I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[34380]
Open Access
Abstract: The structural evolution and electrical behaviour of (1−x) NaNbO3-xCaTiO3 (NN-CT) ceramics were investigated in this study. X-ray diffraction and full-pattern Rietveld refinement confirm that CT incorporation disrupts the long-range antipolar orthorhombic Pbcm phase. The dielectric permittivity peak shifts to lower temperatures as the CT concentration increases. The highest permittivity of 2365 was obtained for x = 0.15 at room temperature. Synchrotron X-ray scattering coupled with pair distribution function (PDF) analysis reveals the existence of a short-range ordered polar orthorhombic P21ma (Q) phase with a correlation length of approximately 5 nm. A slim ferroelectric polarisation-electric field (P-E) loop, consistent with short-range ordered behaviour, was obtained in the NN-0.15CT, yielding an enhanced recoverable energy density by over 300 % at 150 kV cm−1 compared to pure NN. These findings establish the role of CT doping in modifying structural and dielectric properties, contributing to the understanding of crystal symmetry evolution and its impact on the dielectric response of this promising, environmentally friendly lead-free perovskite oxide for high-performance dielectric applications.
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Oct 2025
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I15-1-X-ray Pair Distribution Function (XPDF)
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Zixuan
Li
,
Rui
Qi
,
Yi
Yuan
,
Lechen
Yang
,
Lijiang
Song
,
Ashok S.
Menon
,
Louis F. J.
Piper
,
Didier
Wermeille
,
Paul
Thompson
,
Robert A.
House
,
Peter G.
Bruce
,
Alex W.
Robertson
Open Access
Abstract: Aqueous zinc-ion batteries (ZIBs) suffer from sustained capacity loss at the zinc metal anode due to side reactions with the electrolyte, even under idle conditions. The concept of an anode-free ZIB would address this degradation by eliminating the metal anode source. A key requirement for such systems is a cathode that contains zinc in its pristine state and supports initial charging. Here, we report the synthesis and characterization of cation-disordered rocksalt (DRX) ZnMnO2, a new cathode material suitable for anode-free ZIBs. ZnMnO2 meets the essential criteria for anode-free operation of natively containing Zn in the pristine state, enabling an initial charge, as well as offering high initial charge capacity (312.8 mAh g−1), and discharge voltage (1.36 V). We show that the dominant energy storage mechanism involves Mn dissolution and redeposition, with a smaller contribution arising from reversible Zn intercalation into a spinel phase that forms in situ during cycling. We further demonstrate the versatility of DRX cathodes by extending the concept to ZnFeO2. These findings establish DRX materials as a promising platform for the development of cathodes suitable for anode-free ZIBs.
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Oct 2025
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B07-B1-Versatile Soft X-ray beamline: High Throughput ES1
I15-1-X-ray Pair Distribution Function (XPDF)
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Daniel
Muñoz-Gil
,
Celia
Castillo-Blas
,
Dawid Krystian
Feler
,
Isabel
Gómez-Recio
,
Miguel
Tinoco
,
Ana
Querejeta-Fernández
,
Rodrigo
González-Prieto
,
Felipe
Gandara
,
Romualdo
Santos Silva
,
Pilar
Ferrer
,
Carlos
Prieto
,
Luc
Lajaunie
,
José Luis
Martinez-Peña
,
María Luisa
Ruiz-González
,
María Luisa
Ruiz-González
,
José María
González-Calbet
Diamond Proposal Number(s):
[40307, 40403]
Open Access
Abstract: Layered double hydroxides (LDH) based on transition metals are highly flexible in tailoring their dimensionality, lattice, and electronic structures, making them promising candidates as multifunctional 2D materials for the development of clean energy technologies and boosting the use of hydrogen as an energy vector. In this paper, strategic anion substitution in cobalt LDH is an appealing strategy to produce a material with two-fold functionality, electrochemical and magnetocaloric response, offering a sustainable alternative to existing electrocatalysts and cryogenic refrigerants. It is unambiguously demonstrated that (poly)oxomolybdate-based specimens interleave in Co LDH nanosheets up to a Co:Mo = 1:0.4 ratio, leading to an interstratified material. This intercalation greatly benefits the kinetics of the oxygen evolution reaction for H2 production, boosting the catalytic sites due to the expansion of the interlayer space, induced by the bulky molybdates which also partially modify the Co oxidation state of αCo(OH)2 nanolayers, favoring charge transfer. In parallel, the interleaved Mo species strengthen superexchange interactions compared with pristine α-Co(OH)2, effectively adjusting the operating temperature toward the liquid hydrogen range (2030 K). This specific temperature range allows to fill a critical gap in magnetocaloric materials, as few systems can simultaneously achieve both large magnetic entropy changes and structural stability.
