I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[8742]
Open Access
Abstract: Can we control the crystallization of solid CaCO3 from supersaturated aqueous solutions and thus mimic a natural process predicted to occur in living organisms that produce biominerals? Here we show how we achieved this by confining the reaction between Ca2+ and CO32− ions to the environment of nanosized water cores of water-in-oil microemulsions, in which the reaction between the ions is controlled by the intermicellar exchange processes. Using a combination of in situ small-angle X-ray scattering, high-energy X-ray diffraction, and low-dose liquid-cell scanning transmission electron microscopy, we elucidate how the presence of micellar interfaces leads to the formation of a solute CaCO3 phase/species that can be stabilized for extended periods of time inside micellar water nano-droplets. The nucleation and growth of any solid CaCO3 polymorph, including the amorphous phase, from such nano-droplets is prevented despite the fact that the water cores in the used microemulsion are highly supersaturated with respect to all known calcium carbonate solid phases. On the other hand the presence of the solute CaCO3 phase inside of the water cores decreases the rigidity of the micellar surfactant/water interface, which promotes the aggregation of micelles and the formation of large (>2 μm in diameter) globules. The actual precipitation and crystallization of solid CaCO3 could be triggered “on-demand” through the targeted removal of the organic–inorganic interface and hence the destabilization of globules carrying the CaCO3 solute.
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May 2018
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I08-Scanning X-ray Microscopy beamline (SXM)
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Diamond Proposal Number(s):
[19228, 23583]
Open Access
Abstract: X-ray Raman scattering (XRS) spectroscopy is an emerging inelastic scattering technique which uses hard X-rays to study the X-ray absorption edges of low-Z elements (e.g. C, N, O) in bulk. This study applies XRS spectroscopy to pyrolysis and hydrothermal carbons. These materials are thermochemically-produced carbon from renewable resources and represent a route for the sustainable production of carbon materials for many applications. Results confirm local structural differences between biomass-derived (Oak, Quercus Ilex) pyrolysis and hydrothermal carbon. In comparison with NEXAFS, XRS spectroscopy has been shown to be more resilient to experimental artefacts such as self-absorption. Density functional theory XRS calculations of potential structural sub-units confirm that hydrothermal carbon is a highly disordered carbon material formed principally of furan units linked by the α carbon atoms. Comparison of two pyrolysis temperatures (450 °C and 650 °C) shows the development of an increasingly condensed carbon structure. Based on our results, we have proposed a semi-quantitative route to pyrolysis condensation.
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Jul 2020
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B18-Core EXAFS
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Diamond Proposal Number(s):
[10411]
Abstract: We report on results of a comprehensive investigation on reaction mechanisms occurring during Li uptake and release of the composite NiFe2O4/CNT. Operando X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) data collected simultaneously using one in situ cell allowed thorough elucidation of structural and electronic alterations happening during Li uptake. From the beginning of Li uptake, the Bragg intensity of the spinel reflections decreases which can be explained by reduction of Fe3+ ions and simultaneous movement of the Fe2+ cations from tetrahedral 8a to empty octahedral 16c sites. The reduction of Fe3+ is clearly evidenced by XAS. The occupation of tetrahedral sites by Li+ can be excluded based on results of density functional theory calculations. Increasing the Li content leads to formation of a new crystalline phase resembling a monoxide with a NaCl-like structure. The appearance of the new phase is accompanied by a steady decrease of the sizes of coherently scattering domains of the spinel and a growth of the domains of the monoxide phase. After uptake of about 2.5 Li per NiFe2O4, all Fe3+ cations are reduced to Fe2+ and the tetrahedral 8a sites are empty (XAS spectra). Careful Rietveld refinements of X-ray powder patterns demonstrate that the tetrahedral 8a site is successively depleted with increasing Li content. Interestingly, the occupancy of the octahedral 16d site is also slightly reduced. Increasing the Li content beyond 2.5 Li/NiFe2O4 leads to successive reduction of the cations to very small metal particles embedded in a Li2O matrix (as evidenced by 7Li MAS NMR investigations). During Li release metallic Ni and Fe are reoxidized to Ni2+ resp. Fe3+. The cycling stability of NiFe2O4/CNT is significantly improved compared to pure NiFe2O4 or a mechanical mixture of NiFe2O4 and CNTs.
