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27 items found (0 items not approved), displaying 1 to 10.[First/Prev] 1, 2, 3 [Next/Last]

Instruments / Technical Area	Publication Details	Published
I12-JEEP: Joint Engineering, Environmental and Processing	In situ observation of topotactic linker reorganization in the aperiodic metal–organic framework TRUMOF-1 Guy Greenbaum , Patrick W. Doheny , Robert A. I. Paraoan , Yevheniia Kholina , Stefan Michalik , Simon J. Cassidy , Hamish H.-M. Yeung , Andrew L. Goodwin Journal Of The American Chemical Society DOI: 10.1021/jacs.4c09487 Diamond Proposal Number(s): [34953] Open Access Show Abstract ▼ Abstract: We use in situ synchrotron X-ray diffraction measurements to monitor the solvothermal crystallization mechanism of the aperiodic metal–organic framework TRUMOF-1. Following an initial incubation period, TRUMOF-1 forms as a metastable intermediate that subsequently transforms into an ordered product with triclinic crystal symmetry. We determine the structure of this ordered phase, which we call msw-TRUMOF-1, and show that it is related to TRUMOF-1 through topotactic reorganization of linker occupancies. Our results imply that the connectivity of TRUMOF-1 can be reorganized, as required for data storage and manipulation applications.	Sep 2024
I11-High Resolution Powder Diffraction	K-ion slides in prussian blue analogues John Cattermull , Nikolaj Roth , Simon J. Cassidy , Mauro Pasta , Andrew L. Goodwin Journal Of The American Chemical Society 84 DOI: 10.1021/jacs.3c08751 Diamond Proposal Number(s): [29776] Open Access Show Abstract ▼ Abstract: We study the phenomenology of cooperative off-centering of K+ ions in potassiated Prussian blue analogues (PBAs). The principal distortion mechanism by which this off-centering occurs is termed a “K-ion slide”, and its origin is shown to lie in the interaction between local electrostatic dipoles that couple through a combination of electrostatics and elastic strain. Using synchrotron powder X-ray diffraction measurements, we determine the crystal structures of a range of low-vacancy K2M[Fe(CN)6] PBAs (M = Ni, Co, Fe, Mn, Cd) and establish an empirical link between composition, temperature, and slide-distortion magnitude. Our results reflect the common underlying physics responsible for K-ion slides and their evolution with temperature and composition. Monte Carlo simulations driven by a simple model of dipolar interactions and strain coupling reproduce the general features of the experimental phase behavior. We discuss the implications of our study for optimizing the performance of PBA K-ion battery cathode materials and also its relevance to distortions in other, conceptually related, hybrid perovskites.	Oct 2023
I11-High Resolution Powder Diffraction	Lithium intercalation into the excitonic insulator candidate Ta2NiSe5 P. A. Hyde , J. Cen , S, J. Cassidy , N. H. Rees , P. Holdship , R. I. Smith , Bonan Zhu , David O. Scanlon , S. J. Clarke Inorganic Chemistry DOI: 10.1021/acs.inorgchem.3c01510 Diamond Proposal Number(s): [18786, 25166] Open Access Show Abstract ▼ Abstract: A new reduced phase derived from the excitonic insulator candidate Ta2NiSe5 has been synthesized via the intercalation of lithium. LiTa2NiSe5 crystallizes in the orthorhombic space group Pmnb (no. 62) with lattice parameters a = 3.50247(3) Å, b = 13.4053(4) Å, c = 15.7396(2) Å, and Z = 4, with an increase of the unit cell volume by 5.44(1)% compared with Ta2NiSe5. Significant rearrangement of the Ta-Ni-Se layers is observed, in particular a very significant relative displacement of the layers compared to the parent phase, similar to that which occurs under hydrostatic pressure. Neutron powder diffraction experiments and computational analysis confirm that Li occupies a distorted triangular prismatic site formed by Se atoms of adjacent Ta2NiSe5 layers with an average Li–Se bond length of 2.724(2) Å. Li-NMR experiments show a single Li environment at ambient temperature. Intercalation suppresses the distortion to monoclinic symmetry that occurs in Ta2NiSe5 at 328 K and that is believed to be driven by the formation of an excitonic insulating state. Magnetometry data show that the reduced phase has a smaller net diamagnetic susceptibility than Ta2NiSe5 due to the enhancement of the temperature-independent Pauli paramagnetism caused by the increased density of states at the Fermi level evident also from the calculations, consistent with the injection of electrons during intercalation and formation of a metallic phase.	Jul 2023
