Understanding Time Dependence on Zinc Metal-Organic Framework Growth Using in Situ Liquid Secondary Ion Mass Spectrometry

Sandip Sabale; Dushyant Barpaga; Jennifer Yao; Libor Kovarik; Zihua Zhu; Sayandev Chatterjee; B. Peter McGrail; Radha Kishan Motkuri; Xiao Ying Yu

doi:10.1021/acsami.9b19991

Understanding Time Dependence on Zinc Metal-Organic Framework Growth Using in Situ Liquid Secondary Ion Mass Spectrometry

Sandip Sabale, Dushyant Barpaga, Jennifer Yao, Libor Kovarik, Zihua Zhu, Sayandev Chatterjee, B. Peter McGrail, Radha Kishan Motkuri, Xiao Ying Yu

Advanced Nuclear Materials

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

13 Scopus citations

Abstract

The abundance of novel metal-organic framework (MOF) materials continues to increase as more applications are discovered for these highly porous, well-ordered crystalline structures. The simplicity of constituents allows for the design of new MOFs with virtue of functionality and pore topology toward target adsorbates. However, the fundamental understanding of how these frameworks evolve during nucleation and growth is mostly limited to speculation from simulation studies. In this effort, we utilize a unique vacuum compatible system for analysis at the liquid vacuum interface (SALVI) microfluidic interface to analyze the formation and evolution of the benchmark MOF-74 framework using time-of-flight secondary ion mass spectrometry (ToF-SIMS). Principal component analysis of the SIMS mass spectra, together with ex situ electron microscopy, powder X-ray diffractometry, and porosimetry, provides new insights into the structural growth, metal-oxide cluster formation, and aging process of Zn-MOF-74. Samples collected over a range of synthesis times and analyzed closely with in situ ToF-SIMS, transmission electron microscopy, and gas adsorption studies verify the developing pore structure during the aging process.

Original language	English
Pages (from-to)	5090-5098
Number of pages	9
Journal	ACS Applied Materials and Interfaces
Volume	12
Issue number	4
DOIs	https://doi.org/10.1021/acsami.9b19991
State	Published - Jan 29 2020

Funding

S.S. is thankful to University Grants Commission, New Delhi, India, for awarding Raman Postdoctoral Fellowship to work at PNNL (F. No. 5-105/2016 (IC)). This research was supported by (i) Laboratory Directed Research and Development Program at the Pacific Northwest National Laboratory (SEED EED) and (ii) the U.S. Department of Energy (DOE)’s Geothermal Technologies Office (GTO) for MOF materials development. X.-Y.Y. thanks the MS3 Initiative at the Pacific Northwest National Laboratory (PNNL) for support. Part of this research was performed at Environmental Molecular Sciences Laboratory, a national scientific user facility at Pacific Northwest National Laboratory (PNNL) managed by the Department of Energy’s Office of Biological and Environmental Research. PNNL is operated by Battelle for the U.S. Department of Energy (DOE) under contract no. DE-AC05-76RL01830.

Keywords

in situ liquid SIMS
metal-organic framework
molecular imaging
SALVI
structure and growth

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10.1021/acsami.9b19991

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title = "Understanding Time Dependence on Zinc Metal-Organic Framework Growth Using in Situ Liquid Secondary Ion Mass Spectrometry",

abstract = "The abundance of novel metal-organic framework (MOF) materials continues to increase as more applications are discovered for these highly porous, well-ordered crystalline structures. The simplicity of constituents allows for the design of new MOFs with virtue of functionality and pore topology toward target adsorbates. However, the fundamental understanding of how these frameworks evolve during nucleation and growth is mostly limited to speculation from simulation studies. In this effort, we utilize a unique vacuum compatible system for analysis at the liquid vacuum interface (SALVI) microfluidic interface to analyze the formation and evolution of the benchmark MOF-74 framework using time-of-flight secondary ion mass spectrometry (ToF-SIMS). Principal component analysis of the SIMS mass spectra, together with ex situ electron microscopy, powder X-ray diffractometry, and porosimetry, provides new insights into the structural growth, metal-oxide cluster formation, and aging process of Zn-MOF-74. Samples collected over a range of synthesis times and analyzed closely with in situ ToF-SIMS, transmission electron microscopy, and gas adsorption studies verify the developing pore structure during the aging process.",

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Understanding Time Dependence on Zinc Metal-Organic Framework Growth Using in Situ Liquid Secondary Ion Mass Spectrometry

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