Mechanical properties of zeolitic metal-organic frameworks: Mechanically flexible topologies and stabilization against structural collapse

We report the low elastic modulus of a zeolitic MOF, along with stabilization against structural collapse by filling with solvent.This is the author-accepted manuscript. It is under embargo for 12 months after publication. The final version of this article is published by RSC in CrystEngComm and can be found here: http://dx.doi.org/10.1039/c4ce02145

Mechanically and chemically robust ZIF-8 monoliths with high volumetric adsorption capacity

The resultant monoliths are mechanically robust structures and present up to 3 times higher volumetric adsorption capacities than the conventional, powder MOF.This work was funded by the EPSRC IAA Partnership Development Award (RG/75759). D.F.-J. thanks the Royal Society for funding through a University Research Fellowship. T.D.B would like to thank Trinity Hall for funding and Professor Anthony Cheetham for use of lab facilities and equipmentThis is the accepted manuscript of a paper published in the Journal of Materials Chemistry A (Tian T, Velazquez-Garcia J, Bennett TD, Fairen-Jimenez D, Journal of Materials Chemistry A, 2015, 3, 2999-3005, doi:10.1039/c4ta05116e). The final version is available at http://dx.doi.org/10.1039/c4ta05116e

Highlights from the Faraday discussion on new directions in porous crystalline materials, Edinburgh, UK, June 2017

A lively discussion on new directions in porous crystalline materials took place in June 2017, with the beautiful city of Edinburgh as a backdrop, in the context of the unique Faraday Discussions format. Here, 5 minute presentations were given on papers which have been submitted in advance of the conference, with copious time allocated for in-depth discussion of the work presented. Professor Mircea Dincă (MIT), chair of the scientific committee, opened the conference by welcoming the many different nationalities attending, and outlining the format of discussions

Improving the mechanical stability of zirconium-based metal-organic frameworks by incorporation of acidic modulators

Acidic modulating ligands have been shown to stabilize UiO metal-organic frameworks against structural collapse under ball-milling.T.D.B. would like to thank Trinity Hall for funding, along with Professor Anthony K. Cheetham for use of lab facilities. D.D.V. is grateful to IWT (MOF Shape), KU Leuven for support in the Metusalem grant CASAS and IAP 7/05 Functional Supramolecular Systems. I.S. and B.B. thank Research Foundation – Flanders (FWO) for Ph.D. fellowships.This is the accepted manuscript. The final published version is available from RSC at http://pubs.rsc.org/en/Content/ArticleLanding/2015/TA/c4ta06396a#!divAbstract

Metal-organic framework glasses with permanent accessible porosity.

To date, only several microporous, and even fewer nanoporous, glasses have been produced, always via post synthesis acid treatment of phase separated dense materials, e.g. Vycor glass. In contrast, high internal surface areas are readily achieved in crystalline materials, such as metal-organic frameworks (MOFs). It has recently been discovered that a new family of melt quenched glasses can be produced from MOFs, though they have thus far lacked the accessible and intrinsic porosity of their crystalline precursors. Here, we report the first glasses that are permanently and reversibly porous toward incoming gases, without post-synthetic treatment. We characterize the structure of these glasses using a range of experimental techniques, and demonstrate pores in the range of 4 - 8 Å. The discovery of MOF glasses with permanent accessible porosity reveals a new category of porous glass materials that are elevated beyond conventional inorganic and organic porous glasses by their diversity and tunability

Coordination cages as permanently porous ionic liquids

Porous materials are widely used in industry for applications that include chemical separations and gas scrubbing. These materials are typically porous solids, although the liquid state can be easier to manipulate in industrial settings. The idea of combining the size and shape selectivity of porous domains with the fluidity of liquids is a promising one and porous liquids composed of functionalized organic cages have recently attracted attention. Here we describe an ionic-liquid, porous, tetrahedral coordination cage. Complementing the gas binding observed in other porous liquids, this material also encapsulates non-gaseous guests—shape and size selectivity was observed for a series of isomeric alcohols. Three gaseous chlorofluorocarbon guests, trichlorofluoromethane, dichlorodifluoromethane and chlorotrifluoromethane, were also shown to be taken up by the liquid coordination cage with an affinity that increased with their size. We hope that these findings will lead to the synthesis of other porous liquids whose guest-uptake properties may be tailored to fulfil specific functions

Connecting defects and amorphization in UiO-66 and MIL-140 metal-organic frameworks: a combined experimental and computational study.

