Welcoming Gallium- and Indium-Fumarate MOFs to the Family: Synthesis, Comprehensive Characterization, Observation of Porous Hydrophobicity, and CO<sub>2</sub> Dynamics

Zhang, Yue; Lucier, Bryan E. G.; McKenzie, Sarah M.; Arhangelskis, Mihails; Morris, Andrew J.; Friščić, Tomislav; Reid, Joel W.; Terskikh, Victor V.; Chen, Man-Sheng; Huang, Yining

doi:10.1021/acsami.8b08562

Cited by 35 publications

(34 citation statements)

References 73 publications

(211 reference statements)

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“…In recent years, we have examined CO 2 dynamics in three types of MOFs where the CO 2 molecules are adsorbed at the framework hydrogen atoms: (i) MIL-53 (M), M = Al, Ga; 66 (ii) α-Mg 3 (HCOO) 6 ; 39 and (iii) Al-fumarate. 67 In (i) and (iii), the CO 2 molecules are adsorbed at the hydrogens of the bridging hydroxyl groups, whereas in (ii) the CO 2 molecules are adsorbed at the hydrogens of the formate linkers. The common motion experienced by CO 2 in these types of MOFs is the local rotation or wobbling motion.…”

Section: Resultsmentioning

confidence: 99%

Exploring Host–Guest Interactions in the α-Zn₃(HCOO)₆ Metal-Organic Framework

Wong

Boyle

et al. 2019

ACS Omega

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Metal-organic frameworks (MOFs) are promising gas adsorbents. Knowledge of the behavior of gas molecules adsorbed inside MOFs is crucial for advancing MOFs as gas capture materials. However, their behavior is not always well understood. In this work, carbon dioxide (CO 2 ) adsorption in the microporous α-Zn 3 (HCOO) 6 MOF was investigated. The behavior of the CO 2 molecules inside the MOF was comprehensively studied by a combination of single-crystal X-ray diffraction (SCXRD) and multinuclear solid-state magnetic resonance spectroscopy. The locations of CO 2 molecules adsorbed inside the channels of the framework were accurately determined using SCXRD, and the framework hydrogens from the formate linkers were found to act as adsorption sites. 67 Zn solid-state NMR (SSNMR) results suggest that CO 2 adsorption does not significantly affect the metal center environment. Variable-temperature 13 C SSNMR experiments were performed to quantitatively examine guest dynamics. The results indicate that CO 2 molecules adsorbed inside the MOF channel undergo two types of anisotropic motions: a localized rotation (or wobbling) upon the adsorption site and a twofold hopping between adjacent sites located along the MOF channel. Interestingly, 13 C SSNMR spectroscopy targeting adsorbed CO 2 reveals negative thermal expansion (NTE) of the framework as the temperature rose past ca. 293 K. A comparative study shows that carbon monoxide (CO) adsorption does not induce framework shrinkage at high temperatures, suggesting that the NTE effect is guest-specific.

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Section: Resultsmentioning

confidence: 99%

Exploring Host–Guest Interactions in the α-Zn₃(HCOO)₆ Metal-Organic Framework

Wong

Boyle

et al. 2019

ACS Omega

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“…The motion of CO 2 and the interactions with framework in various MOFs were comprehensively studied by VT 13 C static NMR experiments. [81] Diamine-appended MOFs are highly efficient for CO 2 adsorption from various gas mixtures. [82] Recently, multinuclear SSNMR spectroscopy has been utilized to characterize CO 2 chemisorption in diamine-appended metal-organic frameworks.…”

Section: Co 2 In Mofsmentioning

confidence: 99%

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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“…This may, in part, explain why most of the studies found in the literature of Ga 3+ -CP/MOFs report only their structures. Furthermore, most of the applications that have been studied are related to those that are also found for Al 3+ -CP/MOFs (Banerjee et al, 2011;Zhang et al, 2018;Reinsch & De Vos, 2014;Canivet et al, 2014;Zhou et al, 2012). For certain applications, Ga 3+ -CP/ MOFs excel, even surpassing the performance of the Al 3+ -CP/ MOFs (Coudert et al, 2014;Ramaswamy et al, 2017;Weber et al, 2016;Gao et al, 2014).…”

Section: Chemical Contextmentioning

confidence: 99%