Advanced Fabrication Method for the Preparation of MOF Thin Films: Liquid-Phase Epitaxy Approach Meets Spin Coating Method

Chernikova, Valeriya; Shekhah, Osama; Eddaoudi, Mohamed

doi:10.1021/acsami.6b04701

Cited by 201 publications

(157 citation statements)

References 32 publications

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“…We especially investigate the specific activation energies for diffusion experiments and for the cisto-trans isomerization of a prototype photo switchable molecule, azobenzene, and we examine the charge transport of electrons. [6] Different LbL techniques, including spray coating, [7] spin coating, [8] and dip coating, [9] can be used for the SURMOF syntheses. Here, the specific advantages of SURMOFs will be highlighted.…”

Section: Introductionmentioning

confidence: 99%

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: Introductionmentioning

confidence: 99%

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

2019

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“…Numerous studies have well‐documented details on how to prepare MOFs thin film using the stepwise LPE method . So far, several new techniques of this method have been developed for MOF thin film preparation, namely pump, spray, dipping robot and spin coating methods.…”

Section: Methods For Fabrication Of Oriented Mof Thin Filmmentioning

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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“…However,t he synthesis of these finely tuned thin-films is laboriousa nd often expensive, although progress has been mader ecently,f or example, by usings pin-coating mediated syntheses. [7] The metal clusters can act as Lewis-acid sites, whereas certain ligands( or defects ites) can be tuned to induce basicityo ra cidity. [8] Considering that mostSURMOFs are not stable at elevated temperaturesa nd pressures, catalytic processes at milder conditions are required.…”

Section: Introductionmentioning

confidence: 99%

Nanoweb Surface‐Mounted Metal–Organic Framework Films with Tunable Amounts of Acid Sites as Tailored Catalysts

Mandemaker

Rivera‐Torrente

et al. 2019

Chemistry A European J

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Metal-organic frameworks (MOFs) are ap romising class of materials form any applications, due to their high chemical tunability and superb porosity.B yg rowing MOFs as (thin-)films, additional properties and potentiala pplications become available. Here, copper( II) 1,3,5-benzenetricarboxylate (Cu-BTC) metal-organic framework (MOF) thin-films are reported, which were synthesized by spin-coating, resulting in "nanowebs", that is, fiber-like structures. These surface-mounted MOFs (SURMOFs) were studied by using photoinduced force microscopy (PiFM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The optimal concentration of precursors (10 mm)w as determined that resulted in chemically homogeneous, pure nanowebs. Furthermore, the morphology and (un)coordinated Cu sites in the web were tuned by varyingt he rotation speed of the spin-coating process. X-ray diffraction (XRD) analysis showed that ro-tation speeds ! 2000 rpm (with precursors in aw ater/ethanol solution) generatet he catena-triaqua-m-(1,3,5-benzenetricarboxylate)-copper(II), or Cu(BTC)(H 2 O) 3 coordinationp olymer.X -ray photoelectrons pectroscopy (XPS) highlighted the strongd ecrease in number of (defective) Cu + sites, as the nanowebs mainly consist of coordinated Cu 2 + Lewis acid sites (LAS) and organic linker-linker,f or example, hydrogenbonding, interactions. Finally, the Lewis-acidic character of the Cu sites is illustrated by testing the films as catalysts in the isomerization of a-pineneo xide. The highern umber of LAS (! 3000 rpm), result in higher campholenic aldehyde selectivity reachingu pt o87.7 %. Furthermore, the strength of ac ombined micro-and spectroscopica pproach in understandingt he nature of MOF thin-films in as patially resolved manner is highlighted.[a] L.

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Advanced Fabrication Method for the Preparation of MOF Thin Films: Liquid-Phase Epitaxy Approach Meets Spin Coating Method

Cited by 201 publications

References 32 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

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

Nanoweb Surface‐Mounted Metal–Organic Framework Films with Tunable Amounts of Acid Sites as Tailored Catalysts

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