The mechanism and products of the structural collapse of the metal-organic frameworks (MOFs) , and upon ball-milling are investigated through solid state (13)C NMR and pair distribution function (PDF) studies, finding amorphization to proceed by the breaking of a fraction of metal-ligand bonding in each case. The amorphous products contain inorganic-organic bonding motifs reminiscent of the crystalline phases. Whilst the inorganic Zr6O4(OH)4 clusters of remain intact upon structural collapse, the ZrO backbone of the frameworks undergoes substantial distortion. Density functional theory calculations have been performed to investigate defective models of and show, through comparison of calculated and experimental (13)C NMR spectra, that amorphization and defects in the materials are linked.The manuscript was written through contributions of all authors. TDB conceived the initial project. T.D.B. acknowledges Trinity Hall (University of Cambridge) and Professor Anthony K. Cheetham for use of lab facilities. D.G.R. acknowledges the UK MRC for financial support. The authors acknowledge Diamond Light Source for the provision of synchrotron access to Beamline I15 (ex p. EE9691) and Philip A. Chater and Andrew Cairns for assistance with data collection. T.K.T. and C.M.D. thank the French National Research Agency (ANR project: HOPFAME ANR-13-BS07-0002-01) and the Foundation de l'Orangerie for funding. The calculations have been performed using the HPC resources from GENCI (CINES/TGCC/IDRIS) through Grant (2015-097343 and -091461). B.B., B.V.d.V. and D.D.V . gratefully acknowledge the FWO for funding (aspirant grant).This is the final version of the article. It was first available from the Royal Society of Chemistry via http://dx.doi.org/10.1039/C5CP06798

Manufacturing Macroporous Monoliths of Microporous Metal-Organic Frameworks

We report the first use of a pressure-assisted sintering technique on metal-organic framework (MOF) powders allowing for fast production of crystalline macro-porous monoliths. Mechanical and micro-structural characterization of the monoliths is presented. The interconnected macro-porosity of the compacts can be adjusted providing an immense interface for gas-solid interaction. The sintering technique is well-established and commercially available, allowing industrial scale-up of the process

Liquid metal–organic frameworks

Metal–organic frameworks are a family of chemically diverse materials, with applications in a wide range of fields covering engineering, physics, chemistry, biology and medicine. Until recently research has focused almost entirely on crystalline structures, yet now a clear trend is emerging shifting the emphasis onto disordered states including “defective by design” crystals, as well as amorphous phases such as glasses and gels. Here we introduce a strongly associated MOF liquid, obtained by melting a zeolitic imidazolate framework (ZIF). We combine in-situ variable temperature X-ray, ex-situ neutron pair distribution function experiments, and first principles molecular dynamics simulations to study the melting phenomenon and the nature of the liquid obtained. We demonstrate from structural, dynamical, and thermodynamical information that the chemical configuration, coordinative bonding, and porosity of the parent crystalline framework survive upon formation of the MOF liquid.This work benefitted from the financial support of ANRT (thèse CIFRE 2015/0268). We acknowledge access to HPC platforms provided by a GENCI grant (A0010807069). TDB would like to thank the Royal Society for a University Research Fellowship

Towards Quantum Repeaters with Solid-State Qubits: Spin-Photon Entanglement Generation using Self-Assembled Quantum Dots

In this chapter we review the use of spins in optically-active InAs quantum dots as the key physical building block for constructing a quantum repeater, with a particular focus on recent results demonstrating entanglement between a quantum memory (electron spin qubit) and a flying qubit (polarization- or frequency-encoded photonic qubit). This is a first step towards demonstrating entanglement between distant quantum memories (realized with quantum dots), which in turn is a milestone in the roadmap for building a functional quantum repeater. We also place this experimental work in context by providing an overview of quantum repeaters, their potential uses, and the challenges in implementing them.Comment: 51 pages. Expanded version of a chapter to appear in "Engineering the Atom-Photon Interaction" (Springer-Verlag, 2015; eds. A. Predojevic and M. W. Mitchell