Application of solid-state NMR techniques for structural characterization of metal-organic frameworks

He, Caiyan; Li, Shenhui; Xiao, Yilin; Xu, Jing; Deng, Feng

doi:10.1016/j.ssnmr.2022.101772

Cited by 18 publications

(19 citation statements)

References 128 publications

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“…Other more sophisticated but less accessible techniques include, for example, high-resolution TEM (HRTEM), cryogenic TEM (cryo-TEM), or annular dark-field imaging in scanning transmission electron microscopy (HAADF-STEM) for atomic-scale resolution. Recent trends in characterization techniques target, among others, the in situ analysis of MOF crystal growth [ 101 ], and the fine study of the spatial proximity between linkers, metal clusters, and the eventual guest molecules/particles [ 102 ].…”

Section: Challenges and Perspectivesmentioning

confidence: 99%

Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards real-world applications

2023

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The deployment of metal–organic frameworks (MOFs) in a plethora of analytical and bioanalytical applications is a growing research area. Their unique properties such as high but tunable porosity, well-defined channels or pores, and ease of post-synthetic modification to incorporate additional functional units make them ideal candidates for sensing applications. This is possible because the interaction of analytes with a MOF often results in a change in its structure, eventually leading to a modification of the intrinsic physicochemical properties of the MOF which is then transduced into a measurable signal. The high porosity allows for the adsorption of analytes very efficiently, while the tunable pore sizes/nature and/or installation of specific recognition groups allow modulating the affinity towards different classes of compounds, which in turn lead to good sensor sensitivity and selectivity, respectively. Some figures are given to illustrate the potential of MOF-based sensors in the most relevant application fields, and future challenges and opportunities to their possible translation from academia (i.e., laboratory testing of MOF sensing properties) to industry (i.e., real-world analytical sensor devices) are critically discussed. Graphical abstract

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Section: Challenges and Perspectivesmentioning

confidence: 99%

Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards real-world applications

2023

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“…[87] In addition, nuclear magnetic resonance spectroscopy (NMR) is widely been used for the determination of the purity of MOF, linker-metal ratio, unexploited modulators, and the presence or absence of solvent after activation. [88][89][90][91][92][93][94] Lucier and co-workers scrutinized the local structures of several metal centers in respective MOF structures by solid-state nuclear magnetic resonance (SS NMR) in correlating local structures. [89] Then, they effectively discovered the origin of disorders around metals, refined local metal geometry, and explored activation and adsorption effects on the metal local environment and in situ MOF changes.…”

Section: Characterization Techniques Of Mof Electrocatalystsmentioning

confidence: 99%

“…In addition, nuclear magnetic resonance spectroscopy (NMR) is widely been used for the determination of the purity of MOF, linker‐metal ratio, unexploited modulators, and the presence or absence of solvent after activation [88–94] . Lucier and co‐workers scrutinized the local structures of several metal centers in respective MOF structures by solid‐state nuclear magnetic resonance (SS NMR) in correlating local structures [89] .…”

Section: Metal‐organic Framework and Derivativesmentioning

confidence: 99%

Metal‐Organic Frameworks for Efficient Electrochemical Reduction of Carbon Dioxide

et al. 2023

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The large concentration of carbon dioxide (CO2) in the atmosphere can be utilized in industrial production using effective electrocatalysts such as metal‐organic frameworks (MOFs). Due to good properties such as high surface area, designable functionality, and uniform constitution, MOFs are regarded as promising electrocatalysts for the carbon dioxide electrochemical reduction reaction (eCO2RR). This review covers the importance, challenges, and mechanism of eCO2RR, and simply discusses the progress in the synthesis methods and characterization of MOFs. The review also thoroughly discusses the advances of single metal‐based MOFs, mixed metal‐based MOFs, and MOF derivatives as electrocatalysts for efficient eCO2RR.

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“…Nevertheless, the information about the host–guest interaction between solvents and internal MOF framework in hydrophobic MOF composites is scarce due to the lack of experimental evidences. Solid-state NMR is a versatile spectroscopic tool for the investigation of host–guest interactions between MOFs and confined small molecules. − The dynamic behaviors of adsorbed gaseous molecules such as CH 4 , H 2 , CO 2 , CO, C 2 H 6 , C 2 H 4 , C 3 H 8 , and C 3 H 6 on a variety of MOFs have been unraveled from variable temperature solid-state NMR experiments. − Moreover, the detailed interactions between confined guest solvents and MOFs frameworks have been comprehensively explored by multinuclear and multidimensional solid-state NMR spectroscopy. ,,,− Herein, solid-state NMR is utilized to explore the solvent permeability on hydrophobic PDMS-coated MIL-53 upon loadings of water, methanol, acetone, benzene, toluene, and ethylbenzene solvents. The structure–property relationship between the hydrophobic nature of PDMS-coated MIL-53 and host–guest interaction with various guest solvents is established based on the experimental observations.…”

Section: Introductionmentioning

confidence: 99%

Surface Hydrophobicity and Guest Permeability in Polydimethylsiloxane-Coated MIL-53 as Studied by Solid-State Nuclear Magnetic Resonance Spectroscopy

He,

Li,

Jiang

et al. 2023

ACS Appl. Mater. Interfaces

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Experimental characterization of the hydrophobic porous materials at the atomic and molecular levels is of great significance, but exploring their hydrophobicity characteristics and interactions with guest molecules with distinct polarity is still challenging. In this work, solid-state NMR is employed to characterize the surface hydrophobicity and explore the guest solvent permeability in polydimethylsiloxane (PDMS)-coated MIL-53. It was found that the PDMS-coated MIL-53 was hydrophobic to water and infiltrated to methanol, acetone, benzene, toluene, and ethylbenzene solvents. In addition, two types of guest solvents (methanol, acetone, benzene, toluene, and ethylbenzene), inside the pore and outside the pore of PDMS-coated MIL-53, were clearly identified using two-dimensional 1 H− 1 H homo-nuclear correlation NMR experiments. Moreover, the membrane thickness of the PDMS-coated MIL-53 could be determined from the analysis of the 1 H− 1 H spin diffusion buildup curves. Furthermore, the permeability of benzene, toluene, and ethylbenzene at different PDMS coating levels was extracted from 1 H MAS NMR. The increase of the hydrophobic PDMS layer resulted in a decrease of the penetration of aromatic guests to the internal pore of MIL-53. This work provides deep insights into the understanding of guest solvent permeability of hydrophobic layer-coated MOFs in the application fields of catalysis and separation.

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Application of solid-state NMR techniques for structural characterization of metal-organic frameworks

Cited by 18 publications

References 128 publications

Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards real-world applications

Recent progress of metal–organic frameworks as sensors in (bio)analytical fields: towards real-world applications

Metal‐Organic Frameworks for Efficient Electrochemical Reduction of Carbon Dioxide

Surface Hydrophobicity and Guest Permeability in Polydimethylsiloxane-Coated MIL-53 as Studied by Solid-State Nuclear Magnetic Resonance Spectroscopy

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