SURMOFs: Liquid-Phase Epitaxy of Metal-Organic Frameworks on Surfaces

Heinke, Lars; Gliemann, Hartmut; Tremouilhac, Pierre; Wöll, Christof

doi:10.1002/9783527693078.ch17

Cited by 9 publications

(10 citation statements)

References 86 publications

(89 reference statements)

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“…An overview on in situ monitoring of the formation of crystalline solids in general and in situ studies on MOF syntheses have been summarized by N. Pienack and W. Bensch [178], N. Stock and S. Biswas [155], R. Walton and F. Millange [179] and I. Senkovska and V. Bon [177]. In situ studies carried out by the groups of R. A. Fischer and C. Wöll on layer-by-layer growth of SURMOFs [180] will be covered in Section 5.8.…”

Section: In Situ Characterization During Synthesismentioning

confidence: 99%

Metal–organic frameworks in Germany: From synthesis to function

Evans

Garai

Reinsch

et al. 2019

Coordination Chemistry Reviews

107

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Metal-organic frameworks (MOFs) are constructed from a combination of inorganic and organic units to produce materials which display high porosity, among other unique and exciting properties. MOFs have shown promise in many wide ranging applications, such as catalysis and gas separations. In this review, we highlight MOF research conducted by Germany-based research groups. Specifically, we feature approaches for the synthesis of new MOFs, high-throughput MOF production, advanced characterization methods and examples of advanced functions and properties.

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Section: In Situ Characterization During Synthesismentioning

confidence: 99%

Metal–organic frameworks in Germany: From synthesis to function

Evans

Garai

Reinsch

et al. 2019

Coordination Chemistry Reviews

107

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“…On suitably functionalized substrates (e.g., gold, silicon, quartz, glass, and metal oxides), highly oriented monolithic crystals can be grown that direct the nucleation site, orientation, and structure of the deposited SURMOF (Figure ). Here we describe only key elements and very briefly some landmark results in SURMOF formation. A detailed description of the surface/interface chemistry can be found in previous reviews. − …”

Section: Introductionmentioning

confidence: 99%

Metal–Organic Framework-Templated Biomaterials: Recent Progress in Synthesis, Functionalization, and Applications

et al. 2019

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The integration of a porous crystalline framework with soft polymers to create novel biomaterials has tremendous potential yet remains very challenging to date. Metal−organic framework (MOF)-templated polymers (MTPs) have emerged as persistent modular materials that can be tailored for desired biofunctions. These represent a novel class of hierarchically structured assemblies that combine the advantages of MOFs (precisely controlled structure, enormous diversity in framework topology, and high porosity) with the intrinsic behaviors of polymers (soft texture, flexibility, biocompatibility, and improved stability under physiological conditions). Transformation of surface-anchored MOFs (SURMOFs) via orthogonal covalent crosslinking yields surface-anchored polymeric gels (SURGELs) that open up exciting new opportunities to create soft nanoporous materials. SURGELs overcome the main drawbacks of SURMOFs, such as their limited stability under physiological conditions and their potential to release toxic metal ions, a substantial problem for applications in life sciences. MOF (SURMOF)-templated polymerization processes control the synthesis on a molecular level. Additionally, the morphology of the original MOF crystal template is replicated in the final network polymers. The MOF-templated polymerization can be induced by light, a catalyst, or temperature using several types of reactions, including thiol−ene, metalfree alkyne−azide click reactions, and Glaser−Hay coupling. In the case of photoinduced reactions, the cross-linking process can be locally confined, allowing control of the macroscopic patterning of the resulting network polymer. The use of layer-by-layer (lbl) techniques in the SURMOF synthesis serves the purpose of precise, layer-selective incorporation of functionalities via the combination of the postsynthetic modification and heteroepitaxy strategies. Transforming the functionalized SURMOF into a SURGEL allows the fabrication of polymers with desired bioactive functions at the internal or external surfaces. This Account highlights our ongoing research and inspiring progress in transforming SURMOFs into persistent, modular nanoporous materials tailored with biofunctions. Using cell culture studies, we present various aspects of SURGEL materials, such as the ability to deliver bioactive molecules to adhering cells on SURGEL surfaces, applications to advanced drug delivery systems, the ability to tune cell adhesion via surface modification, and the development of porphyrin-based SURGEL thin films with antimicrobial properties. Then we critically examine the challenges and limitations of current systems and discuss future research directions and new approaches for advancing MOF-templated biocompatible materials, emphasizing the need to include responsive and adaptive functionalities into the system. We emphasize that the hierarchical structure, ranging from the molecular to the macroscopic scale, allows for optimization of the material properties across all length scales relevant for cell− material interactio...

