Tunable coordinative defects in UHM-3 surface-mounted MOFs for gas adsorption and separation: A combined experimental and theoretical study

Wang, Zhengbang; Sezen, Hikmet; Liu, Jinxuan; Yang, Chengwu; Roggenbuck, Stephanie E.; Peikert, Katharina; Fröba, Michael; Mavrandonakis, Andreas; Supronowicz, Barbara; Heine, Thomas; Gliemann, Hartmut; Wöll, Christof

doi:10.1016/j.micromeso.2014.12.033

Cited by 34 publications

(36 citation statements)

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“…In the case of HKUST-1, CO molecules bound to Cu ++ ions of the defect-free structure exhibit IR bands at 2179 cm −1 , whereas Cu + species, which result from defect formation, cause an ≈60-cm −1 -shift to 2121 cm −1 . [14] Heating the samples significantly increased the defect concentration (Figure 2a left). The density of the most common defect, missing linkers, can be as low as 3%-4%.…”

Section: Mof Thin Films With Very Low Defect Densitymentioning

confidence: 98%

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Surface‐Mounted Metal–Organic Frameworks: Crystalline and Porous Molecular Assemblies for Fundamental Insights and Advanced Applications

2019

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with open voids attract significant interest, not only for use in gas storage and separation applications, [1b] but also as model systems used for fundamental investigations on molecular interactions. After being introduced about two decades ago, [2] this new type of crystalline coordination network created considerable excitement and much effort was devoted toward the discovery of new types of these compounds. In early 2017, after 20 years of intense research, the literature contains reports on more than 70 000 structurally characterized examples of this class. [3] Since MOFs can be assembled by combining molecular building blocks, specifically ditopic or higher-topic organic linkers and metal or metal-oxo nodes, a virtually unlimited number of structures can be realized. Moreover, essentially every organic molecule can be modified by the addition of appropriate coupling groups, e.g., carboxylic acid groups or pyridine units, to yield a ditopic linker. Therefore, the number of possible MOF structures is far greater than the number of known structures. In line with this consideration, more than a million of these compounds have been simulated using combinatorial approaches. [4] As MOFs are both crystalline and porous, they have fascinating and often surprising properties. Not only does the immense chemical space spanned by these compounds create enormous potential for advancing materials science, it also provides ideal matrices for reference experiments exploring fundamental spectroscopic and physicochemical properties. The framework provides a well-defined, crystalline, porous environment that can host guest molecules, thus permitting systematic spectroscopic investigations. In contrast to solvents or polymer matrices, MOFs provide a strictly periodic, very well defined structural framework, where the molecular environment is identical for each embedded guest molecule. In this respect, MOFs outperform amorphous noble-gas guest matrices [5] in which the environment surrounding varies from site to site, leading to inhomogeneous broadening of the embedded guest's spectroscopic features, including vibrational bands.Herein, we discuss the use of MOFs and, in particular, of surface-mounted metal-organic frameworks (SURMOFs), to provide well-defined environments for precisely determining Metal-organic frameworks (MOFs) are crystalline coordination polymers, assembled from inorganic nodes connected by organic linker molecules. An enormous surface area, huge compositional variety, regular structure, and favorable mechanical properties are among their outstanding properties. Monolithic MOF thin films, i.e., surface-mounted metalorganic frameworks (SURMOFs), with high degree of structural order and adjustable defect density, can be prepared on solid substrates using layer-by-layer techniques. Recent studies where SURMOFs served as model systems for quantitative studies of molecular interactions in porous media, including diffusion, are reviewed. Moreover, SURMOFs are ideally suited for the incorporation of photoactive mo...

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Section: Mof Thin Films With Very Low Defect Densitymentioning

confidence: 98%

“…Pulsed-field gradient nuclear magnetic resonance and quasi-elastic neutron scattering, which are conventionally used to investigate diffusion in nanoporous materials, [25] are usually not suitable for determining diffusion coefficients smaller than 10 −12 m 2 s −1 . [14] Copyright 2015, Elsevier. Mater.…”

Section: Unique Model System For Diffusion Experimentsmentioning

confidence: 99%

Surface‐Mounted Metal–Organic Frameworks: Crystalline and Porous Molecular Assemblies for Fundamental Insights and Advanced Applications

