B18-Core EXAFS
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Diamond Proposal Number(s):
[42455]
Open Access
Abstract: The direct synthesis of amorphous metal–organic frameworks (aMOFs) is an appealing yet often avoided approach due to the perceived unpredictability of amorphous network formation. Here, we develop a strategy for aMOF synthesis using pre-formed nanoclusters and rigid organic linkers, providing enhanced control over disorder and defect chemistry while bypassing the traditional crystallise–amorphise approach. By systematically comparing this approach to other direct synthesis routes and using X-ray pair distribution function, thermogravimetric, and statistical analyses, we establish key design principles governing aMOF formation. We demonstrate that kinetic control—fast reactions under basic conditions at room temperature—suppresses crystallisation and drives amorphous network formation. The nanocluster approach consistently yields highly disordered frameworks with the shortest coherence lengths among direct synthesis methods. Additionally, we show that tuning metal composition through doping with kinetically inert cations restricts coordination reversibility, significantly increasing defect density and structural disorder. Structural analysis reveals that while aMOFs share motifs with crystalline polymorphs, they cannot be directly mapped onto known structures, highlighting the importance of more nuanced characterisation approaches. By developing a systematic approach to aMOF design, this work provides a foundation for tailoring structural disorder, expanding their potential for catalysis, adsorption, and transport applications.
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Apr 2026
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I11-High Resolution Powder Diffraction
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Jamie W.
Gittins
,
Chloe J.
Balhatchet
,
James
Hill
,
Teedhat
Trisukhon
,
Malina
Seyffertitz
,
Seung-Jae
Shin
,
Yashna
Khakre
,
Kangkang
Ge
,
Thomas
Kress
,
Smaranda C.
Marinescu
,
Aron
Walsh
,
Oskar
Paris
,
Ieuan D.
Seymour
,
Alexander C.
Forse
Diamond Proposal Number(s):
[34243]
Open Access
Abstract: Understanding how ions interact with electrode surfaces at the molecular level is essential for improving the performance of energy storage devices and electrocatalysts. However, progress has been limited by the structural disorder and poorly defined surface chemistries of conventional carbon-based electrodes. In this work, we use layered metal–organic frameworks (MOFs) as model systems to investigate how different functional groups influence electric double-layer capacitance. We find that electrodes with deprotonated M–O and M–S groups exhibit significantly enhanced capacities with alkali metal cations, most notably Li+, compared to tetraethylammonium (TEA+), while no enhancement is observed for MOFs with protonated M–NH groups. The largest capacity increase is seen for MOF electrodes with metal–hydroxy linkages paired with Li+ electrolytes, which we attribute to strong Li–O interactions and improved charge screening. This mechanism is supported by solid-state nuclear magnetic resonance spectroscopy experiments and molecular simulations, which reveal specific Li+ binding at oxygen-rich sites, while operando X-ray techniques rule out cation intercalation as a contributing factor. Overall, these results highlight a chemically tunable strategy for enhancing charge storage in porous electrodes and offer new insights into how surface functionality impacts electric double-layer behavior.
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Apr 2026
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B18-Core EXAFS
I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[34409, 37864, 35948]
Open Access
Abstract: The persistent contamination of water sources by perfluorooctanoic acid (PFOA) poses a major environmental and public health challenge. PFOA is a representative member of per- and polyfluoroalkyl substances (PFAS), a class of compounds characterized by high chemical stability, bioaccumulation potential, and toxicity. Conventional water treatment processes are not fully effective in removing PFOA, underscoring the urgent need for advanced remediation strategies. Here, we report the development of Fe-MOF-808, a novel porous material obtained by incorporating binuclear iron species into the Zr6O8 nodes of the MOF-808 framework. Comprehensive structural characterization was performed, including ex/in situ synchrotron-based techniques combined with computational modeling. The results confirm successful iron integration without compromising the structural integrity and accessibility of the porous network. Moreover, the presence of multiple, spatially accessible binding sites enables Fe-MOF-808 to capture PFAS through a combination of electrostatic, hydrophobic and coordinative interactions. This resulted in high removal efficiencies across various water matrices and for a wide range of PFAS pollutants and concentrations. Fe-MOF-808 notably achieves complete PFOA removal within minutes and demonstrates excellent recyclability over multiple adsorption cycles. The material also reaches experimental uptake and a maximum Langmuir adsorption capacity of 2081 and 3120 mg PFOA g–1, respectively, vastly outperforming the pristine MOF-808 and other state-of-the-art MOF materials. Overall, mechanistic insights gained from this study highlight the critical role of designing specific chemical environments within MOFs to maximize pollutant-sorbent interactions.