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Oct 2025
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I15-1-X-ray Pair Distribution Function (XPDF)
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Adam F.
Sapnik
,
Philip A.
Chater
,
Dean S.
Keeble
,
John S. O.
Evans
,
Federica
Bertolotti
,
Antonietta
Guagliardi
,
Lise J.
Støckler
,
Elodie A.
Harbourne
,
Anders B.
Borup
,
Rebecca S.
Silberg
,
Adrien
Descamps
,
Clemens
Prescher
,
Benjamin D.
Klee
,
Axel
Phelipeau
,
Imran
Ullah
,
Kárel G.
Medina
,
Tobias A.
Bird
,
Viktoria
Kaznelson
,
William
Lynn
,
Andrew L.
Goodwin
,
Bo B.
Iversen
,
Celine
Crepisson
,
Emil S.
Bozin
,
Kirsten M. Ø.
Jensen
,
Emma E.
Mcbride
,
Reinhard B.
Neder
,
Ian
Robinson
,
Justin S.
Wark
,
Michał
Andrzejewski
,
Ulrike
Boesenberg
,
Erik
Brambrink
,
Carolina
Camarda
,
Valerio
Cerantola
,
Sebastian
Goede
,
Hauke
Höppner
,
Oliver S.
Humphries
,
Zuzana
Konopkova
,
Naresh
Kujala
,
Thomas
Michelat
,
Motoaki
Nakatsutsumi
,
Alexander
Pelka
,
Thomas R.
Preston
,
Lisa
Randolph
,
Michael
Roeper
,
Andreas
Schmidt
,
Cornelius
Strohm
,
Minxue
Tang
,
Peter
Talkovski
,
Ulf
Zastrau
,
Karen
Appel
,
David A.
Keen
Diamond Proposal Number(s):
[39017]
Open Access
Abstract: High-quality total scattering data, a key tool for understanding atomic-scale structure in disordered materials, require stable instrumentation and access to high momentum transfers. This is now routine at dedicated synchrotron instrumentation using high-energy X-ray beams, but it is very challenging to measure a total scattering dataset in less than a few microseconds. This limits their effectiveness for capturing structural changes that occur at the much faster timescales of atomic motion. Current X-ray free-electron lasers (XFELs) provide femtosecond-pulsed X-ray beams with maximum energies of ∼24 keV, giving the potential to measure total scattering and the attendant pair distribution functions (PDFs) on femtosecond timescales. We demonstrate that this potential has been realized using the HED scientific instrument at the European XFEL and present normalized total scattering data for 0.35 Å−1 < Q < 16.6 Å−1 and their PDFs from a broad spectrum of materials, including crystalline, nanocrystalline and amorphous solids, liquids and clusters in solution. We analyzed the data using a variety of methods, including Rietveld refinement, small-box PDF refinement, joint reciprocal–real-space refinement, cluster refinement and Debye scattering analysis. The resolution function of the setup is also characterized. We conclusively show that high-quality data can be obtained from a single ∼30 fs XFEL pulse for multiple different sample types. Our efforts not only significantly increase the existing maximum reported Q range for an S(Q) measured at an XFEL but also mean that XFELs are now a viable X-ray source for the broad community of people using reciprocal-space total scattering and PDF methods in their research.
