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Instruments / Technical Area	Publication Details	Published
I15-1-X-ray Pair Distribution Function (XPDF) I22-Small angle scattering & Diffraction	Liquid phase blending of metal-organic frameworks Louis Longley , Sean Collins , Chao Zhou , Glen J. Smales , Sarah E. Norman , Nick J. Brownbill , Christopher W. Ashling , Philip A. Chater , Robert Tovey , Carola-bibiane Schönlieb , Thomas F. Headen , Nicholas J. Terrill , Yuanzheng Yue , Andrew J. Smith , Frédéric Blanc , David Keen , Paul A. Midgley , Thomas Bennett Nature Communications 9 DOI: 10.1038/s41467-018-04553-6 Diamond Proposal Number(s): [171151, 18236] Open Access Show Abstract ▼ Abstract: The liquid and glass states of metal–organic frameworks (MOFs) have recently become of interest due to the potential for liquid-phase separations and ion transport, alongside the fundamental nature of the latter as a new, fourth category of melt-quenched glass. Here we show that the MOF liquid state can be blended with another MOF component, resulting in a domain structured MOF glass with a single, tailorable glass transition. Intra-domain connectivity and short range order is confirmed by nuclear magnetic resonance spectroscopy and pair distribution function measurements. The interfacial binding between MOF domains in the glass state is evidenced by electron tomography, and the relationship between domain size and Tg investigated. Nanoindentation experiments are also performed to place this new class of MOF materials into context with organic blends and inorganic alloys.	Jun 2018
I11-High Resolution Powder Diffraction I19-Small Molecule Single Crystal Diffraction	Near-Ideal Xylene Selectivity in Adaptive Molecular Pillar[n]arene Crystals Kecheng Jie , Ming Liu , Yujuan Zhou , Marc A. Little , Angeles Pulido , Samantha Y. Chong , Andrew Stephenson , Ashlea R. Hughes , Fumiyasu Sakakibara , Tomoki Ogoshi , Frédéric Blanc , Graeme M. Day , Feihe Huang , Andrew I. Cooper Journal Of The American Chemical Society DOI: 10.1021/jacs.8b02621 Diamond Proposal Number(s): [15777, 12336, 17193] Show Abstract ▼ Abstract: The energy-efficient separation of alkylaromatic compounds is a major industrial sustainability challenge. The use of selectively porous extended frameworks, such as zeolites or metal–organic frameworks, is one solution to this problem. Here, we studied a flexible molecular material, perethylated pillar[n]arene crystals (n = 5, 6), which can be used to separate C8 alkylaromatic compounds. Pillar[6]arene is shown to separate para-xylene from its structural isomers, meta-xylene and ortho-xylene, with 90% specificity in the solid state. Selectivity is an intrinsic property of the pillar[6]arene host, with the flexible pillar[6]arene cavities adapting during adsorption thus enabling preferential adsorption of para-xylene in the solid state. The flexibility of pillar[6]arene as a solid sorbent is rationalized using molecular conformer searches and crystal structure prediction (CSP) combined with comprehensive characterization by X-ray diffraction and 13C solid state NMR spectroscopy. The CSP study, which takes into account the structural variability of pillar[6]arene, breaks new ground in its own right and showcases the feasibility of applying CSP methods to understand and ultimately to predict the behaviour of soft, adaptive molecular crystals.	May 2018
I11-High Resolution Powder Diffraction I15-Extreme Conditions	Stable and ordered amide frameworks synthesised under reversible conditions which facilitate error checking David Stewart , Dmytro Antypov , Matthew S. Dyer , Michael J. Pitcher , Alexandros P. Katsoulidis , Philip A. Chater , Frederic Blanc , Matthew Rosseinsky Nature Communications DOI: 10.1038/s41467-017-01423-5 Diamond Proposal Number(s): [12336, 9282] Open Access Show Abstract ▼ Abstract: Covalent organic frameworks (COFs) are network polymers with long-range positional order whose properties can be tuned using the isoreticular chemistry approach. Making COFs from strong bonds is challenging because irreversible rapid formation of the network produces