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Apr 2026
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Shan
Dai
,
Longzhang
Dong
,
Yinlin
Chen
,
Jiangnan
Li
,
Justyna
Rogacka
,
Yuhang
Yang
,
Zi
Wang
,
Benjamin J.
Moore
,
Daniel
Lee
,
Yongqiang
Cheng
,
Svemir
Rudic
,
Bogdan
Kuchta
,
Mark D.
Frogley
,
Lucy
Saunders
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[39702, 41731]
Abstract: The desulfurization of flue gas requires sorbents capable of selective and reversible SO2 capture. However, top-performing materials operate through either strong binding sites or the use of narrow pores, leading to difficulties in desorption and materials regeneration. Here, we report the efficient capture of trace SO2 using a robust and scalable aluminum-based metal–organic framework, MIL-120, which shows an exceptional SO2 uptake of 2.1 mmol g–1 at 2500 ppm and 298 K, coupled with optimal heats of adsorption (19–42 kJ mol–1) and fully reversible desorption at room temperature. Direct visualization of adsorbed SO2 molecules reveals host–guest and guest–guest interactions, collectively affording an SO2 packing density of 1.92 g cm–3, formally surpassing that of solid SO2 (1.62 g cm–3). Breakthrough experiments demonstrate that MIL-120 exhibits remarkable trace SO2 capture in the presence of dry or wet NO2 (another corrosive gas present in flue gas) with a record dynamic selectivity of 124, confirming the potential for MIL-120 to separate SO2/NO2 mixtures. This work sets a new benchmark for sorbent materials for reversible trace SO2 capture and separation.
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Apr 2026
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[42583]
Open Access
Abstract: Ethane-selective sorbents can enable single-step purification of ethylene but remain elusive to date. We report a Zn-based metal-organic framework (ZAI-3N) decorated with amino-based ‘molecular gates’ that exhibit highly selective adsorption of C2H6 over C2H4. Upon activation, ZAI-3N (zinc-adenine-3-aminoisonicotinic acid) features contractions of both Zn─N bonds and pores (from 2.009 to 1.914 Å and from 4.88 × 3.40 to 3.47 × 2.75 Å2, respectively). At 313 K and 1 bar, ZAI-3N exhibits an exceptional ratio of 10.6 for C2H6/C2H4 uptakes and a benchmark selectivity of 11.7, outperforming state-of-the-art porous solids. Synchrotron X-ray powder diffraction and modelling reveal that the methyl group in C2H6 can trigger amino rotation and facilitate gate opening, while π-electrons of C2H4 hinder such a process with a notably increased barrier (～5 and 11 kJ mol−1, respectively). Dynamic breakthrough experiments confirm the efficient separation of C2H6/C2H4 (v/v = 5/5 and 1/9), affording C2H4 with a high purity of 99.4% in single step with excellent recyclability and an C2H4 productivity of 10.3 mL g−1. This work demonstrates the judicious choice of ‘molecular gate’ as a promising protocol for challenging industrial gas separations.
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Apr 2026
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[37864]
Open Access
Abstract: Contamination of surface and groundwater sources by emerging persistent pollutants has presented a global environmental challenge that demands advanced remediation materials. This work exploits the large mesopores and unsaturated inorganic nodes in MIP-206-based metal–organic frameworks (MOFs) for the highly efficient adsorption of perfluorocarboxylic acids (PFCAs) from water. The materials display excellent performance for long-chain PFCAs, achieving removal efficiencies up to >99% within seconds. Detailed mechanistic studies, including synchrotron analyses, provide key insights into the development of optimized PFCA sorbents via multiple interaction types
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Apr 2026
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
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Shan
Dai
,
Xiangdi
Zeng
,
Benjamin J.
Moore
,
Yuxiang
Zhu
,
Yuhang
Yang
,
Zi
Wang
,
Luyan
Li
,
Te
Wang
,
Ivan
Da Silva
,
Luke
Keenan
,
Floriana
Tuna
,
Daniel
Lee
,
Sarah
Day
,
Lucy
Saunders
,
Martin
Schroeder
,
Sihai
Yang
Abstract: Metal–organic framework (MOF) materials share some common features with metalloenzymes including site-isolated metal centers that template dynamic substrate activation within a functionalized cavity or pocket. We report the light-induced reversible binding of CO2 in a cerium-based MOF, Ce-UiO-66-NH2, incorporating an amino functionalized linker, which enables photoreduction of CO2 to CO in H2O without using sacrificial agents. A production rate for CO of 126 μmol·g–1·h–1 with 100% selectivity is observed, outperforming its non-amine analogue (Ce-UiO-66) and benchmark catalysts reported to date. In situ infrared, X-ray absorption, electron paramagnetic resonance and transient absorption spectroscopy reveal that photoexcitation induces a ligand-to-metal charge transfer to generate transient open Ce(III) sites that bind CO2 in a μ-(η1-O)(η1-C) binding mode. This binding is reversible and activates CO2 for subsequent photoreduction to CO. This work will promote the design of photocatalysts capable of synthesizing fuels from CO2.