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Sep 2025
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I15-1-X-ray Pair Distribution Function (XPDF)
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Ming
Gao
,
Hankun
Xu
,
Kun
Lin
,
Andrea
Sanson
,
Alessandro
Venier
,
Alessandro
Puri
,
Jochi
Tseng
,
Guodong
Li
,
Qian
Zhang
,
Xuyu
Dong
,
Yili
Cao
,
Qiang
Li
,
Xianran
Xing
Diamond Proposal Number(s):
[31899]
Abstract: Negative thermal expansion (NTE) is an unusual yet highly useful phenomenon that has been extensively studied in numerous crystals, including ceramics, alloys, and metal-organic frameworks. This Letter reports an unprecedented NTE in an amorphous Fe87.5Y3Zr1.5B8 alloy that lacks a periodic atomic arrangement. Such an NTE is significant for metallic materials and extends over a wide temperature range (𝛼1=−6.9×10−6 K−1, 200–375 K). We demonstrate that this NTE is intrinsic to the amorphous nature of the alloy and is correlated with Fe moment. Extended x-ray absorption fine structure reveals a strong NTE for nearest neighboring Fe-Fe pairs. Further analysis using a x-ray pair distribution function indicates that the amorphous Fe87.5Y3Zr1.5B8 alloy, serving as a transition state, exhibits a tendency toward local ordered atomic arrangement. A complex interplay among local structure, magnetic interaction, and thermal relaxation results in volume contraction upon heating below 𝑇𝐶. This Letter introduces amorphous alloys as a new family of materials with NTE functionality, offering interesting prospects for both scientific research and practical applications.
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Sep 2025
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[34797]
Open Access
Abstract: MOF@COF composites have emerged as a promising class of engineered materials with unique functionalities, combining the high porosity and tunability of metal-organic frameworks (MOFs) with the chemical and mechanical stability of covalent-organic frameworks (COFs). While their advantageous properties are well-recognized, their structural intricacies and the nature of the interfacial interactions remain insufficiently explored. In this study, a Fe-MOF@COF composite is presented, exhibiting dual functionalities for the efficient removal of organic pollutants from water. The enhanced performance is attributed to the unique properties of the MOF-COF interface, where synergistic interactions between the two porous materials play a critical role. Advanced synchrotron techniques were employed to probe interfacial interactions at the atomic and molecular levels. These findings underscore the potential of Fe-MOF@COF composite as a highly effective material for water remediation, providing deeper insights into their structural behavior and interfacial properties.
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Aug 2025
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I15-1-X-ray Pair Distribution Function (XPDF)
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Chumei
Ye
,
Lauren N.
Mchugh
,
Pierre
Florian
,
Ruohan
Yu
,
Celia
Castillo-Blas
,
Celia
Chen
,
Arad
Lang
,
Yuhang
Dai
,
Jingwei
Hou
,
David A.
Keen
,
Sian E.
Dutton
,
Thomas D.
Bennett
Diamond Proposal Number(s):
[35405]
Open Access
Abstract: Hybrid organic-inorganic perovskites (HOIPs) have garnered significant attention for their crystalline properties, yet recent findings reveal that they can also form liquid and glassy phases, offering an alternative platform for understanding non-crystalline materials. In this study, we present a detailed investigation into the structural dynamics of the melting and glass formation process of a two-dimensional (2D) HOIP, (S−(−)−1-(1−naphthyl)ethylammonium)2PbBr4. Compared to its crystalline counterpart, the glass exhibits superior mechanical properties, including higher Young’s modulus and hardness. Our structural studies reveal that the liquid and glass formed from the 2D HOIP exhibit network-forming behaviour, featuring limited short-range order within individual octahedra, partial retention of metal-halide-metal connectivity between neighbouring octahedra, and residual structural correlations mediated by organic cations. We then combine in situ variable-temperature X-ray total scattering experiments, terahertz far-infrared absorption spectroscopy and solid-state nuclear magnetic resonance techniques to study the melting mechanism and the nature of the HOIP liquid obtained. Our results deepen the understanding of the structural evolution and property relationships in HOIP glasses, providing a foundation for their potential applications in advanced phase-change material technologies.
