysis of electron beam damage of the zeolitic imidazolate framework (ZIF-8) during liquid cell transmission electron microscopy (LCTEM). Our analysis reveals ZIF-8 morphology is strongly affected by solvent used (water vs dimethylformamide), electron flux applied, and imaging mode (i.e., TEM vs STEM), while ZIF-8 crystallinity is primarily affected by accumulated electron fluence. Our observations indicate that the stability of ZIF-8 morphology is higher in dimethylformamide (DMF) than in water. However, in situ electron diffraction indicates that ZIF-8 nanocrystals lose crystallinity at critical fluence of ∼80 e-Å-2 independent of the presence of solvent. Furthermore, 4D-STEM analysis as a post-mortem method reveals the extent of electron beam damage beyond the imaging area and indicates that radiolytic reactions are more pronounced in TEM mode than in STEM mode. These results illustrate the significance of radiolysis occurring while imaging ZIF-8 and present a workflow for assessing damage in LCTEM experiments.

AB - We report a systematic analysis of electron beam damage of the zeolitic imidazolate framework (ZIF-8) during liquid cell transmission electron microscopy (LCTEM). Our analysis reveals ZIF-8 morphology is strongly affected by solvent used (water vs dimethylformamide), electron flux applied, and imaging mode (i.e., TEM vs STEM), while ZIF-8 crystallinity is primarily affected by accumulated electron fluence. Our observations indicate that the stability of ZIF-8 morphology is higher in dimethylformamide (DMF) than in water. However, in situ electron diffraction indicates that ZIF-8 nanocrystals lose crystallinity at critical fluence of ∼80 e-Å-2 independent of the presence of solvent. Furthermore, 4D-STEM analysis as a post-mortem method reveals the extent of electron beam damage beyond the imaging area and indicates that radiolytic reactions are more pronounced in TEM mode than in STEM mode. These results illustrate the significance of radiolysis occurring while imaging ZIF-8 and present a workflow for assessing damage in LCTEM experiments.

KW - 4D-STEM

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KW - liquid cell transmission electron microscopy

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Extent of Radiolytic Damage from Liquid Cell TEM Experiments on Metal-Organic Frameworks via Post-Mortem 4D-STEM

Abstract

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