Understanding The Fascinating Origins of CO<sub>2</sub> Adsorption and Dynamics in MOFs

Chen, Shoushun; Lucier, Bryan E. G.; Boyle, Paul D.; Huang, Yining

doi:10.1021/acs.chemmater.6b02239

Cited by 71 publications

(102 citation statements)

References 124 publications

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“…In particular, a low‐temperature 13 C SSNMR spectroscopic study of CO 2 ‐loaded CdSDB suggests that CO 2 occupies two nonequivalent sites in the CdSDB framework . In addition, single X‐ray diffraction of the CO 2 ‐loaded CdSDB framework confirmed that the two nonequivalent adsorption sites (labelled as C1A and C1B) are constituted by two different π pockets from the phenyl rings of the SDB ligands (Figure a, b) . As demonstrated by both SSNMR and single‐crystal XRD studies, the nature of the interaction between CO 2 molecules and both MOF frameworks is that the quadrupole moment of CO 2 interacts with the π electrons of the two phenyl rings .…”

Section: Resultsmentioning

confidence: 87%

“…However, the number of CO 2 adsorption sites and the nature of guest–host interactions may be substantially different from those at high pressures and can be efficiently tuned by external compression. In particular, a low‐temperature 13 C SSNMR spectroscopic study of CO 2 ‐loaded CdSDB suggests that CO 2 occupies two nonequivalent sites in the CdSDB framework . In addition, single X‐ray diffraction of the CO 2 ‐loaded CdSDB framework confirmed that the two nonequivalent adsorption sites (labelled as C1A and C1B) are constituted by two different π pockets from the phenyl rings of the SDB ligands (Figure a, b) .…”

Section: Resultsmentioning

confidence: 90%

“…The CO 2 adsorption study and guest–host interactions for both CdSDB and PbSDB frameworks at near ambient conditions have been extensively reported . However, the number of CO 2 adsorption sites and the nature of guest–host interactions may be substantially different from those at high pressures and can be efficiently tuned by external compression.…”

Section: Resultsmentioning

confidence: 99%

“…Among these SDB‐based MOFs, CdSDB has been shown to have an excellent CO 2 /N 2 selectivity compared to that of the other MOFs in the SDB family . In particular, the CO 2 adsorption mechanisms of the PbSDB and CdSDB frameworks were recently investigated using solid‐state nuclear magnetic resonance (SSNMR) spectroscopy at ambient pressure and low temperatures …”

Section: Introductionmentioning

confidence: 99%

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Elucidation of the Structural Origins and Contrasting Guest–Host Interactions in CO₂‐Loaded CdSDB and PbSDB Metal–Organic Frameworks at High Pressures

Jiang

Chen

et al. 2018

Chemistry A European J

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PbSDB and CdSDB (SDB=4,4′‐sulfonyldibenzoate) are two structurally related SDB‐based metal–organic frameworks (MOFs) that demonstrate promising potential for selective CO2 adsorption capabilities. The structural stabilities and guest–host interactions between CO2 and PbSDB or CdSDB frameworks at high pressures up to 13 GPa in situ were comparatively investigated by Raman spectroscopy, FTIR spectroscopy, and synchrotron X‐ray diffraction. Although both empty frameworks exhibited high chemical stabilities upon compression, they show different pressure‐induced modifications in crystallinity. This difference can be attributed to their different coordination topologies that result in near isotropic contraction of unit cells for the CdSDB framework but anisotropic for the PbSDB framework. Furthermore, the CO2‐loaded PbSDB and CdSDB frameworks at high pressures show strongly contrasting guest–host interactions in terms of the pressure‐regulated CO2 adsorption sites. In both frameworks, pressure can highly efficiently promote the formation of new CO2 adsorption sites and the enhancement of guest–host interactions. In the CO2‐loaded PbSDB framework, in particular, the peculiar pressure‐tuned CO2 population was observed preferentially on one of the two adsorption sites in response to external compression. These unique guest–host interaction behaviors can also be unambiguously correlated to their different topological origins. These findings for the PbSDB and CdSDB frameworks provide in‐depth understanding of the structure–property relationship, which is of fundamental importance for CO2 storage application in SDB‐based MOFs.

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Section: Resultsmentioning

confidence: 87%

Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Elucidation of the Structural Origins and Contrasting Guest–Host Interactions in CO₂‐Loaded CdSDB and PbSDB Metal–Organic Frameworks at High Pressures

Jiang

Chen

et al. 2018

Chemistry A European J

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“…Solid‐state NMR (SSNMR) spectroscopy is a sensitive probe of short‐range structures and can provide detailed information on the guest adsorption, structure, mobility, and host–guest interactions in MOFs ,,. NMR interactions are generally anisotropic and are affected by dynamics in a predictable manner, therefore, information regarding guest mobility and adsorption can be extracted from SSNMR spectra of gases within MOFs .…”

Section: Introductionmentioning

confidence: 99%

A Multifaceted Study of Methane Adsorption in Metal–Organic Frameworks by Using Three Complementary Techniques

