B18-Core EXAFS
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Biswajit
Bhattacharyya
,
Christian
Balischewski
,
Jiyong
Kim
,
Tiago
Duarte
,
Lianshe
Fu
,
Rute A.s.
Ferreira
,
Alkit
Beqiraj
,
Iuliia
Mikulska
,
Diego
Gianolio
,
Eric
Sperlich
,
Felix
Stete
,
Wouter
Koopman
,
Christina
Günter
,
Katlen
Brennenstuhl
,
Daniel
Van Opdenbosch
,
Cordt
Zollfrank
,
Armin
Wedel
,
Beth J.
Murray
,
Małgorzata
Swadźba-Kwaśny
,
Tillmann
Klamroth
,
Michael U.
Kumke
,
Verónica
De Zea Bermudez
,
Andreas
Taubert
Open Access
Abstract: Low-melting ionic solids with stirring luminescent properties hold significant promise for optoelectronic applications. Here, we compare and contrast the structural and spectroscopic correlations of two highly luminescent organic-inorganic manganese halides (C4Py)2[MnCl4] and (C4Py)2[MnBr4], synthesized from their respective manganese halides and N-butyl pyridinium halide ionic liquids. Although both compounds exhibit very similar bulk structures (determined by single-crystal and powder X-ray diffraction) and overall similar electronic structures (as indicated by the density of states), they differ notably in their optical properties. The chloride salt, (C4Py)2[MnCl4], has a photoluminescence decay lifetime ten times longer than its bromide analogue, (C4Py)2[MnBr4]. Furthermore, PL-quantum yield of (C4Py)2[MnBr4] is 1.6 times higher than that of (C4Py)2[MnCl4], which was attributed to the heavy atom effect of bromine atoms, based on periodic density functional calculations (with and without spin-orbit coupling). Although photoluminescence is only exhibited in the solid state, EXAFS analysis confirms that the coordination environment of manganese is remarkably similar in crystalline and molten states, potentially suggesting that photoluminescence is associated with the long-range crystalline order, which is lost upon melting. Building on these fundamental studies, the potential of (C4Py)2[MnCl4] as a luminescent security ink for anticounterfeiting applications has been demonstrated.
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Feb 2026
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B18-Core EXAFS
I18-Microfocus Spectroscopy
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Swaroop
Chakraborty
,
Iuliia
Mikulska
,
Pankti
Dhumal
,
Nathan
Langford
,
Susan
Nehzati
,
Rhiannon
Boseley
,
Sang
Pham
,
Christian
Pfrang
,
Manpreet
Kaur
,
Eugenia
Valsami-Jones
,
Konstantin
Ignatyev
,
Dhruv
Menon
,
Superb K.
Misra
,
Iseult
Lynch
Diamond Proposal Number(s):
[33674, 35117, 35776, 40080, 40942]
Open Access
Abstract: Metal–organic frameworks (MOFs) hold immense potential for applications from separations to catalysis, yet their long-term behavior across real-world environments remains unclear. Here we introduce a hierarchical exposure framework that tracks the structural and chemical transformations in the archetypal zirconium MOF UiO-66 across sequential compartments─atmospheric gases, air, aqueous media and a biological host─and resolves how prior exposures condition or prime subsequent transformations. Using synchrotron-based spectroscopy, we find that oxidative/reactive gases leave the Zr-carboxylate nodes essentially intact, whereas exposure to environmentally relevant aqueous media initiates partial shifts in local Zr coordination and introduces oxygen into the pores─with transformation extent governed by the chemistry of the environmental matrices. Strikingly, acute exposure (24 h) to the water flea Daphnia magna drives profound framework degradation and respeciation to Zr hydroxide species. Microfocus XRF maps show that Zr is highly localized in the animal’s digestive tract, and region-specific XANES confirms uniform speciation across its tissues. Our findings establish a paradigm shifting cross-compartment transformation hierarchy in which biological processes can dominate the fate of stable MOFs even when abiotic exposures appear benign. Thus, organism-level biotransformation should be performed as a necessary part of environmental safety assessments and materials design.
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Jan 2026
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B18-Core EXAFS
I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[33674, 35117, 35776, 40942]
Open Access
Abstract: Metal–organic frameworks (MOFs) are entering water technologies on the premise that abiotic stability predicts ecological safety. We overturn this assumption by showing that UiO-66 – often regarded as chemically and structurally robust – remains intact after 7-day aging in natural borehole water yet undergoes rapid in vivo transformation in Daphnia magna. Synchrotron Microfocus X-ray absorption spectroscopy (XAS) revealed collapse of the ordered Zr–carboxylate coordination into disordered Zr–O environments within the gut; Extended X-ray Absorption Fine Structure (EXAFS) showed loss of second-shell features, and Transmission Electron Microscopy (TEM) confirmed loss of crystallinity with nanoscale aggregates appearing within 24 h of ingestion. Although acute immobilization was limited (48 h EC50 ≈ 26.5 μg mL–1), a sublethal, environmentally relevant exposure (10 μg mL–1) caused pronounced chronic effects: brood initiation was delayed by 3–5 days and cumulative reproduction decreased by ∼74% without mortality. We attribute these outcomes to gut-level transformation and associated energetic/physiological burdens, not captured by standard acute tests. These results show that abiotic stability does not necessarily imply biological inertness and highlight the need to integrate in vivo transformation pathways with chronic end points in environmental risk assessment for water-sector materials. This perspective provides a mechanistic basis to inform Safe-and-Sustainable-by-Design (SSbD) MOFs before widespread deployment in water treatment.
