Zeolitic Imidazolate Frameworks: Next‐Generation Materials for Energy‐Efficient Gas Separations

Pimentel, Brian R.; Parulkar, Aamena; Zhou, Erkang; Brunelli, Nicholas A.; Lively, Ryan P.

doi:10.1002/cssc.201402647

Cited by 253 publications

(221 citation statements)

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“…The reasons are obvious: the 1st could solve the energy transferring problem, while the 2nd is responsible for global warming. There are several review papers presenting collections of MOFs and their youngest brothers-covalent organic frameworks, 16,17 zeolitic imidazolate frameworks 18,19 etc., with very high performance in gas storage.…”

Section: Introductionmentioning

confidence: 99%

Chemically intuited, large-scale screening of MOFs by machine learning techniques

et al. 2017

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A novel computational methodology for large-scale screening of MOFs is applied to gas storage with the use of machine learning technologies. This approach is a promising trade-off between the accuracy of ab initio methods and the speed of classical approaches, strategically combined with chemical intuition. The results demonstrate that the chemical properties of MOFs are indeed predictable (stochastically, not deterministically) using machine learning methods and automated analysis protocols, with the accuracy of predictions increasing with sample size. Our initial results indicate that this methodology is promising to apply not only to gas storage in MOFs but in many other material science projects.npj Computational Materials (2017) 3:40 ; doi:10.1038/s41524-017-0045-8 INTRODUCTION Metal-organic frameworks (MOFs) or porous coordination polymers are a rapidly growing family of hybrid inorganic-organic nanoporous materials, which belong to the category of coordination polymers.1-3 These relatively new materials consist of a threedimensional periodic network, constructed from molecular building blocks, such as metal clusters and organic linkers (Fig. 1). The possible combinations of these numerous building blocks under different topologies result is an almost unlimited number of potential MOFs! Since their discovery 4 MOFs have attracted significant scientific attention due to their extraordinary properties. As "skeleton" materials, they pose very large pores and outstanding apparent surface area. If we were able to unwrap the surface of only one gram of these "very empty" materials, we could cover the area of a football court! These unique characteristics of the MOFs made them excellent candidates for catalysis and gas storage applications.MOFs have shown exceptional performance in gas storage and separation. Both useful and harmful gases can be absorbed in their pores in very large amounts. The storage of hydrogen,

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Section: Introductionmentioning

confidence: 99%

Chemically intuited, large-scale screening of MOFs by machine learning techniques

et al. 2017

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“…It is noticeable for ZIF-8 that the agreement between experiment and calculation for Ω is poorer than for the other ZIFs, perhaps reflecting the dynamics of the -CH 3 group. More complex ZIFs can be synthesised using more than one type of linker, producing materials that not only have different pore shapes and sizes, but that can also have different chemical properties (e.g., hydrophobic or hydrophilic pores) [2,[4][5][6][7][8][9]. The 13 C CP MAS NMR spectra of ZIF-68, ZIF-70 and ZIF-78 are shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

“…1a shows the structure of ZIF-65, which is synthesised with 2-nitroimidazolate as the linker, and exhibits the well-known sodalite (SOD) framework topology [3]. ZIFs have attracted considerable recent attention, owing to their potential applications in gas storage and separation, fluid separation, sensing, encapsulation and controlled delivery of drug molecules [2,[4][5][6][7][8][9]. The range of applications can be widened by using functionalised imidazolate linkers, altering the chemical nature of the pores produced, while maintaining the framework topology [10].…”

Section: Introductionmentioning

confidence: 99%

Investigation of zeolitic imidazolate frameworks using 13 C and 15 N solid-state NMR spectroscopy