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Aug 2025
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[34748]
Open Access
Abstract: n the quest for greener alternatives to conventional organic solvents, Deep Eutectic Solvents (DESs) have gained significant attention due to their sustainability, biodegradability, and tunability. The use of water as an active and genuine component has recently led to the emergence of water-based DESs (wb-DESs). Here, a careful experimental characterization was performed on choline acetate (ChAc)/water mixtures across a range of water:ChAc molar ratios (n = 2–6). Differential Scanning Calorimetry (DSC) revealed glass transitions between 150 and 180 K, with no first-order transitions, leading to a classification of these mixtures as Low Transition-Temperature Mixtures (LTTMs). Physicochemical measurements, including density, viscosity, electrical conductivity, and refractive index, were conducted over a broad temperature range. NMR analyses provided insights into dynamics and solvation environments, with 1H T1slow relaxation times reaching their lowest value at n = 2, consistent with the formation of a strong hydrogen-bonding network. The n = 2 mixture was further investigated using Small and Wide-Angle X-ray Scattering (S-WAXS) and ab initio molecular dynamics (AIMD). These studies, jointly with 1H NMR choline diffusion coefficient, directly challenge previous claims of the existence of aggregation phenomena in wb-DES. The simulation revealed a well-organized solvation structure, where acetate and water synergistically stabilize the choline cation through a cooperative hydrogen-bonding network. These findings highlight the impact and significance of an integrated physicochemical study in guiding the rational development of new sustainable systems, such as wb-DESs.
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Aug 2025
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I15-1-X-ray Pair Distribution Function (XPDF)
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Bartholomew T.
Payne
,
Mikkel
Juelsholt
,
Miguel A.
Pérez-Osorio
,
Dominic L. R.
Melvin
,
Gabriel J.
Cuello
,
Emmanuelle
Suard
,
Daniel J. M.
Irving
,
Nicholas
Rees
,
Mark
Feaviour
,
Enrico
Petrucco
,
Stephen
Day
,
Gregory J.
Rees
,
Peter G.
Bruce
Open Access
Abstract: The rate performance of all-solid-state batteries can be limited by the low conductivity of the solid electrolyte in the composite cathode. A conductivity of 10 mS cm⁻¹ is required, which exceeds that of many solid electrolytes. This limitation can be attributed to intra- and inter-grain ion transport. Understanding the limitations of ion transport is a multi-length scale problem ranging from single bond hops to particle-particle transport. Here we show that spark plasma sintering of Li6PS5Cl not only enhances ion transport on the macroscopic length scale but also on the microscopic scale. On the macroscopic length scale, greater densification improves particle-to- particle contact. On the nanoscale, short-range order (SRO) of the neighbouring 4a/4a and 4d/4d Wyckoff sites present in the cold-pressed Li6PS5Cl produces unfavourable Li ion pathways through the cell. Spark plasma heating removes the SRO, creating a connected network of microscopic pathways for the Li to migrate. Finally, on the atomistic level, spark plasma heating increases the amount of Cl− residing on the 4d site and S2− on the 4a site. By understanding the limitations of ion mobility across a range of length scales, one can target methods to produce solid-state argyrodite electrolytes with higher ionic conductivities.
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Aug 2025
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[31642]
Open Access
Abstract: Metal–organic framework (MOF) glasses combine the structural tunability of crystalline MOFs with the processability of amorphous materials, offering exciting opportunities for functional hybrid materials. Here, a one-pot, solvent-free synthesis is reported of an Fe2+-based MOF glass, gFe-tBubipy, with the composition [Fe2(im)3.12(bim)0.88(tBubipy)0.11]·[Fe(Cp)2]0.09 (im− = imidazolate, bim− = benzimidazolate, tBubipy = 4,4′-di-tert-butyl-2,2′-bipyridine, Cp− = cyclopentadienyl anion). This material forms a continuous random network structure of four-connected tetrahedral and octahedral Fe2+ nodes and exhibits an exceptionally low glass transition temperature (Tg = 87 °C). Despite its amorphous nature and complex composition, gFe-tBubipy exhibits a high degree of local structural order that enables strong antiferromagnetic exchange interactions between Fe2+ centers. Remarkably, it exhibits clear signatures of spin-glass behavior, with a well-defined magnetic freezing transition ≈14 K. This combination of a MOF glass exhibiting a distinct glass transition with spin-glass magnetism arising from topological disorder and frustrated, short-range magnetic interactions represent a significant advance. This discovery underscores the transformative potential of MOF glasses as a versatile platform for exploring the interplay between structural disorder and cooperative magnetic phenomena in hybrid materials.
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Aug 2025
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