Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks

Morris, William; Volosskiy, Boris; Demir, Selçuk; Gándara, Felipe; McGrier, Psaras L.; Furukawa, Hiroyasu; Cascio, Duilio; Stoddart, J. Fraser; Yaghi, Omar M.

doi:10.1021/ic300825s

Cited by 815 publications

(670 citation statements)

References 15 publications

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“…In Figure 1b, the crystal structures of pristine MOF‐525, PEDOT NTs, and MOF‐525–PEDOT NTs nanocomposite were characterized by X‐ray diffractometer (XRD). Diffraction peaks of MOF‐525 nanocrystals appear at 2θ = 4.6°, 6.5°, 8.0°, and 9.2°; these peaks agree well with the previously reported XRD pattern,21 whereas the XRD pattern of PEDOT NTs showed no obvious peaks owing to the amorphous structure 22. The MOF‐525–PEDOT NT nanocomposite had diffraction peaks at 2θ = 4.5°, 6.4°, and 7.8°, indicating the same characteristic structure of MOF‐525.…”

Section: Resultssupporting

confidence: 91%

“…The N2 adsorption–desorption curves of MOF‐525 nanocrystals and MOF‐525–PEDOT NTs nanocomposite are shown in Figure 1 a. The MOF‐525 nanocrystals show a Brunauer–Emmett–Teller (BET) specific surface area of 2690 m 2 g −1 , which is similar to other works 20, 21. Incorporating PEDOT caused the BET specific surface area of MOF‐525–PEDOT NTs to decrease to 1650 m 2 g −1 .…”

Section: Resultssupporting

confidence: 80%

“…Both curves had similar microporous adsorption–desorption behavior, indicating that the MOF‐525–PEDOT NT nanocomposites maintain the characteristic porous properties of the parent MOF‐525 nanocrystals. The MOF‐525 had a pore size of 1.84 nm as calculated by the density functional theory method using a cylindrical‐pore model (Figure 1a; inset) 20, 21. The MOF‐525–PEDOT NT nanocomposites exhibited a similar pore size, showing that the nanocomposites contain the pure, highly crystalline MOF‐525 nanocrystals.…”

Section: Resultsmentioning

confidence: 97%

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Enhanced Charge Collection in MOF‐525–PEDOT Nanotube Composites Enable Highly Sensitive Biosensing

et al. 2017

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With the aim of a reliable biosensing exhibiting enhanced sensitivity and selectivity, this study demonstrates a dopamine (DA) sensor composed of conductive poly(3,4‐ethylenedioxythiophene) nanotubes (PEDOT NTs) conformally coated with porphyrin‐based metal–organic framework nanocrystals (MOF‐525). The MOF‐525 serves as an electrocatalytic surface, while the PEDOT NTs act as a charge collector to rapidly transport the electron from MOF nanocrystals. Bundles of these particles form a conductive interpenetrating network film that together: (i) improves charge transport pathways between the MOF‐525 regions and (ii) increases the electrochemical active sites of the film. The electrocatalytic response is measured by cyclic voltammetry and differential pulse voltammetry techniques, where the linear concentration range of DA detection is estimated to be 2 × 10−6–270 × 10−6 m and the detection limit is estimated to be 0.04 × 10−6 m with high selectivity toward DA. Additionally, a real‐time determination of DA released from living rat pheochromocytoma cells is realized. The combination of MOF5‐25 and PEDOT NTs creates a new generation of porous electrodes for highly efficient electrochemical biosensing.

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Section: Resultssupporting

confidence: 91%

Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 97%

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Enhanced Charge Collection in MOF‐525–PEDOT Nanotube Composites Enable Highly Sensitive Biosensing

et al. 2017

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“…PSM offers a vast array of opportunities for the functionalisation of Zr MOFs, although this has typically been limited to ligand/metal‐ion exchange,18 ligand metalation13a, 19 and covalent modifications of pendant functional groups 20. Across all MOFs, postsynthetic bromination has been attempted mainly on tethered moieties,21 with limited success obtained for integral units 22.…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Halogenation of Integral Unsaturated C‐C Bonds in Chemically and Mechanically Robust Zr and Hf MOFs

