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):
[29957]
Open Access
Abstract: The development of metal-organic framework (MOF) crystal-glass composites (CGCs) has been hindered by the scarcity of MOF glass matrices with low glass transition temperatures (Tgs). Here, we investigate a CGC consisting of a low-Tg MOF glass, (agZIF-UC-7) and UiO-66. Powder X-ray diffraction and stability tests in phosphate buffer saline solution showed UiO-66 was stabilised in the glass matrix. Additionally, the composite exhibited enhanced dye uptake and gas adsorption relative to agZIF-UC-7.
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Jul 2025
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Emily V.
Shaw
,
Celia
Castillo Blas
,
Timothy
Lambden
,
Beatriz
De Santos
,
Bethan
Turner
,
Giulio I.
Lampronti
,
Joonatan E. M.
Laulainen
,
Georgina
Robertson
,
Ashleigh M.
Chester
,
Chumei
Ye
,
Shaoliang
Guan
,
Joshua
Karlsson
,
Valentina
Martinez
,
Ivana
Brekalo
,
Bahar
Karadeniz
,
Silvia
Cabrera
,
Lauren N.
Mchugh
,
Krunoslav
Užarević
,
Jose
Aleman
,
Alberto
Fraile
,
Rachel C
Evans
,
Paul
Midgley
,
David A.
Keen
,
Xavier
Moya
,
Thomas D.
Bennett
Open Access
Abstract: In this work, we investigated the response of the metal-organic framework MIL-125-NH2 to ball-milling. Both localised and bulk analyses revealed that prolongued ball-milling results in a complete loss of long-range structural order. Investigation of this disorder revealed partial retention of the local bonding of the secondary building unit, suggesting structure collapse progressed primarily through metal-linker bond breakage. We explored the photocatalytic performance of the materials, and examined the materials’ band gap using UV-Vis reflectance spectroscopy.
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Feb 2025
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I15-1-X-ray Pair Distribution Function (XPDF)
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Bikash Kumar
Shaw
,
Lucia
Corti
,
Joshua M.
Tuffnell
,
Celia
Castillo-Blas
,
Patrick
Schlachta
,
Georgina P.
Robertson
,
Lauren
Mchugh
,
Adam F.
Sapnik
,
Sebastian A.
Hallweger
,
Philip A.
Chater
,
Gregor
Kieslich
,
David A.
Keen
,
Sian E.
Dutton
,
Frédéric
Blanc
,
Thomas D.
Bennett
Diamond Proposal Number(s):
[20038]
Open Access
Abstract: ABX3-type hybrid organic–inorganic structures have recently emerged as a new class of meltable materials. Here, by the use of phenylphosphonium derivatives as A cation, we study liquid- and glass-forming behavior of a new family of hybrid structures, (RPh3P)[Mn(dca)3] (R = Me, Et, Ph; dca = dicyanamide). These new compounds melt at 196–237 °C (Tm) and then vitrify upon cooling to room temperature, forming glasses. In situ glass formation of this new family of materials was probed on a large scale using a variable-temperature PXRD experiment. Structure analyses of the crystalline and the glasses were carried out by solid-state nuclear magnetic resonance spectroscopy and synchrotron X-ray total scattering techniques for using the pair distribution function. The mechanical properties of the glasses produced were evaluated showing promising durability. Thermal and electrical conductivities showed low thermal conductivities (κ ∼ 0.07–0.09 W m–1 K–1) and moderate electrical conductivities (σ ∼ 10–4–10–6 S m–1) at room temperature, suggesting that by the precise control of the A cation, we can tune meltable hybrid structures from moderate conductors to efficient thermal insulators. Our results raise attention on the practical use of this new hybrid material in applications including, e.g., photovoltaic devices to prevent light-deposited heat (owing to low κRT), energy harvesting thermoelectric, etc., and advance the structure–property understanding.
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Dec 2024
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I15-1-X-ray Pair Distribution Function (XPDF)
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Chumei
Ye
,
Giulio
Lampronti
,
Lauren N.