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Dec 2025
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B18-Core EXAFS
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Diamond Proposal Number(s):
[34510, 39677]
Open Access
Abstract: Excessive nitrogen fertiliser use has resulted in reactive nitrogen losses to the environment through gaseous N emissions, like N2O, resulting in agriculture being a major anthropogenic source of N2O gas emissions globally. Using engineered nanomaterials to deliver reactive nitrogen can aid in more efficient nutrient delivery to crops, maximising yield and crop quality, while minimising reactive losses to the environment. ZSM-5-15, a nano-zeolite, increased cumulative N2O emissions by 134% when applied in combination with a 50% dose of conventional nitrogen fertiliser. This is theorised to be through ion exchange of ZSM-5-15’s extra-framework NH4+ ion load being released, allowing nitrifying microbes to act on the newly released NH4+ and increase N2O emissions. BEA-19, a similar zeolite to ZSM-5-15 but with a slightly altered Si:Al ratio, size and charge, causes no increase in N2O emissions. While ZSM-5-15 increases reactive N emissions it also drives improved lettuce growth, with 13% more biomass accumulation compared to a half dose of conventional fertiliser. Ce0.75Zr0.25O2, a nano-metal oxide, improves growth by 6% and maintains the nutritive quality of lettuce, with higher Zn, Cu, Mg, K, Fe and Mn contents, without increasing N2O emissions. Nano-Ce0.75Zr0.25O2 transforms in soil to form CeO2 and Ce0.9Zr0.1O2, leaching Zr4+ ions some of which partly form ZrCl4. These compounds may then act on lettuce roots and soil microbes independently. These results indicate how nanomaterials may impact reactive nitrogen emissions through effects on soil microbial communities.
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Sep 2025
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[33172, 14239]
Open Access
Abstract: Recent reviews have highlighted borate polyanion systems as promising high-voltage cathode candidates for rechargeable Mg-ion batteries (RMBs) [Coordination Chemistry Reviews, 427, 213551 (2021)]. However, evaluating the electrochemical performance of cathodes for Mg-ion batteries is challenging, with many reports relying on an observed electrochemical capacity rather than demonstrating Mg-ion (de)intercalation. To address these two points, we study three classes of borate polyanions: orthoborates M3(BO3)2, ludwigites M3BO5, and pyroborates M2B2O5 and use a suite of experimental techniques to investigate de-magnesiation on charging vs Li metal with a Li electrolyte. We select five representative materials Mg2Mn(BO3)2, Mg2Ni(BO3)2, Mg2FeBO5, MgFeB2O5 and MgFe0.5Mn0.5B2O5. Whilst promising first charge capacities up to 200 mAh g−1 are observed for ball-milled cathodes cycled at 55°C in a Li containing electrolyte, extensive post-cycling analysis using ex-situ X-ray Photoelectron Spectroscopy (XPS) and ex-situ Synchrotron Powder X-ray Diffraction (SXRD), combined with operando X-ray Absorption Spectroscopy (XAS) and operando Online Electrochemical Mass Spectrometry (OEMS), show that the capacities obtained are not associated with Mg2+ mobility in the cathodes, de-magnesiation or transition-metal redox. The observed capacity originates from a process enhanced by ball-milling, which is common to all borate polyanions investigated in this work. This process is in part attributed to the irreversible reaction of an amorphous surface layer on the polycrystalline particle, rich in carbonate and glassy borate phases. Here we present the first systematic study of the viability of transition-metal borate polyanions as intercalation cathode materials for RMBs and conclude that, despite the promising electrochemistry, these materials do not de-magnesiate under our tested conditions.
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Sep 2025
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B18-Core EXAFS
I14-Hard X-ray Nanoprobe
I18-Microfocus Spectroscopy
I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[33674, 35117, 35776, 40942, 37789]
Open Access
Abstract: Achieving safe and sustainable nanomaterials remains challenging—not necessarily from limited synthetic innovation but due to gaps in observing structural and chemical transformations under environmental conditions. Here, we make a call for a tri-beam operando characterization strategy, integrating synchrotron, neutron, and X-ray free-electron laser (XFEL) techniques into one synergistic experimental framework. Unlike traditional methods providing disconnected snapshots, tri-beam analysis dynamically tracks nanomaterial evolution from atomic-scale changes to structural collapse under near-real-world/quasi-realistic conditions. This holistic approach reveals previously hidden degradation pathways, transient states, and physicochemical thresholds that reshape definitions of material safety. Enhanced by robotic automation, machine learning, and findable, accessible, interoperable, and reusable (FAIR) data principles, our method directly supports Europe’s safe and sustainable by design (SSbD) initiative. We propose embedding tri-beam datasets into regulatory standards, predictive models, and AI-driven screening workflows. Ultimately, tri-beam operando characterization represents a transformative platform for designing resilient, high-performance nanomaterials that meet the environmental and societal demands of the 21st century.