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Jun 2018
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I11-High Resolution Powder Diffraction
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Abstract: We report the structural changes that occur during the thermal removal of organic template molecules that occlude the pores of small pore nanoporous zeolitic solids, AlPO-18, SAPO-18, CoAlPO-18, ZnAlPO-18 and CoSAPO-18. The calcination process is a necessary step in the formation of active catalysts. The studies performed using time-resolved High Resolution Powder Diffraction (HRPD) and High Energy X-ray Diffraction (HEXRD) techniques at various temperatures reveal that changes that take place are dependent on the type of heteroatom present in the nanoporous solids. While time-resolved HRPD shows clear changes in lattice parameters during the removal of physisorbed water molecules and subsequent removal of the organic template, HEXRD data show changes in various near neighbour distances in AlPO-18, SAPO-18, CoAlPO-18, CoSAPO-18 and ZnAlPO-18 during the calcination process. In particular HEXRD reveals the presence of water molecules coordinated to Al(III) ions in the as-synthesised materials. Upon removal of the template and water, these solids show contraction in the cell volume at elevated temperatures while first and second neighbour distances remained almost unchanged.
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Apr 2013
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[171151]
Abstract: In this work, we explore the thermodynamic evolution in a melt-quenched metal–organic framework glass, formed from ZIF-62 upon heating to the melting point (Tm), and subsequent enthalpy relaxation. The temperature dependence of the difference in Gibbs free energy between the liquid and crystal states of ZIF-62 in the temperature range from the glass transition temperature (Tg) to Tm is found to be weaker than those of other types of glasses, e.g., metallic glasses. Additionally, we find that the stretched exponent of the enthalpy relaxation function in the glass varies significantly (β = 0.44–0.76) upon changing the extent of sub-Tg annealing, compared to metallic and oxide glasses with similar Tgs, suggesting a high degree of structural heterogeneity. Pair distribution function results suggest no significant structural changes during the sub-Tg relaxation in ZIF-62 glass.
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Jun 2018
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I11-High Resolution Powder Diffraction
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W. I. F.
David
,
S. K.
Callear
,
M. O.
Jones
,
P. C.
Aeberhard
,
S. D.
Culligan
,
A. H.
Pohl
,
S. R.
Johnson
,
K. R.
Ryan
,
J. E.
Parker
,
P. P.
Edwards
,
C. J.
Nuttall
,
A.
Amieiro-fonseca
Diamond Proposal Number(s):
[1211]
Abstract: The structure of the cubic polymorph of magnesium tetrahydroborate (γ-Mg(BH4)2) has been determined in space group Ia[3 with combining macron]d from a structural database of the isoelectronic compound SiO2; this has been corroborated by DFT calculations. The structure is found to concur with that recently determined by Filinchuk et al. (Y. Filinchuk, B. Richter, T. R. Jensen, V. Dmitriev, D. Chernyshov and H. Hagemann, Angew. Chem. Int. Ed., 2011, DOI: 10.1002/anie.201100675). The phase transformations and subsequent decomposition of γ-Mg(BH4)2 on heating have been ascertained from variable-temperature synchrotron X-ray diffraction data combined with thermogravimetric and mass spectrometry measurements. At ∼160 °C, conversion to a disordered variant of the β-Mg(BH4)2 phase (denoted as β′) is observed along with a further unidentified polymorph. There is evidence of amorphous phases during decomposition but there is no direct crystallographic indication of the existence of Mg(B12H12) or other intermediate Mg–B–H compounds. MgH2 and finally Mg are observed in the X-ray diffraction data after decomposition.
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Jul 2012
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I07-Surface & interface diffraction
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Diamond Proposal Number(s):
[6306]
Abstract: The plant defence proteins ?1- and ?2-purothionin (Pth) are type 1 thionins from common wheat (Triticum aestivum). These highly homologous proteins possess characteristics common amongst antimicrobial peptides and proteins, that is, cationic charge, amphiphilicity and hydrophobicity. Both ?1- and ?2-Pth possess the same net charge, but differ in relative hydrophobicity as determined by C18 reversed phase HPLC. Brewster angle microscopy, X-ray and neutron reflectometry, external reflection FTIR and associated surface pressure measurements demonstrated that ?1 and ?2-Pth interact strongly with condensed phase 1,2-dipalmitoyl-sn-glycero-3-phospho-(1?-rac-glycerol) (DPPG) monolayers at the air/liquid interface. Both thionins disrupted the in-plane structure of the anionic phospholipid monolayers, removing lipid during this process and both penetrated the lipid monolayer in addition to adsorbing as a single protein layer to the lipid head-group. However, analysis of the interfacial structures revealed that the ?2-Pth showed faster disruption of the lipid film and removed more phospholipid (12%) from the interface than ?1-Pth. Correlating the protein properties and lipid binding activity suggests that hydrophobicity plays a key role in the membrane lipid removal activity of thionins.
