B18-Core EXAFS
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Diamond Proposal Number(s):
[42410]
Open Access
Abstract: Photocatalytic reforming offers a route to valorize biomass and plastic waste into clean H2 under ambient conditions. However, the scalability of photocatalyst sheets is limited by high-temperature processing, binders and complex co-catalyst deposition. Here a [Co4Zr2O(OnPr)10(acac)4] single-source precursor is deposited onto Al-doped SrTiO3 and immobilized on glass substrates to fabricate photocatalyst sheets using multiple techniques, including high-throughput spray coating. The resulting sheets enable photoreforming of cellulose- and polyethylene terephthalate-derived feedstocks, producing H2 alongside value-added organics such as formate, acetate, glycolate and glycolaldehyde dimer. The system is demonstrated from the centimeter- to meter-squared scale, culminating in a 1-m2 outdoor reactor operating under natural sunlight. After 6 h, H2 yields reached 5.24 and 1.51 mmol m−2 for glucose and pretreated cellulose, respectively, with concurrent formation of oxygenates. Techno-economic analysis based on real-world data estimates an H2 cost of £0.93 mmol−1. This work advances scalable photocatalytic reforming and provides a step towards practical deployment.
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Jun 2026
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Open Access
Abstract: Metal–organic frameworks (MOFs) are often assessed for stability using end-point structural metrics, yet their exposure-relevant chemical identity at the metal center may evolve on much shorter time scales in realistic aqueous environments. Here we examine nanoscale copper–imidazolate (CuIm) MOFs transformation across three benchmark matrices representing an abiotic-to-biorelevant gradient: a freshwater-like groundwater matrix (borehole water), a marine-like high-salinity matrix (artificial seawater), and a ligand-rich, protein-free cell-culture medium (serum-free DMEM) used here as a chemically complex challenge matrix. Using ex situ time-resolved separation of particle-associated and dissolved/complexed fractions coupled with copper-centered speciation analysis, we resolve a distinct kinetic hierarchy. CuIm remains largely conserved in borehole water, exhibits gradual reorganization in artificial seawater, and undergoes rapid transformation in serum-free DMEM, with the particle-associated fraction converging to an apparent end-state spectrum by ∼4 h. Medium-dependent copper mobilization to the dissolved/complexed pool accompanies these speciation trajectories. End-point characterization further indicates that framework-like structural signatures can persist while surface chemistry is substantially altered, demonstrating a decoupling between long-range order and node/surface identity. Collectively, these findings show that CuIm follows matrix-selected transformation trajectories with pronounced early-time trajectory shifts and that stability assessments must be grounded in time-resolved chemical identity rather than end-point crystallinity alone.
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Jun 2026
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B18-Core EXAFS
I18-Microfocus Spectroscopy
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Swaroop
Chakraborty
,
Iuliia
Mikulska
,
Rhiannon
Boseley
,
Sang
Pham
,
Prathmesh
Bhadane
,
Pankti
Dhumal
,
Santanu
Majumder
,
Jajati
Mandal
,
Tina
Geraki
,
Superb K.
Misra
,
Christian
Pfrang
,
Iseult
Lynch
Diamond Proposal Number(s):
[33674, 35117, 41674]
Open Access
Abstract: Metal–organic frameworks (MOFs) are increasingly deployed in environmental technologies, yet their fate and hazard under realistic multistep exposure scenarios remain poorly constrained. Here, we track hierarchical transformations of nanoscale ZIF-8 (Zeolitic Imidazolate Framework-8) across an exposure cascade spanning atmospheric aging (air and reactive gases O3/NO2), aqueous aging in environmentally and biologically relevant media, and ingestion by the freshwater crustacean Daphnia magna. Synchrotron Zn K-edge X-ray absorption spectroscopy (XAS), micro-X-ray fluorescence (μ-XRF), X-ray photoelectron spectroscopy (XPS), and electron microscopy show that gas-phase exposure produces only minor surface perturbations, whereas aqueous contact drives pronounced medium-dependent restructuring, including nitrogen depletion and oxygen enrichment at the surface and time-resolved dissolved Zn release with chemistry-imposed plateaus. In vivo, Zn speciation diverges from the pristine Zn–N fingerprint; an unexposed endogenous Zn baseline and linear combination fitting (LCF) indicate a mixture of endogenous Zn with transformed Zn pools dominated by O/P/S-type coordination environments. Acute ecotoxicity assay demonstrates strong concentration dependence (48 h immobilization EC50 ≈0.5 μg mL–1), and chronic exposure at 0.10 μg mL–1 reduces cumulative brood production with increased adult mortality over 24 days. Mechanistically, fractionated toxicity assays show that washed aged particles/precipitates and whole aged suspensions are more potent than particle-free filtrates, indicating that particle-associated transformed Zn pools contribute substantially beyond dissolved Zn alone. Together, these results show that ZIF-8 risk emerges from its sequential transformation trajectory rather than its pristine state, motivating tiered aging protocols coupled to in vivo speciation and fractionated hazard testing for MOF safety assessment.
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May 2026
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
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James M. A.
Steele
,
Joshua D.
Bocarsly
,
Liam A. V.
Nagle-Cocco
,
George S.
Phillips
,
Farheen N.
Sayed
,
Giulio I.
Lampronti
,
Fabio
Orlandi
,
Pascal
Manuel
,
Iuliia
Mikulska
,
Clare P.
Grey
,
Sian E.
Dutton
Diamond Proposal Number(s):
[34243, 32018]
Open Access
Abstract: NaNiO2 is a promising cathode material for sodium-ion batteries due to its high theoretical capacity of 235.8 mAh.g–1. However, as with many Na-ion cathode materials, a series of poorly understood phase transitions occur on electrochemical cycling, inducing volume mismatch-based stress/strain, resulting in particle cracking, electrochemically disconnected particles and, therefore, irreversible capacity loss. This behavior is one key obstacle to developing long-lasting, high-performance Na-ion batteries. Although the series of phases that form as NaxNiO2 is electrochemically cycled have been previously identified, their structures remained unsolved, limiting our ability to understand and control the phase transition behavior. Here, we report structural solutions based on Rietveld refinement against high-resolution synchrotron x-ray diffraction (SXRD) and neutron powder diffraction (NPD) for the phases obtained on desodiation: P″3-Na1/2NiO2, O″3-Na2/5NiO2, and O‴3-Na1/3NiO2. Each phase contains a unique Na+/vacancy ordering, minimizing intralayer electrostatic repulsions between Na+ ions, and Nix+-charge ordering decreasing interlayer repulsions through the location of lower valence Nix+ nearer to vacancies. Using these structures, we conduct sequential Rietveld refinement against operando SXRD data, which supports prior identification of a transient P‴3-Na1/2<x<2/3NiO2 phase, not isolable ex situ. Operando data also identify the presence of a solid-solution phase O″3δ-Na1/3<x<2/5NiO2 and second-order behavior of the O″3-Na2/5NiO2 → O‴3-Na1/3NiO2 phase transition at the top of charge. This work provides unprecedented insight into structural evolution during electrochemical cycling in Ni-rich Na cathodes (and likely Li analogues), paving the way toward rational doping regimes designed to disrupt degradation-inducing phase transitions, increasing capacity and cycle lifetime, thus improving the performance of Co-free Na and Li cathodes.
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May 2026
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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
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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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
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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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