Interplay between defects, disorder and flexibility in metal-organic frameworks

Bennett, Thomas D.; Cheetham, Anthony K.; Fuchs, Alain H.; Coudert, François‐Xavier

doi:10.1038/nchem.2691

Cited by 394 publications

(343 citation statements)

References 55 publications

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“…Utilising modulators in MOF syntheses can result in the creation of defects, in the form of missing linkers and/or clusters with concomitant incorporation of capping modulators, which can impart the MOF with interesting and unusual physical properties. 31,32 Recent studies have shown that modulator incorporation and subsequently defectivity can be correlated to the pK a of the modulating agent.…”

Section: -16mentioning

confidence: 99%

Controlling interpenetration through linker conformation in the modulated synthesis of Sc metal–organic frameworks

et al. 2018

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Interpenetration in metal-organic frameworks (MOFs), where multiple nets of metal ions or clusters linked by organic ligands are nested within each other's pore spaces, affects important physical properties such as stability and gas uptake, and can be controlled through ligand sterics and modifying synthetic conditions. Herein, we extend the use of coordination modulation -deliberate addition of competing monotopic ligands to syntheses -to prepare Sc MOFs containing related biphenyl-4,4 0 -dicarboxylate (bpdc) and 2,2 0 -bipyridine-5,5 0 -dicarboxylate (bpydc) linkers. The Sc-bpdc MOF adopts a two-fold interpenetrated structure, however, the Sc-bpydc MOF is non-interpenetrated, despite only minor electronic modifications to the ligand. A comprehensive experimental and theoretical examination reveals that ligand twisting (energetically favourable for bpdc but not bpydc) and associated p-stacking interactions are a prerequisite for interpenetration. The more rigid Sc-bpdc is susceptible to modulation, resulting in differences in morphology, thermal stability and the synthesis of a highly defective, acetate-capped mesoporous material, while the large pore volume of Sc-bpydc allows postsynthetic metallation with CuCl 2 in a single-crystal to single-crystal manner. Controlling interpenetration through linker conformation could result in design of new materials with desirable properties such as bifunctional solidstate catalysts.

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Section: -16mentioning

confidence: 99%

Controlling interpenetration through linker conformation in the modulated synthesis of Sc metal–organic frameworks

et al. 2018

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“…[176] Studies of the mechanical properties and energy absorption in single crystals of four isostructural samples belonging to the UiO type of MOF highlighted plasticity and endothermicity during deformation. [179] At stresses higher than 2 GPa, energy absorption reaches 3-4 kJ per gram (for reference, about 4 kJ of energy per gram is released on the explosion of TNT, trinitrotoluol equivalent).…”

Section: Mechanical Metamaterialsmentioning

confidence: 99%

Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives

et al. 2019

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Owing to the synergistic combination of a hybrid organic–inorganic nature and a chemically active porous structure, metal–organic frameworks have emerged as a new class of crystalline materials. The current trend in the chemical industry is to utilize such crystals as flexible hosting elements for applications as diverse as gas and energy storage, filtration, catalysis, and sensing. From the physical point of view, metal–organic frameworks are considered molecular crystals with hierarchical structures providing the structure‐related physical properties crucial for future applications of energy transfer, data processing and storage, high‐energy physics, and light manipulation. Here, the perspectives of metal–organic frameworks as a new family of functional materials in modern physics are discussed: from porous metals and superconductors, topological insulators, and classical and quantum memory elements, to optical superstructures, materials for particle physics, and even molecular scale mechanical metamaterials. Based on complementary properties of crystallinity, softness, organic–inorganic nature, and complex hierarchy, a description of how such artificial materials have extended their impact on applied physics to become the mainstream in material science is offered.

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“…Porous crystalline solids are an important class of heterogeneous catalysts with, for example, zeolites as one of the most prominent examples ,. Metal‐Organic Frameworks (MOFs) are an emerging class of crystalline porous solids that recently have received a lot of attention . There are a several major reasons that MOFs are popular in (catalysis) research.…”

Section: Introductionmentioning

confidence: 99%

Behavior of a Metal Organic Framework Thin‐Film at Elevated Temperature and Pressure as Studied with an Autoclave‐Inserted Atomic Force Microscope

Brand

Mandemaker

et al. 2018

ChemPhysChem

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Bridging the gap in studying surface reactions, processes, and morphology and measuring at (catalytic) relevant conditions is crucial for our understanding of the working principles of porous crystalline materials. Scanning tunneling microscopy is limited because of the required conductivity of the sample, whereas atomic force microscopy (AFM) is often challenging in use owing to the physical mechanism underlying the technique. Herein, we report a tailor-made autoclave-inserted AFM, able to measure at ∼20 bar and ∼110 °C. First, we show the ability to obtain nanometer resolution on well-defined test samples at before-mentioned conditions. Second, to demonstrate the possibilities of analyzing morphological evolutions at elevated temperatures and pressures, we use this setup to measure the stability of a surface-anchored metal-organic framework (SURMOF) in-situ at pressures of 1-20 bar in the temperature range between 20 and 60 °C. It was found that the showcase HKUST-1 material has a good physical stability, as it is hardly damaged from exposure to pressures up to 20 bar. However, its thermal stability is weaker, as exposure to elevated T damaged the material by influencing the interaction between organic linker and metal cluster. In-situ measurements at elevated T also showed an increased mobility of the material when working at such conditions. Combining the strength of AFM at elevated T and p with ex-situ AFM and spectroscopic measurements on this MOF showcases an example of how porous materials can be studied at (industrially) relevant conditions using the autoclave-inserted AFM.

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Interplay between defects, disorder and flexibility in metal-organic frameworks

Cited by 394 publications

References 55 publications

Controlling interpenetration through linker conformation in the modulated synthesis of Sc metal–organic frameworks

Controlling interpenetration through linker conformation in the modulated synthesis of Sc metal–organic frameworks

Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives

Behavior of a Metal Organic Framework Thin‐Film at Elevated Temperature and Pressure as Studied with an Autoclave‐Inserted Atomic Force Microscope

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