Probing molecular motions in metal-organic frameworks with solid-state NMR

Fu, Yao; Guan, Hang; Yin, Jinglin; Kong, Xueqian

doi:10.1016/j.ccr.2020.213563

Cited by 32 publications

(18 citation statements)

References 213 publications

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“…[10,11] This technique is particularly useful for studies of intercalated phosphates, [12] where the behavior of deuterated guests can be well characterized by experiments on the 2 H nuclei. [13][14][15][16] Recently, by conducting 2 H and 31 P{ 1 H} solid-state MAS NMR experiments on a crystalline layered α-zirconium phosphate system, Zr (HPO 4 ) 2 Á0.35 D 2 O (1-D 2 O), including 31 P and 2 H T 1 measurements, [17] it has been revealed that there exists an unusual dynamic/bonding mode of the water, which is hydrogen bonded to the zirconium-coordinated oxygen and experiences a fast rotation (on the time scale of the NMR Larmor frequency) around this bond (Figure 1). At temperatures >253 K, the intercalated water unprecedentedly shows two spectrally distinguished deuterons.…”

Section: Introductionmentioning

confidence: 99%

Elucidating structure and dynamics of crystalline α‐zirconium phosphates intercalated with water and methanol by multinuclear solid‐state MAS NMR: A comprehensive NMR approach

Bakhmutov

Contreras-Ramírez

Drake

et al. 2022

Magnetic Reson in Chemistry

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Solid‐state NMR experiments on 2H, 31P, 13C, and 1H nuclei, including 31P T1, 1H T1, and 1H T1ρ measurements, as well as on the kinetics of proton‐phosphorus cross‐polarization have been performed to characterize the crystalline and amorphous α‐zirconium phosphates, which were intercalated with D2O and/or CD3OD. The 13C{1H} CP MAS NMR experiment performed for compound 1‐CD3OD (Zr (HPO4)2.0.2CD3OD) with carbon cross‐polarization via protons of phosphate groups has provided a prove that the methanol was intercalated into the interlayer spaces of this compound. The variable‐temperature 2H solid‐echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD3 rotations around the C3‐axis. It has been demonstrated that the intercalated species, D2O and CD3OD, do not affect the high‐frequency motions of the phosphate groups. By utilizing local structural models that satisfy the constraints of the experimental data, it has been suggested that the immobile methanol molecules are located in the cavity between two neighboring layers of the zirconium phosphates. Thus, the present work illustrates the reliable criteria in a comprehensive NMR approach to structural and dynamic studies of such systems.

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Section: Introductionmentioning

confidence: 99%

Elucidating structure and dynamics of crystalline α‐zirconium phosphates intercalated with water and methanol by multinuclear solid‐state MAS NMR: A comprehensive NMR approach

Bakhmutov

Contreras-Ramírez

Drake

et al. 2022

Magnetic Reson in Chemistry

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“…MOFs are attractive candidates for CO 2 capture because of their large surface area, structural diversity, and tunability. − The dynamics of CO 2 adsorption on MOFs, especially at high pressure, is of interest in gas separation methods such as pressure-swing adsorption and MOF-based membrane separation. The local motions of CO 2 , which include wobbling on and hopping among adsorption sites, reflect the strength of host–guest interactions and locations of CO 2 in the pores. − The rate of CO 2 diffusion and its dependence on pore geometry influence the gas permeability of MOF-based membranes . Therefore, the investigation of CO 2 dynamics in MOFs is crucial to improving their CO 2 separation capability and utilization in industrial processes.…”

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confidence: 99%

Slow CO₂ Diffusion Governed by Steric Hindrance of Rotatory Ligands in Small Pores of a Metal–Organic Framework

Kurihara

Inukai

Mizuno

2022

J. Phys. Chem. Lett.

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Understanding the adsorption and diffusional dynamics of CO 2 in metal− organic frameworks (MOFs) is essential in the application of these materials to CO 2 capture and separation. We show that the dynamics of adsorbed CO 2 is related to the rotational motion of ligands located in the narrow pore windows of a MOF using solid-state nuclear magnetic resonance (NMR) spectroscopy. NMR analyses of local dynamics reveal that CO 2 adsorbed in the pore hinders the rotation of the ligands. The rate of diffusion of adsorbed CO 2 monitored by 13 C NMR is much less than that in the larger pores of MOFs and decreases cooperatively with ligand mobility, which indicates that the rate of diffusion is influenced by the steric hindrance of the rotatory ligands. Adsorbed CH 4 also showed slow diffusion in the MOF, suggesting molecular size-selective effect of the mobile steric hindrance on the rate of adsorbate diffusion.

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“…Diverse examples can be found based on spectroscopic methods such as Raman and infrared (IR) spectroscopy, nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR). [159][160][161] These methods provide detailed information on the frameworks and on the host-guest interactions revealing the nature of these binding interactions.…”

Section: Mechanistic Insights and Operando Studies For Co 2 Capture I...mentioning

confidence: 99%

Understanding the opportunities of metal–organic frameworks (MOFs) for CO₂capture and gas-phase CO₂conversion processes: a comprehensive overview

et al. 2021

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Probing molecular motions in metal-organic frameworks with solid-state NMR

Cited by 32 publications

References 213 publications

Elucidating structure and dynamics of crystalline α‐zirconium phosphates intercalated with water and methanol by multinuclear solid‐state MAS NMR: A comprehensive NMR approach

Elucidating structure and dynamics of crystalline α‐zirconium phosphates intercalated with water and methanol by multinuclear solid‐state MAS NMR: A comprehensive NMR approach

Slow CO₂ Diffusion Governed by Steric Hindrance of Rotatory Ligands in Small Pores of a Metal–Organic Framework

Understanding the opportunities of metal–organic frameworks (MOFs) for CO₂capture and gas-phase CO₂conversion processes: a comprehensive overview

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Probing molecular motions in metal-organic frameworks with solid-state NMR

Cited by 32 publications

References 213 publications

Elucidating structure and dynamics of crystalline α‐zirconium phosphates intercalated with water and methanol by multinuclear solid‐state MAS NMR: A comprehensive NMR approach

Elucidating structure and dynamics of crystalline α‐zirconium phosphates intercalated with water and methanol by multinuclear solid‐state MAS NMR: A comprehensive NMR approach

Slow CO2 Diffusion Governed by Steric Hindrance of Rotatory Ligands in Small Pores of a Metal–Organic Framework

Understanding the opportunities of metal–organic frameworks (MOFs) for CO2capture and gas-phase CO2conversion processes: a comprehensive overview

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Slow CO₂ Diffusion Governed by Steric Hindrance of Rotatory Ligands in Small Pores of a Metal–Organic Framework

Understanding the opportunities of metal–organic frameworks (MOFs) for CO₂capture and gas-phase CO₂conversion processes: a comprehensive overview