Zhang

Fischer

Gan

et al. 2018

Chemistry A European J

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Methane is a promising clean and inexpensive energy alternative to traditional fossil fuels, however, its low volumetric energy density at ambient conditions has made devising viable, efficient methane storage systems very challenging. Metal-organic frameworks (MOFs) are promising candidates for methane storage. In order to improve the methane storage capacity of MOFs, a better understanding of the methane adsorption, mobility, and host-guest interactions within MOFs must be realized. In this study, methane adsorption within α-Mg (HCO ) , α-Zn (HCO ) , SIFSIX-3-Zn, and M-MOF-74 (M=Mg, Zn, Ni, Co) has been comprehensively examined. Single-crystal X-ray diffraction (SCXRD) experiments and DFT calculations of the methane adsorption locations were performed for α-Mg (HCO ) , α-Zn (HCO ) , and SIFSIX-3-Zn. The SCXRD thermal ellipsoids indicate that methane possesses significant mobility at the adsorption sites in each system. H solid-state NMR (SSNMR) experiments targeting deuterated CH D guests in α-Mg (HCO ) , α-Zn (HCO ) , SIFSIX-3-Zn, and MOF-74 yield an interesting finding: the H SSNMR spectra of methane adsorbed in these MOFs are significantly influenced by the chemical shielding anisotropy in addition to the quadrupolar interaction. The chemical shielding anisotropy contribution is likely due mainly to the nuclear independent chemical shift effect on the MOF surfaces. In addition, the H SSNMR results and DFT calculations strongly indicate that the methane adsorption strength is linked to the MOF pore size and that dispersive forces are responsible for the methane adsorption in these systems. This work lays a very promising foundation for future studies of methane adsorption locations and dynamics within adsorbent MOF materials.

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Recent Advances of Solid‐State NMR Spectroscopy for Microporous Materials

Lafon

Wang

et al. 2020

Advanced Materials

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< 2 nm), such as zeolites, metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and porous aromatic frameworks (PAFs), combine high specific surface areas, large pore volumes and shape-selectivity effects, which makes them key materials for a wide range of applications, including catalysis, gas separation/purification, ion exchange, gas storage, and sensing. The diverse framework compositions and functionalities of microporous materials represent a huge challenge for their structural characterization as well as evaluation of their performances. Analytic tools such as X-ray diffraction (XRD), electron microscopy and adsorption-desorption isotherms are now routinely employed for characterization of microporous materials in order to establish the structure-property relationships, and hence, to facilitate the rational design of advanced materials with improved property. However, the structure determination of porous materials using single crystal XRD requires high crystallinity and long-range ordering of the framework. Solid-state NMR (SSNMR) has emerged as a powerful spectroscopic technique with atomic-level resolution, complementary to XRD, in the investigation of structures in Microporous materials have attracted a rapid growth of research interest in materials science and the multidisciplinary area because of their wide applications in catalysis, separation, ion exchange, gas storage, drug release, and sensing. A fundamental understanding of their diverse structures and properties is crucial for rational design of high-performance materials and technological applications in industry. Solid-state NMR (SSNMR), capable of providing atomic-level information on both structure and dynamics, is a powerful tool in the scientific exploration of solid materials. Here, advanced SSNMR instruments and methods for characterization of microporous materials are briefly described. The recent progress of the application of SSNMR for the investigation of microporous materials including zeolites, metal-organic frameworks, covalent organic frameworks, porous aromatic frameworks, and layered materials is discussed with representative work. The versatile SSNMR techniques provide detailed information on the local structure, dynamics, and chemical processes in the confined space of porous materials. The challenges and prospects in SSNMR study of microporous and related materials are discussed.

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Understanding The Fascinating Origins of CO₂ Adsorption and Dynamics in MOFs

Cited by 71 publications

References 124 publications

Elucidation of the Structural Origins and Contrasting Guest–Host Interactions in CO₂‐Loaded CdSDB and PbSDB Metal–Organic Frameworks at High Pressures

Elucidation of the Structural Origins and Contrasting Guest–Host Interactions in CO₂‐Loaded CdSDB and PbSDB Metal–Organic Frameworks at High Pressures

A Multifaceted Study of Methane Adsorption in Metal–Organic Frameworks by Using Three Complementary Techniques

Recent Advances of Solid‐State NMR Spectroscopy for Microporous Materials

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Understanding The Fascinating Origins of CO2 Adsorption and Dynamics in MOFs

Cited by 71 publications

References 124 publications

Elucidation of the Structural Origins and Contrasting Guest–Host Interactions in CO2‐Loaded CdSDB and PbSDB Metal–Organic Frameworks at High Pressures

Elucidation of the Structural Origins and Contrasting Guest–Host Interactions in CO2‐Loaded CdSDB and PbSDB Metal–Organic Frameworks at High Pressures

A Multifaceted Study of Methane Adsorption in Metal–Organic Frameworks by Using Three Complementary Techniques

Recent Advances of Solid‐State NMR Spectroscopy for Microporous Materials

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Understanding The Fascinating Origins of CO₂ Adsorption and Dynamics in MOFs

Elucidation of the Structural Origins and Contrasting Guest–Host Interactions in CO₂‐Loaded CdSDB and PbSDB Metal–Organic Frameworks at High Pressures

Elucidation of the Structural Origins and Contrasting Guest–Host Interactions in CO₂‐Loaded CdSDB and PbSDB Metal–Organic Frameworks at High Pressures