amorphous materials with locked-in disorder. Reversibility in bond formation is essential to generate ordered networks, as it allows the error-checking that permits the network to crystallise, and so candidate network-forming chemistries such as amide that are irreversible under conventional low temperature bond-forming conditions have been underexplored. Here we show that we can prepare two- and three-dimensional covalent amide frameworks (CAFs) by devitrification of amorphous polyamide network polymers using high-temperature and high-pressure reaction conditions. In this way we have accessed reversible amide bond formation that allows crystalline order to develop. This strategy permits the direct synthesis of practically irreversible ordered amide networks that are stable thermally and under both strong acidic and basic hydrolytic conditions.	Oct 2017
I11-High Resolution Powder Diffraction	La 3 Li 3 W2O 12 : Ionic Diffusion in a Perovskite with Lithium on Both A- and BSites Alma B. Santibáñez-mendieta , Christophe Didier , Kenneth K. Inglis , Alex J. Corkett , Michael Pitcher , Marco Zanella , J. Felix Shin , Luke Daniels , Aydar Rakhmatullin , Ming Li , Matthew S. Dyer , John B. Claridge , Frédéric Blanc , Matthew J. Rosseinsky Chemistry Of Materials DOI: 10.1021/acs.chemmater.6b03220 Diamond Proposal Number(s): [12336] Show Abstract ▼ Abstract: The structure and Li+ ion dynamics of a new class of ABO3 perovskite with Li on both the A- and B-sites are described. La3Li3W2O12 is synthesised by solid state reaction at 900°C and shown by powder X-ray diffraction to adopt the structure of a monoclinic double perovskite (A2)BBꞌO6, (La1.5Li0.5)WLiO6, with rock salt order of W6+ and Li+ on the B-site. High resolution powder neutron diffraction locates A-site Li in a distorted tetrahedron displaced from the conventional perovskite A-site, which differs considerably from the sites occupied by Li in the well studied La2/3-xLi3xTiO3 family. This is confirmed by the observation of a lower coordinated Li+ ion in the 6Li magic angle spinning nuclear magnetic resonance (NMR) spectra, in addition to the B-site LiO6, and supported computationally by density functional theory (DFT), which also suggests local order of A-site La3+ and Li+. DFT shows that the vacancies necessary for transport can arise from Frenkel or La excess defects, with an energetic cost of ~0.4 eV/vacancy in both cases. Ab initio molecular dynamics establishes that the Li+ ion dynamics occur by a pathway involving a series of multiple localised Li hops between two neighbouring A-sites with an overall energy barrier of ~0.25 eV, with additional possible pathways involving Li exchange between the A- and B-sites. A similar activation energy for Li+ ion mobility (~0.3 eV) was obtained from variable temperature 6Li and 7Li line narrowing and relaxometry NMR experiments, suggesting that the barrier to Li hopping between sites in La3Li3W2O12 is comparable to the best oxide Li+ ion conductors. AC impedance-derived conductivities confirm that Li+ ions are mobile but that the long-range Li+ diffusion has a higher barrier (~0.5 eV) which may be associated with blocking of transport by A-site La3+ ions.	Sep 2016
B18-Core EXAFS	Melt-Quenched Glasses of Metal-Organic Frameworks Thomas Bennett , Yuanzheng Yue , Peng Li , Ang Qiao , Haizheng Tao , Neville Greaves , Tom Richards , Giulio Lampronti , Simon Redfern , Frédéric Blanc , Omar K. Farha , Joseph T. Hupp , Anthony K. Cheetham , David Keen Journal Of The American Chemical Society DOI: 10.1021/jacs.5b13220 Diamond Proposal Number(s): [14249] Show Abstract ▼ Abstract: Crystalline solids dominate the field of metal-organic frameworks (MOFs), with access to the liquid and glass states of matter usually prohibited by relatively low temperatures of thermal decomposition. In this work, we give due consideration to framework chemistry and topology to expand the phenomenon of the melting of three-dimensional MOFs, linking crystal chemistry to framework melting temperature and kinetic fragility of the glass-forming liquids. Here we show that melting temperatures can be lowered by altering the chemistry of the crystalline MOF state, which provides a route to facilitate the melting of other MOFs. The glasses formed upon vitrification are chemically and structurally distinct from the three other existing categories of melt-quenched glasses (inorganic non-metallic, organic and metallic), and retain the basic metal-ligand connectivity of crystalline MOFs, which connects their mechanical properties to starting chemical composition. The transfer of functionality from crystal to glass points towards new routes to tunable, functional hybrid glasses.	Feb 2016