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“…7,8 SURMOFs are grown as thin films on substrate surfaces, usually via a liquid phase epitaxy (LPE) procedure. 9 Prior to the synthesis, the substrate's surface is modified with different functional groups, most commonly through the use of self-assembled monolayers (SAMs), such as the ones formed by thiols or silanes. 10 The modification of the substrate's surface is necessary in order to allow a strong bonding with the SURMOF via the coordination of the terminal group of the SAM to the metal clusters of the MOF at the interface.…”

Section: Introductionmentioning

confidence: 99%

“…Despite all these advantages, MOFs have one main problem when it comes to device integration: they are usually obtained in the form of bulk powder via hydro-/solvothermal synthesis . This technical limitation was partially solved with the development of surface anchored metal–organic frameworks (SURMOFs). , SURMOFs are grown as thin films on substrate surfaces, usually via a liquid phase epitaxy (LPE) procedure . Prior to the synthesis, the substrate’s surface is modified with different functional groups, most commonly through the use of self-assembled monolayers (SAMs), such as the ones formed by thiols or silanes .…”

Section: Introductionmentioning

confidence: 99%

Impact of Synthetic Conditions on the Morphology and Crystallinity of FDMOF-1(Cu) Thin Films

Lugier

Pokharel

Castellanos

2020

Crystal Growth & Design

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Metal-organic frameworks (MOFs) have attracted a lot of interest for their numerous properties. However they are usually obtained as a powder (bulk) or as single crystals, which complicates their implementation into devices that could further exploit these properties. The development of Surface Anchored MOFs (SURMOFs), allowed to synthesize MOFs' thin films chemisorbed to a substrate, creating a viable solution to the device integration problem. Yet, the fundamental understanding of the mechanisms governing their growth remains limited and the systematic optimization of synthetic parameters is tedious. More studies on SURMOFs growth are needed before MOFbased devices become the norm. In this paper, a pillared-layer MOF with fluorinated terephthalate linkers, Cu 2 (fbdc) 2 (dabco) or F-DMOF-1(Cu), was synthesized on functionalized gold surfaces using a layer-by-layer method of Liquid Phase Epitaxy (LPE). The effects of temperature, linker concentration, type of surface functionalization and sonication during the rinsing step on coverage, film morphology and crystal orientation were studied. We found that the concentration of the linker has a strong impact on the morphology of the crystallites formed as well as on the surface coverage. It was noticed that the crystalline orientation is not only governed by the functionalization of the substrate, supporting the hypothesis that SURMOF thin films can switch their crystalline orientation during growth. This study adds information on which variables affect the formation of the first layers of a prototypical SURMOF.

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SURMOFs: Liquid-Phase Epitaxy of Metal-Organic Frameworks on Surfaces

Cited by 9 publications

References 86 publications

Metal–organic frameworks in Germany: From synthesis to function

Metal–organic frameworks in Germany: From synthesis to function

Metal–Organic Framework-Templated Biomaterials: Recent Progress in Synthesis, Functionalization, and Applications

Impact of Synthetic Conditions on the Morphology and Crystallinity of FDMOF-1(Cu) Thin Films

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