2019

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“…[15][16][17][18][19] It is generally accepted that, independent of the deposition method, the key for the growth of homogeneous and highly oriented SUR-MOFs is the suitable adjustment of the surface chemistry,asit determines the interactions between the MOF structure and the surface.Avery convenient method to control the surface chemistry is the use of self-assembled monolayers (SAMs), which can be tailored to expose av ariety of functional groups. [13,22,25,26] Tw oclasses of MOFs,which both are based on secondary building units (SBUs) comprising dinuclear tetracarboxylate clusters [M 2 (O 2 CR) 4 ]h aving the so-called paddle-wheel symmetry,h ave been successfully deposited in the form of highly defined SURMOFs.F irst, the cubic HKUST-1 MOF (Cu 3 btc 2 ;b tc = benzene-1,3,5-tricarboxylate) and its derivatives, [13,27] and second, the tetragonal, layered MOFs of the general formula [M 2 L 2 P],w here M = Cu 2+ or Zn 2+ ,L = a rigid, linear dicarboxylate linker,and P = an optional diamine pillar. -COOH or -NH 2 ), these can directly interact with the metal ions at the interface with the SURMOF,which does not only contribute to at ight binding,b ut also opens opportunities to control the orientation of the growing SURMOF crystallites.…”

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confidence: 99%

“…-COOH or -NH 2 ), these can directly interact with the metal ions at the interface with the SURMOF,which does not only contribute to at ight binding,b ut also opens opportunities to control the orientation of the growing SURMOF crystallites. [13,22,25,26] Tw oclasses of MOFs,which both are based on secondary building units (SBUs) comprising dinuclear tetracarboxylate clusters [M 2 (O 2 CR) 4 ]h aving the so-called paddle-wheel symmetry,h ave been successfully deposited in the form of highly defined SURMOFs.F irst, the cubic HKUST-1 MOF (Cu 3 btc 2 ;b tc = benzene-1,3,5-tricarboxylate) and its derivatives, [13,27] and second, the tetragonal, layered MOFs of the general formula [M 2 L 2 P],w here M = Cu 2+ or Zn 2+ ,L = a rigid, linear dicarboxylate linker,and P = an optional diamine pillar. [22,26,28,29] While the first class of MOFs can be formed very reliably and thus has turned out to be avery robust test system, the pillared-layer system shows al arger structural variability,and thus abroader range of potential applications, because of the basically independent choice of Land P. Aset of rules has been developed to predict the surface growth of these MOFs.W hile for the cubic HKUST-1 systems mostly the density of coordinating groups at the surface seems to determine the SURMOFs orientation, [30] in the tetragonal pillared-layer system the nature of the surface-exposed ligands is of major importance.Thus,monodentate functional groups (e.g.…”

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confidence: 99%

Minimization of Surface Energies and Ripening Outcompete Template Effects in the Surface Growth of Metal–Organic Frameworks

Zhuang

Scherr

et al. 2016

Angewandte Chemie

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As well-oriented, surface-bound metal-organic frameworks become the centerpiece of many new applications, ap rofound understanding of their growth mode becomes necessary.This work shows that the currently favored model of surface templating is in fact as pecial case valid only for systems with am ore or less cubic crystal shape,w hile in less symmetric systems crystal ripening and minimization of surface energies dominate the growth process.

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“…Therefore, the well‐oriented MOF thin films/membranes (membrane most commonly means a thin, selective barrier, but it is sometimes used for films that function as separators, like biological membranes.) can provide an alternative way to explore the adsorption/separation properties in different orientation …”

Section: The Applications Of Crystalline Highly Oriented Mof Filmsmentioning

confidence: 99%

Crystalline, Highly Oriented MOF Thin Film: the Fabrication and Application

2016

Chem. Rec.

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The thin film of metal-organic frameworks (MOFs) is a rapidly developing research area which has tremendous potential applications in many fields. One of the major challenges in this area is to fabricate MOF thin film with good crystallinity, high orientation and well-controlled thickness. In order to address this challenge, different appealing approaches have been studied intensively. Among various oriented MOF films, many efforts have also been devoted to developing novel properties and broad applications, such as in gas separator, thermoelectric, storage medium and photovoltaics. As a result, there has been a large demand for fundamental studies that can provide guidance and experimental data for further applications. In this account, we intend to present an overview of current synthetic methods for fabricating oriented crystalline MOF thin film and bring some updated applications. We give our perspective on the background, preparation and applications that led to the developments in this area and discuss the opportunities and challenges of using crystalline, highly oriented MOF thin film.

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Tunable coordinative defects in UHM-3 surface-mounted MOFs for gas adsorption and separation: A combined experimental and theoretical study

Cited by 34 publications

References 33 publications

Surface‐Mounted Metal–Organic Frameworks: Crystalline and Porous Molecular Assemblies for Fundamental Insights and Advanced Applications

Surface‐Mounted Metal–Organic Frameworks: Crystalline and Porous Molecular Assemblies for Fundamental Insights and Advanced Applications

Minimization of Surface Energies and Ripening Outcompete Template Effects in the Surface Growth of Metal–Organic Frameworks

Crystalline, Highly Oriented MOF Thin Film: the Fabrication and Application

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