I15-Extreme Conditions	A comparison of the amorphization of zeolitic imidazolate frameworks (ZIFs) and aluminosilicate zeolites by ball-milling Emma F Baxter , Thomas D. Bennett , Andrew B. Cairns , Nick J. Brownbill , Andrew L. Goodwin , David A. Keen , Philip A Chater , Frédéric Blanc , Anthony K. Cheetham Dalton Transactions DOI: 10.1039/C5DT03477A PMID: 26575842 Diamond Proposal Number(s): [9691] Open Access Show Abstract ▼ Abstract: X-ray diffraction has been used to investigate the kinetics of amorphization through ball-milling at 20 Hz, for five zeolitic imidazolate frameworks (ZIFs) – ZIF-8, ZIF-4, ZIF-zni, BIF-1-Li and CdIF-1. We find that the rates of amorphization for the zinc-containing ZIFs increase with increasing solvent accessible volume (SAV) in the sequence ZIF-8 > ZIF-4 > ZIF-zni. The Li–B analogue of the dense ZIF-zni amorphizes more slowly than the corresponding zinc phase, with the behaviour showing a correlation with their relative bulk moduli and SAVs. The cadmium analogue of ZIF-8 (CdIF-1) amorphizes more rapidly than the zinc counterpart, which we ascribe primarily to its relatively weak M–N bonds as well as the higher SAV. The results for the ZIFs are compared to three classical zeolites – Na-X, Na-Y and ZSM-5 – with these taking up to four times longer to amorphize. The presence of adsorbed solvent in the pores is found to render both ZIF and zeolite frameworks more resistant to amorphization. X-ray total scattering measurements show that amorphous ZIF-zni is structurally indistinguishable from amorphous ZIF-4 with both structures retaining the same short-range order that is present in their crystalline precursors. By contrast, both X-ray total scattering measurements and 113Cd NMR measurements point to changes in the local environment of amorphous CdIF-1 compared with its crystalline CdIF-1 precursor	Nov 2015
I11-High Resolution Powder Diffraction	Computational identification and experimental realisation of lithium vacancy introduction into the olivine LiMgPO4 Leopoldo Enciso Maldonado , Matthew S. Dyer , Michael D. Jones , Ming Li , Julia Payne , Michael J. Pitcher , Mona K. Omir , John Claridge , Frederic Blanc , Matthew Rosseinsky Chemistry of Materials 27 (6) DOI: 10.1021/cm504518q Diamond Proposal Number(s): [9282] Show Abstract ▼ Abstract: Calculation of the energetics of aliovalent substitution into the olivine LiMgPO4 suggests that replacement of Mg2+ by In3+ is the most effective way to introduce lithium vacancies and thus generate lithium ion conductivity. Experimental synthesis accesses materials with up to 17% Li vacancy content. An order of magnitude increase in the high temperature hopping rates probed by 7 Li NMR spin lattice relaxation, and over two orders of magnitude increase in the room temperature Li+ ion conductivity measured by impedance spectroscopy is observed on introduction of In3+ ions and Li vacancies. NMR spectroscopy and calculations reveal that the energy barrier to site-to-site hopping is 0.3 eV 0.5 eV, comparable with best-in-class non-oxide systems such as argyrodite, but NMR derived hopping rates, and impedance spectroscopy shows that longer range transport is less facile with activation energies in the range of 0.7 1 eV. Calculations suggest that this is because the Li vacancies are strongly bound to the In3+ dopants, suggesting that high lithium mobilities in oxides are accessible but high conductivities require strategies to separate defect from dopant.	Feb 2015

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