Mchugh
,
Celia
Castillo-Blas
,
Ayano
Kono
,
Celia
Chen
,
Georgina P.
Robertson
,
Liam A. V.
Nagle-Cocco
,
Weidong
Xu
,
Samuel D.
Stranks
,
Valentina
Martinez
,
Ivana
Brekalo
,
Bahar
Karadeniz
,
Krunoslav
Užarević
,
Wenlong
Xue
,
Pascal
Kolodzeiski
,
Chinmoy
Das
,
Philip
Chater
,
David A.
Keen
,
Sian E.
Dutton
,
Thomas D.
Bennett
Diamond Proposal Number(s):
[20038]
Open Access
Abstract: Hybrid organic–inorganic perovskites (HOIPs) occupy a prominent position in the field of materials chemistry due to their attractive optoelectronic properties. While extensive work has been done on the crystalline materials over the past decades, the newly reported glasses formed from HOIPs open up a new avenue for perovskite research with their unique structures and functionalities. Melt-quenching is the predominant route to glass formation; however, the absence of a stable liquid state prior to thermal decomposition precludes this method for most HOIPs. In this work, we describe the first mechanochemically-induced crystal-glass transformation of HOIPs as a rapid, green and efficient approach for producing glasses. The amorphous phase was formed from the crystalline phase within 10 minutes of ball-milling, and exhibited glass transition behaviour as evidenced by thermal analysis techniques. Time-resolved in situ ball-milling with synchrotron powder diffraction was employed to study the microstructural evolution of amorphisation, which showed that the crystallite size reaches a comminution limit before the amorphisation process is complete, indicating that energy may be further accumulated as crystal defects. Total scattering experiments revealed the limited short-range order of amorphous HOIPs, and their optical properties were studied by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) spectroscopy.
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Apr 2024
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I15-1-X-ray Pair Distribution Function (XPDF)
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Celia
Castillo-Blas
,
Ashleigh M.
Chester
,
Ronan P.
Cosquer
,
Adam F.
Sapnik
,
Lucia
Corti
,
Roman
Sajzew
,
Bruno
Poletto-Rodrigues
,
Georgina P.
Robertson
,
Daniel J. M.
Irving
,
Lauren N.
Mchugh
,
Lothar
Wondraczek
,
Frédéric
Blanc
,
David A.
Keen
,
Thomas D.
Bennett
Diamond Proposal Number(s):
[29957]
Open Access
Abstract: The interface within a composite is critically important for the chemical and physical properties of these materials. However, experimental structural studies of the interfacial regions within metal–organic framework (MOF) composites are extremely challenging. Here, we provide the first example of a new MOF composite family, i.e., using an inorganic glass matrix host in place of the commonly used organic polymers. Crucially, we also decipher atom–atom interactions at the interface. In particular, we dispersed a zeolitic imidazolate framework (ZIF-8) within a phosphate glass matrix and identified interactions at the interface using several different analysis methods of pair distribution function and multinuclear multidimensional magic angle spinning nuclear magnetic resonance spectroscopy. These demonstrated glass–ZIF atom–atom correlations. Additionally, carbon dioxide uptake and stability tests were also performed to check the increment of the surface area and the stability and durability of the material in different media. This opens up possibilities for creating new composites that include the intrinsic chemical properties of the constituent MOFs and inorganic glasses.