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Aug 2012
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I11-High Resolution Powder Diffraction
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Abstract: Light weight and cheap electrolytes with fast multi-valent ion conductivity can pave the way for future high-energy density solid-state batteries, beyond the lithium-ion battery. Here we present the mechanism of Mg-ion conductivity of monoammine magnesium borohydride, Mg(BH4)2·NH3. Density functional theory calculations (DFT) reveal that the neutral molecule (NH3) in Mg(BH4)2·NH3 is exchanged between the lattice and interstitial Mg2+ facilitated by a highly flexible structure, mainly owing to a network of di-hydrogen bonds, N–Hδ+⋯−δH–B and the versatile coordination of the BH4− ligand. DFT shows that di-hydrogen bonds in inorganic matter and hydrogen bonds in bio-materials have similar bond strengths and bond lengths. As a result of the high structural flexibiliy, the Mg-ion conductivity is dramatically improved at moderate temperature, e.g. σ(Mg2+) = 3.3 × 10−4 S cm−1 at T = 80 °C for Mg(BH4)2·NH3, which is approximately 8 orders of magnitude higher than that of Mg(BH4)2. Our results may inspire a new approach for the design and discovery of unprecedented multivalent ion conductors.
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Mar 2020
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[6749]
Abstract: Following the recent report of Abe and co-workers (Phys. Chem. Chem. Phys., 2012, 14, 5855) of the isolation of a bridging peroxide of a naphthalene-tethered bisimidazolyl diradical, it is reported herein that this degradation pathway is a more general phenomenon for the chromic dimers of 2,4,5-triphenylimidazolyl radical (TPIR) materials, with non-tethered TPIRs forming similar oxygen adducts. The peroxides of two derivatives have been characterised by single crystal X-ray diffraction (SC-XRD) and it is identified that the 4-position of the imidazolyl ring is the site susceptible to reaction with oxygen. Furthermore, mass spectrometry has been used to show that for a range of five known, non-tethered derivatives, peroxide formation can be detected within 30 minutes when samples are irradiated under an oxygen atmosphere, thus presenting a significant challenge to the long term use of this class of material in colour-switching device applications.
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Apr 2013
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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
B18-Core EXAFS
I20-EDE-Energy Dispersive EXAFS (EDE)
I20-Scanning-X-ray spectroscopy (XAS/XES)
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Rachel H.
Blackmore
,
Maria Elena
Rivas
,
George F.
Tierney
,
Khaled M. H.
Mohammed
,
Donato
Decarolis
,
Shusaku
Hayama
,
Federica
Venturini
,
Georg
Held
,
Rosa
Arrigo
,
Monica
Amboage
,
Pip
Hellier
,
Evan
Lynch
,
Mahrez
Amri
,
Marianna
Casavola
,
Tugce
Eralp Erden
,
Paul
Collier
,
Peter P.
Wells
Diamond Proposal Number(s):
[20129, 20200, 22063, 15151]
Open Access
Abstract: The use of mechanochemistry to prepare catalytic materials is of significant interest; it offers an environmentally beneficial, solvent-free, route and produces highly complex structures of mixed amorphous and crystalline phases. This study reports on the effect of milling atmosphere, either air or argon, on mechanochemically prepared LaMnO3 and the catalytic performance towards N2O decomposition (deN2O). In this work, high energy resolution fluorescence detection (HERFD), X-ray absorption near edge structure (XANES), X-ray emission, and X-ray photoelectron spectroscopy (XPS) have been used to probe the electronic structural properties of the mechanochemically prepared materials. Moreover, in situ studies using near ambient pressure (NAP)-XPS, to follow the materials during catalysis, and high pressure energy dispersive EXAFS studies, to mimic the preparation conditions, have also been performed. The studies show that there are clear differences between the air and argon milled samples, with the most pronounced changes observed using NAP-XPS. The XPS results find increased levels of active adsorbed oxygen species, linked to the presence of surface oxide vacancies, for the sample prepared in argon. Furthermore, the argon milled LaMnO3 shows improved catalytic activity towards deN2O at lower temperatures compared to the air milled and sol–gel synthesised LaMnO3. Assessing this improved catalytic behaviour during deN2O of argon milled LaMnO3 by in situ NAP-XPS suggests increased interaction of N2O at room temperature within the O 1s region. This study further demonstrates the complexity of mechanochemically prepared materials and through careful choice of characterisation methods how their properties can be understood.
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Jun 2020
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