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Sep 2025
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Abstract: Metal–organic frameworks hold immense application potential, but their stability and environmental safety remain barriers to industrial translation. Embracing the ‘safe and sustainable by design’ framework would, however, set a transformative pathway to the development of robust, recyclable metal–organic frameworks, ensuring functionality, minimal ecological impact and alignment with circular economy and chemical sustainability goals.
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Jan 2025
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[33172, 34243]
Open Access
Abstract: We investigate magnesium–iron pyroborate MgFeB2O5 as a potential cathode material for rechargeable magnesium-ion batteries. Synchrotron powder X-ray diffraction and Mössbauer spectroscopy confirm its successful synthesis and iron stabilization in the high-spin Fe(II) state. Initial electrochemical testing against a lithium metal anode yields a first charge capacity near the theoretical value (147.45 mAh·g–1), suggesting MgFeB2O5 as a promising cathode candidate. However, multimodal analyses, including scanning electron microscopy energy-dispersive X-ray (SEM-EDS) analysis, operando X-ray absorption near edge spectroscopy (XANES), and Mössbauer spectroscopy, reveal the absence of any Fe redox reactions. Instead, we propose that the source of the observed capacity involves the irreversible reaction of a small (4–7 wt%) Fe metal impurity. These findings highlight the need for diverse characterization techniques in evaluating the performance of new Mg cathode materials, since promising initial cycling may be caused by competing side reactions rather than Mg (de)intercalation.
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Dec 2024
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
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Prathmesh
Bhadane
,
Dhruv
Menon
,
Prateek
Goyal
,
Mohammad Reza
Alizadeh Kiapi
,
Biraj
Kanta Satpathy
,
Arianna
Lanza
,
Iuliia
Mikulska
,
Rebecca
Scatena
,
Stefan
Michalik
,
Priya
Mahato
,
Mehrdad
Asgari
,
Xu
Chen
,
Swaroop
Chakraborty
,
Abhijit
Mishra
,
Iseult
Lynch
,
David
Fairen-Jimenez
,
Superb K.
Misra
Diamond Proposal Number(s):
[39677, 38403]
Abstract: Recycling and recovery of rare earth elements (REEs) from electronic wastes can accelerate efforts to mitigate the environmental burden associated with their excessive mining, while catering for their growing demand. Contemporary recovery strategies are yet to make an impact at an industrial scale due to low REE uptakes, complex mechanisms, and high regeneration energies, leading to an overall poor scalability. Here, we report a two-dimensional metal–organic framework (BNMG-1) featuring a dense arrangement of active adsorption sites for the high uptake of heavy and light REEs. BNMG-1 with a lateral dimension of ca. 350 nm and a thickness of 14 nm was synthesized via a facile one-pot reaction using a green solvent under room temperature and atmospheric pressure. The two-dimensional structure of BNMG-1 was resolved using three-dimensional electron diffraction and EXAFS analysis. Batch experiments showed BNMG-1 to have an adsorption capacity of 355.8 mg/g for Nd3+, 323.1 mg/g for Y3+, 331 mg/g for Dy3+, 329mg/g for Tb3+ and 333 mg/g for Eu3+, which is a near-benchmark performance for a non-functionalised MOF. The adsorption efficiency for Nd3+ reached 99 % by 6 h and 88 % by 48 h for Y3+. The adsorption efficiency did not get affected over a pH range of 3 to 6 and retained > 99 % of its adsorption capacity for up to 4 cycles. For application on real-life samples, CFL lamp waste and waste magnets were used as a reservoir of heavy (Yttrium) and light (Neodymium) REEs. BNMG-1 demonstrates an efficient recovery of 57 % for Neodymium from scrap magnets and 27 % for Yttrium from waste fluorescent lamps. This performance, which is maintained under acidic conditions and over multiple cycles, highlights the competitiveness of BNMG-1 for the economic large-scale recovery of REEs.
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Dec 2024
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B18-Core EXAFS
E02-JEM ARM 300CF
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Diamond Proposal Number(s):
[35687, 38973]
Open Access
Abstract: The induction of structural distortion in a controlled manner through tilt engineering emerges as a potent method to finely tune the physical characteristics of Prussian blue analogues. Notably, this distortion can be chemically induced by filling their pores with cations that can interact with the cyanide ligands. With this objective in mind, we optimized the synthetic protocol to produce the stimuli-responsive Prussian blue analogue AxMn[Fe(CN)6] with A = K+, Rb+, and Cs+, to tune its stimuli-responsive behavior by exchanging the cation inside pores. Our crystallographic analyses reveal that the smaller the cation, the more pronounced the structural distortion, with a notable 20-degree Fe-CN bending when filling the cavities with K+, 10 degrees with Rb+, and 2 degrees with Cs+. Moreover, this controlled distortion offers a means to switch on/off its stimuli-responsive behavior, while modifying its magnetic response. Thereby empowering the manipulation of the PBA's physical properties through cationic exchange.
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Aug 2024
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