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Oct 2023
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I15-1-X-ray Pair Distribution Function (XPDF)
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Open Access
Abstract: Membranes with ultrahigh permeance and practical selectivity could greatly decrease the cost of difficult industrial gas separations, such as CH4/N2 separation. Advanced membranes made from porous materials, such as metal–organic frameworks, can achieve a good gas separation performance, although they are typically formed on support layers or mixed with polymeric matrices, placing limitations on gas permeance. Here an amorphous glass foam, agfZIF-62, wherein a, g and f denote amorphous, glass and foam, respectively, was synthesized by a polymer-thermal-decomposition-assisted melting strategy, starting from a crystalline zeolitic imidazolate framework, ZIF-62. The thermal decomposition of incorporated low-molecular-weight polyethyleneimine evolves CO2, NH3 and H2O gases, creating a large number and variety of pores. This greatly increases pore interconnectivity but maintains the crystalline ZIF-62 ultramicropores, allowing ultrahigh gas permeance and good selectivity. A self-supported circular agfZIF-62 with a thickness of 200–330 µm and area of 8.55 cm2 was used for membrane separation. The membranes perform well, showing a CH4 permeance of 30,000–50,000 gas permeance units, approximately two orders of magnitude higher than that of other reported membranes, with good CH4/N2 selectivity (4–6).
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May 2023
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I11-High Resolution Powder Diffraction
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Michael F.
Thorne
,
Celia
Castillo Blas
,
Lauren N.
Mchugh
,
Alice M.
Bumstead
,
Georgina
Robertson
,
Adam F.
Sapnik
,
Chloe S.
Coates
,
Farheen N.
Sayed
,
Clare P.
Grey
,
David A.
Keen
,
Martin
Etter
,
Ivan
Da Silva
,
Krunoslav
Užarević
,
Thomas D.
Bennett
Diamond Proposal Number(s):
[28349]
Open Access
Abstract: The structure of a new ZIF-8 polymorph with quartz topology (qtz) is reported. This qtz-[Zn(mIm)2] phase was obtained by mechanically amorphising crystalline ZIF-8, before heating the resultant amorphous phase to between 282 and 316 °C. The high temperature phase structure was obtained from X-ray powder diffraction, and its thermal behaviour, CO2 gas sorption properties and dye adsorption ability were investigated.
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Sep 2022
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I15-1-X-ray Pair Distribution Function (XPDF)
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Alice M.
Bumstead
,
Ignas
Pakamore
,
Kieran D.
Richards
,
Michael F.
Thorne
,
Sophia S.
Boyadjieva
,
Celia
Castillo-Blas
,
Lauren N.
Mchugh
,
Adam F.
Sapnik
,
Dean S.
Keeble
,
David A.
Keen
,
Rachel C.
Evans
,
Ross S.
Forgan
,
Thomas D.
Bennett
Diamond Proposal Number(s):
[20038]
Open Access
Abstract: Melt-quenched metal–organic framework (MOF) glasses have gained significant interest as the first new category of glass reported in 50 years. In this work, an amine-functionalized zeolitic imidazolate framework (ZIF), denoted ZIF-UC-6, was prepared and demonstrated to undergo both melting and glass formation. The presence of an amine group resulted in a lower melting temperature compared to other ZIFs, while also allowing material properties to be tuned by post-synthetic modification (PSM). As a prototypical example, the ZIF glass surface was functionalized with octyl isocyanate, changing its behavior from hydrophilic to hydrophobic. PSM therefore provides a promising strategy for tuning the surface properties of MOF glasses.
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Feb 2022
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[20038]
Open Access
Abstract: Four novel dicyanamide-containing hybrid organic-inorganic ABX3 structures are reported, and the thermal behaviour of a series of nine perovskite and non-perovskite [AB(N(CN)2)3] (A = (C3H7)4N, (C4H9)4N, (C5H11)4N; B = Co, Fe, Mn). Structure-property relationships are investigated by varying both A-site organic and B-site transition metal cations. In particular, increasing the size of the A-site cation from (C3H7)4N → (C4H9)4N → (C5H11)4N was observed to result in a decrease in Tm through an increase in ΔSf. Consistent trends in Tm with metal replacement are observed with each A-site cation, with Co < Fe < Mn. The majority of the melts formed were found to recrystallise partially upon cooling, though glasses could be formed through a small degree of organic linker decomposition. Total scattering methods are used to provide a greater understanding of the melting mechanism
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Jan 2022
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