Sneddon

Kahr

Orsi

et al. 2017

Solid State Nuclear Magnetic Resonance

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Zeolitic imidazolate frameworks (ZIFs) are a subclass of metal-organic frameworks (MOFs) with extended threedimensional networks of transition metal nodes (bridged by rigid imidazolate linkers), with potential applications in gas storage and separation, sensing and controlled delivery of drug molecules. Here, we investigate the use of 13 C and 15 N solid-state NMR spectroscopy to characterise the local structure and disorder in a variety of singleand dual-linker ZIFs. In most cases, a combination of a basic knowledge of chemical shifts typically observed in solution-state NMR spectroscopy and the use of dipolar dephasing NMR experiments to reveal information about quaternary carbon species are combined to enable spectral assignment. Accurate measurement of the anisotropic components of the chemical shift provided additional information to characterise the local environment and the possibility of trying to understand the relationships between NMR parameters and both local and long-range structure. First-principles calculations on some of the simpler, ordered ZIFs were possible, and provided support for the spectral assignments, while comparison of these model systems to more disordered ZIFs aided interpretation of the more complex spectra obtained. It is shown that 13 C and 15 N NMR are sufficiently sensitive to detect small changes in the local environment, e.g., functionalisation of the linker, crystallographic inequivalence and changes to the framework topology, while the relative proportion of each linker present can be obtained by comparing relative intensities of resonances corresponding to chemically-similar species in cross polarisation experiments with short contact times. Therefore, multinuclear NMR spectroscopy, and in particular the measurement of both isotropic and anisotropic parameters, offers a useful tool for the structural study of ordered and, in particular, disordered ZIFs.

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“…1,2 Because the M-lm-M angle in ZIF (∼145°) is similar to Si-O-Si angle in conventional silicon-based zeolites, ZIFs give rise to zeolite-type topology. Unlike zeolite, ZIFs are unique in structural flexibility including tunable framework, pore aperture, and surface area.…”

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Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications

et al. 2016

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Zeolitic imidazolate frameworks (ZIFs) have emerged as a novel class of porous metal-organic frameworks (MOFs) for catalysis application because of their exceptional thermal and chemical stability. Inspired by the broad absorption of ZIF-67 in UV-vis-near IR region, we explored its excited state and charge separation dynamics, properties essential for photocatalytic applications, using optical (OTA) and X-ray transient absorption (XTA) spectroscopy. OTA results show that an exceptionally long-lived excited state is formed after photoexcitation. This long-lived excited state was confirmed to be the charge-separated (CS) state with ligand-to-metal charge-transfer NOT THE PUBLISHED VERSION; this is the author's final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page. Society, Vol 138, No. 26 (2016): pg. 8072-8075. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. Journal of the American Chemical3 character using XTA. The surprisingly long-lived CS state, together with its intrinsic hybrid nature, all point to its potential application in heterogeneous photocatalysis and energy conversion.Zeolitic imidazolate frameworks (ZIFs) represent an emerging subclass of metal organic frameworks (MOFs) constructed from tetrahedral coordinated transition-metal cations (M) bridged by imidazole-based ligands (lm).1,2 Because the M-lm-M angle in ZIF (∼145°) is similar to Si-O-Si angle in conventional silicon-based zeolites, ZIFs give rise to zeolite-type topology. Unlike zeolite, ZIFs are unique in structural flexibility including tunable framework, pore aperture, and surface area.1,2 Indeed, over 150 ZIF structures have, to date, been synthesized, many of which are microporous with inherently large surface areas and tunable cavities, and exhibit exceptional thermal and chemical stability.3-6 Thus, ZIFs demonstrate great promise in various applications such as gas separation and storage, 6-11 chemical sensing, 12 and heterogeneous catalysis. 13-17Driven by the increasing global energy demand, recent development in the field has extended the application of ZIF materials toward photocatalysis using visible light. Although still in the early stage of exploration, ZIFs have been used as photocatalysts for dye and phenol degradation as well as CO2 reduction. 15,[17][18][19] In these systems, photoactive nanostructures/molecules are incorporated into the highly porous structure of ZIFs, where ZIFs are used as a simple host or passive medium for dispersing the catalytic active species. This strategy has been widely used in developing zeolite-based photocatalysts 20 and recently in preparing MOF/nanocomposite or MOF/molecular catalyst hybrids, 19,21,22 yet suffers from challenges, notab...

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Zeolitic Imidazolate Frameworks: Next‐Generation Materials for Energy‐Efficient Gas Separations

Cited by 253 publications

References 330 publications

Chemically intuited, large-scale screening of MOFs by machine learning techniques

Chemically intuited, large-scale screening of MOFs by machine learning techniques

Investigation of zeolitic imidazolate frameworks using 13 C and 15 N solid-state NMR spectroscopy

Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications

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