B18-Core EXAFS I11-High Resolution Powder Diffraction	Anion redox as a means to derive layered manganese oxychalcogenides with exotic intergrowth structures Shunsuke Sasaki , Souvik Giri , Simon J. Cassidy , Sunita Dey , Maria Batuk , Daphne Vandemeulebroucke , Giannantonio Cibin , Ronald I. Smith , Philip Holdship , Clare P. Grey , Joke Hadermann , Simon J. Clarke Nature Communications 14 DOI: 10.1038/s41467-023-38489-3 Diamond Proposal Number(s): [25166, 14239] Open Access Show Abstract ▼ Abstract: Topochemistry enables step-by-step conversions of solid-state materials often leading to metastable structures that retain initial structural motifs. Recent advances in this field revealed many examples where relatively bulky anionic constituents were actively involved in redox reactions during (de)intercalation processes. Such reactions are often accompanied by anion-anion bond formation, which heralds possibilities to design novel structure types disparate from known precursors, in a controlled manner. Here we present the multistep conversion of layered oxychalcogenides Sr2MnO2Cu1.5Ch2 (Ch = S, Se) into Cu-deintercalated phases where antifluorite type [Cu1.5Ch2]2.5- slabs collapsed into two-dimensional arrays of chalcogen dimers. The collapse of the chalcogenide layers on deintercalation led to various stacking types of Sr2MnO2Ch2 slabs, which formed polychalcogenide structures unattainable by conventional high-temperature syntheses. Anion-redox topochemistry is demonstrated to be of interest not only for electrochemical applications but also as a means to design complex layered architectures.	May 2023
I21-Resonant Inelastic X-ray Scattering (RIXS)	Delocalized electron holes on oxygen in a battery cathode Robert A. House , Gregory J. Rees , Kit Mccoll , John-Joseph Marie , Mirian Garcia-Fernandez , Abhishek Nag , Ke-Jin Zhou , Simon Cassidy , Benjamin J. Morgan , M. Saiful Islam , Peter G. Bruce Nature Energy 149 DOI: 10.1038/s41560-023-01211-0 Diamond Proposal Number(s): [25589] Show Abstract ▼ Abstract: Oxide ions in transition metal oxide cathodes can store charge at high voltage offering a route towards higher energy density batteries. However, upon charging these cathodes, the oxidized oxide ions condense to form molecular O2 trapped in the material. Consequently, the discharge voltage is much lower than charge, leading to undesirable voltage hysteresis. Here we capture the nature of the electron holes on O2− before O2 formation by exploiting the suppressed transition metal rearrangement in ribbon-ordered Na0.6[Li0.2Mn0.8]O2. We show that the electron holes formed are delocalized across the oxide ions coordinated to two Mn (O–Mn2) arranged in ribbons in the transition metal layers. Furthermore, we track these delocalized hole states as they gradually localize in the structure in the form of trapped molecular O2 over a period of days. Establishing the nature of hole states on oxide ions is important if truly reversible high-voltage O-redox cathodes are to be realized.	Feb 2023
I11-High Resolution Powder Diffraction	High- versus low-spin Ni2+ in elongated octahedral environments: Sr2NiO2Cu2Se2, Sr2NiO2Cu2S2, and Sr2NiO2Cu2(Se1–xSx)2 Robert D. Smyth , Jack N. Blandy , Ziyu Yu , Shuai Liu , Craig V. Topping , Simon J. Cassidy , Catherine F. Smura , Daniel N. Woodruff , Pascal Manuel , Craig L. Bull , Nicholas P. Funnell , Christopher J. Ridley , John E. Mcgrady , Simon J. Clarke Chemistry Of Materials 6 DOI: 10.1021/acs.chemmater.2c02002 Diamond Proposal Number(s): [13284, 18786, 25166] Open Access Show Abstract ▼ Abstract: Sr2NiO2Cu2Se2, comprising alternating [Sr2NiO2]2+ and [Cu2Se2]2– layers, is reported. Powder neutron diffraction shows that the Ni2+ ions, which are in a highly elongated NiO4Se2 environment with D4h symmetry, adopt a high-spin configuration and carry localized magnetic moments which order antiferromagnetically below ∼160 K in a √2a × √2a × 2c expansion of the nuclear cell with an ordered moment of 1.31(2) μB per Ni2+ ion. The adoption of the high-spin configuration for this d8 cation in a pseudo-square-planar ligand field is supported by consideration of the experimental bond lengths and the results of density functional theory (DFT) calculations. This is in contrast to the sulfide analogue Sr2NiO2Cu2S2, which, according to both experiment and DFT calculations, has a much more elongated ligand field, more consistent with the low-spin configuration commonly found for square-planar Ni2+, and accordingly, there is no evidence for magnetic moment on the Ni2+ ions. Examination of the solid solution Sr2NiO2Cu2(Se1–xSx)2 shows direct evidence from the evolution of the crystal structure and the magnetic ordering for the transition from high-spin selenide-rich compounds to low-spin sulfide-rich compounds as a function of composition. Compression of Sr2NiO2Cu2Se2 up to 7.2 GPa does not show any structural signature of a change in the spin state. Consideration of the experimental and computed Ni2+ coordination environments and their subtle changes as a function of temperature, in addition to transitions evident in the transport properties and magnetic susceptibilities in the end members, Sr2NiO2Cu2Se2 and Sr2NiO2Cu2S2, suggest that simple high-spin and low-spin models for Ni2+ may not be entirely appropriate and point to further complexities in these compounds.	Oct 2022