Marshall

Griffin

Wilson

et al. 2016

Chemistry A European J

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Metal–organic frameworks (MOFs) containing ZrIV‐based secondary building units (SBUs), as in the UiO‐66 series, are receiving widespread research interest due to their enhanced chemical and mechanical stabilities. We report the synthesis and extensive characterisation, as both bulk microcrystalline and single crystal forms, of extended UiO‐66 (Zr and Hf) series MOFs containing integral unsaturated alkene, alkyne and butadiyne units, which serve as reactive sites for postsynthetic modification (PSM) by halogenation. The water stability of a Zr–stilbene MOF allows the dual insertion of both −OH and −Br groups in a single, aqueous bromohydrination step. Quantitative bromination of alkyne‐ and butadiyne‐containing MOFs is demonstrated to be stereoselective, as a consequence of the linker geometry when bound in the MOFs, while the inherent change in hybridisation and geometry of integral linker atoms is facilitated by the high mechanical stabilities of the MOFs, allowing bromination to be characterised in a single‐crystal to single‐crystal (SCSC) manner. The facile addition of bromine across the unsaturated C−C bonds in the MOFs in solution is extended to irreversible iodine sequestration in the vapour phase. A large‐pore interpenetrated Zr MOF demonstrates an I2 storage capacity of 279 % w/w, through a combination of chemisorption and physisorption, which is comparable to the highest reported capacities of benchmark iodine storage materials for radioactive I2 sequestration. We expect this facile PSM process to not only allow trapping of toxic vapours, but also modulate the mechanical properties of the MOFs.

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“…Such an approach started with close-packed compounds [45]; the greatest progress may be registered among molecular crystals [46]. Learning from crystal structure prediction done, not by ab initio calculations, but by exploiting known topologies and known building units of related crystals, led to the greatest success among framework materials [47][48][49][50].…”

Section: Pattern Modelling Methods Assisted By Ab Initio Calculationsmentioning

confidence: 99%

Crystal Structures from Powder Diffraction: Principles, Difficulties and Progress

Černý

2017

Crystals

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Abstract:The structure solution from powder diffraction has undergone an intense evolution during the last 20 years, but is far from being routine. Current challenges of powder crystallography include ab initio crystal structure determination on real samples of new materials with specific microstructures, characterization of intermediate reaction products from in situ, in operando studies and novel phases from in situ studies of phase diagrams. The intense evolution of electron diffraction in recent years, providing an experimental (precession) and theoretical (still under intense development) solution to strong dynamic scattering of electrons, smears the traditional frontier between poly-and single-crystal diffraction. Novel techniques like serial snapshot X-ray crystallography point in the same direction. Finally, for the computational chemistry, theoreticians hand-in-hand with crystallographers develop tools where the theory meets experiment for crystal structure refinement, which becomes an unavoidable step in the validation of crystal structures obtained from powder diffraction.Keywords: powder diffraction; structure solution; X-ray diffraction; DFT calculations; electron diffraction The structure solution means in this article determination of the (average) 3D-periodic arrangement of the atoms in the crystal using mainly the information content of Bragg scattering in the diffraction pattern. The case of aperiodic crystals (modulated and quasicrystals), of short-range order (diffuse scattering), as well as of nano-crystals (crystals without measurable Bragg signals) will not be discussed here. The structure prediction, on the other hand, will be used in the sense of the determination of the 3D arrangement of the atoms in the crystal using mainly first-principle calculations, and any experimental observation, like the diffraction pattern, is used only for the validation of the predicted structural model. Indexing: Still a BottleneckDespite an intense development of indexing algorithms in the last 20 years, the detection of the correct lattice may still be a bottleneck of the structure solution in the case of low resolution powder patterns or in the case of monoclinic and triclinic symmetry. A review of known indexing algorithms may be found in Chapter 7 of [3], Chapter 5 of [6] and Chapter 7 of [7]. Each crystallographer and each crystal may work better with a particular algorithm, but as is said in another excellent indexing The advantage of the dichotomy algorithm is its speed (especially in Fox) and its robustness towards low data quality. Indexing is followed by space group determination, which is based on systematic extinction analysis supported by the knowledge of crystal physical properties, like piezoelectricity, the presence of which excludes centrosymmetric space groups. Fairly robust algorithms for space group determination are based on full pattern fitting (Le Bail or Pawley), available in most software packages. The indexing can be quite difficult for the crystals lying on opposite ends of the s...

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Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks

Cited by 815 publications

References 15 publications

Enhanced Charge Collection in MOF‐525–PEDOT Nanotube Composites Enable Highly Sensitive Biosensing

Enhanced Charge Collection in MOF‐525–PEDOT Nanotube Composites Enable Highly Sensitive Biosensing

Stereoselective Halogenation of Integral Unsaturated C‐C Bonds in Chemically and Mechanically Robust Zr and Hf MOFs

Crystal Structures from Powder Diffraction: Principles, Difficulties and Progress

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