I11-High Resolution Powder Diffraction	Topochemical intercalation reactions of ZrSe3 Mahmoud Elgaml , Simon J. Cassidy , Simon J. Clarke Journal Of Solid State Chemistry 10 DOI: 10.1016/j.jssc.2022.123436 Diamond Proposal Number(s): [18786, 25166] Open Access Show Abstract ▼ Abstract: Intercalation of alkali and alkaline earth metals into ZrSe3 via soft chemical routes injects electrons and has a significant effect on the selenide-selenide bonding. K, Rb and Cs intercalates of ZrSe3 prepared at low temperatures (−78 °C) from metal ammonia solutions contrast with related polymorphs obtained at high temperature (850 °C). KxZrSe3 synthesised at low temperatures crystallises in orthorhombic Cmc21, while the polymorph obtained at high temperatures crystallises in Immm. The two structures prepared under drastically different conditions differ by relative shifting of ZrSe3 layers. In contrast, CsxZrSe3 shows the Immm polymorph at low temperature and the Cmc21 polymorph at high temperatures, while a single RbxZrSe3 polymorph in Immm is formed at both temperatures. Intercalation of Ca from liquid ammonia facilitates the co-intercalation of the solvent because of the strong solvation of Ca2+. This compound has severe faulting due to the flexibility in the relative shifts of adjacent ZrSe3 layers.	Jul 2022
I11-High Resolution Powder Diffraction	Uncovering the interplay of competing distortions in the prussian blue analogue K2Cu[Fe(CN)6] John Cattermull , Krishnakanth Sada , Kevin Hurlbutt , Simon J. Cassidy , Mauro Pasta , Andrew L. Goodwin Chemistry Of Materials DOI: 10.1021/acs.chemmater.2c00288 Diamond Proposal Number(s): [25166] Open Access Show Abstract ▼ Abstract: We report the synthesis, crystal structure, thermal response, and electrochemical behavior of the Prussian blue analogue (PBA) K2Cu[Fe(CN)6]. From a structural perspective, this is the most complex PBA yet characterized: its triclinic crystal structure results from an interplay of cooperative Jahn–Teller order, octahedral tilts, and a collective “slide” distortion involving K-ion displacements. These different distortions give rise to two crystallographically distinct K-ion channels with different mobilities. Variable-temperature X-ray powder diffraction measurements show that K-ion slides are the lowest-energy distortion mechanism at play, as they are the only distortion to be switched off with increasing temperature. Electrochemically, the material operates as a K-ion cathode with a high operating voltage and an improved initial capacity relative to higher-vacancy PBA alternatives. On charging, K+ ions are selectively removed from a single K-ion channel type, and the slide distortions are again switched on and off accordingly. We discuss the functional importance of various aspects of structural complexity in this system, placing our discussion in the context of other related PBAs.	May 2022
I11-High Resolution Powder Diffraction I12-JEEP: Joint Engineering, Environmental and Processing	Intercalates of Bi2Se3 studied in situ by time-resolved powder X-ray diffraction and neutron diffraction Machteld E. Kamminga , Simon J. Cassidy , Partha P. Jana , Mahmoud Elgaml , Nicola D. Kelly , Simon J. Clarke Dalton Transactions 7 DOI: 10.1039/D1DT00960E Diamond Proposal Number(s): [18786, 20375] Open Access Show Abstract ▼ Abstract: Intercalation of lithium and ammonia into the layered semiconductor Bi2Se3 proceeds via a hyperextended (by >60%) ammonia-rich intercalate, to eventually produce a layered compound with lithium amide intercalated between the bismuth selenide layers which offers scope for further chemical manipulation.	Aug 2021
I11-High Resolution Powder Diffraction I12-JEEP: Joint Engineering, Environmental and Processing	Single-step synthesis and interface tuning of core–shell metal–organic framework nanoparticles Kieran W. P. Orr , Sean M. Collins , Emily M. Reynolds , Frank Nightingale , Hanna L. B. Bostroem , Simon J. Cassidy , Daniel M. Dawson , Sharon E. Ashbrook , Oxana Magdysyuk , Paul A. Midgley , Andrew L. Goodwin , Hamish H.-M. Yeung Chemical Science 13 DOI: 10.1039/D0SC03940C Diamond Proposal Number(s): [20946, 18786] Open Access Show Abstract ▼ Abstract: Control over the spatial distribution of components in metal–organic frameworks has potential to unlock improved performance and new behaviour in separations, sensing and catalysis. We report an unprecedented single-step synthesis of multi-component metal–organic framework (MOF) nanoparticles based on the canonical ZIF-8 (Zn) system and its Cd analogue, which form with a core–shell structure whose internal interface can be systematically tuned. We use scanning transmission electron microscopy, X-ray energy dispersive spectroscopy and a new composition gradient model to fit high-resolution X-ray diffraction data to show how core–shell composition and interface characteristics are intricately controlled by synthesis temperature and reaction composition. Particle formation is investigated by in situ X-ray diffraction, which reveals that the spatial distribution of components evolves with time and is determined by the interplay of phase stability, crystallisation kinetics and diffusion. This work opens up new possibilities for the control and characterisation of functionality, component distribution and interfaces in MOF-based materials.	Feb 2021

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