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Mar 2026
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E02-JEM ARM 300CF
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Elif
Tezel
,
Beatrice
Garetto
,
Davide
Salusso
,
Dag K.
Sannes
,
Izar
Capel Berdiell
,
Sahra
Ahmed
,
Prantik
Sarkar
,
Stian
Svelle
,
Michael
Hirscher
,
Unni
Olsbye
,
Elisa
Borfecchia
,
Petra Ágota
Szilágyi
Diamond Proposal Number(s):
[41108]
Open Access
Abstract: This study investigates the catalytic performance of palladium nanoparticles supported on UiO-67, a zirconium-based metal–organic framework (MOF), for CO2 hydrogenation to methanol, emphasising the influence of the size and location of Pd particles in relation to the MOF matrix. Depending on the synthesis conditions, Pd particles were either supported on the outer surface of the MOF, forming larger nanoparticles (∼11–18 nm), or embedded within the MOF pores as smaller particles (∼1 nm), with their size constrained by the host framework. Advanced characterisation techniques, including X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and transmission electron microscopy (TEM), coupled with catalytic testing, revealed that Pd clusters embedded within the MOF exhibited higher CO2 conversion and methanol selectivity. This superior performance is attributed not only to the increased surface area-to-volume ratio of the smaller Pd clusters, but also to the enlarged metal–MOF interface, which promotes favourable electronic interactions and enhances the accessibility of active sites. Notably, the confined Pd clusters suppressed methane formation, producing CO as the sole by-product. Despite local distortions at elevated temperatures, the UiO-67 framework maintained its structural integrity under reaction conditions, highlighting its thermal and chemical robustness. These findings deepen the understanding of structure–activity relationships in MOF-based catalysts and underscore the critical role of precise control over metal dispersion and metal-support interfaces in optimising catalytic efficiency and selectivity for CO2 hydrogenation.
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Mar 2026
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B22-Multimode InfraRed imaging And Microspectroscopy
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Diamond Proposal Number(s):
[40142]
Open Access
Abstract: Triboelectric nanogenerators (TENGs), which convert mechanical energy into electrical signals, have emerged as apromising platform for self-powered motion sensing. However, the development of high-sensitivity TENG sensors remains limited by the availability of tunable and efficient tribo-positive materials, which are electron donors. In this work, we present a material design strategy based on the incorporation of electron-donating functionalized metal–organic framework (MOF) fillers into a polyurethane (PU) polymer matrix. Three functional groups (−CH3, −NH2, and −OH) were systematically studied to investigate their influence on triboelectric performance. The resulting composite membranes demonstrated tunable charge-donating behavior and improved electrical output, with the −OH-modified MOF yielding the highest electrical output of 197.6 ± 1.3 V and 0.47 ± 0.08 μA/cm2, which are 2.3 and 3.2 times higher than that of the pristine PU. The enhanced charge-donating mechanism was elucidated through a combination of advanced micro- and nanoscale chemical and mechanical analysis. Theoretical calculations employing ab initio density functional theory (DFT) were performed to reveal the electron distribution within the periodic MOF structure. Furthermore, the practical application of the optimized TENG device was demonstrated in a single-electrode shear sensor configuration, exhibiting high sensitivity in sliding motion detection. This study highlights a scalable and biocompatible strategy for improving tribo-positive materials and advancing the performance of tunable TENG-based sensors to enable shear force monitoring.
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Mar 2026
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I15-Extreme Conditions
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Zhencai
Li
,
Zihao
Wang
,
Huotian
Zhang
,
Xuan
Ge
,
Ivan
Hung
,
Bozhao
Yin
,
Fengming
Cao
,
Pritam
Banerjee
,
Tianzhao
Xu
,
Lars R.
Jensen
,
Joerg
Jinschek
,
Morten M.
Smedskjaer
,
Zhehong
Gan
,
Laurent
Calvez
,
Guoping
Dong
,
Jianbei
Qiu
,
Donghong
Yu
,
Feng
Gao
,
Haomiao
Zhu
,
Yuanzheng
Yue
Diamond Proposal Number(s):
[39002]
Open Access
Abstract: Some zeolitic imidazolate frameworks (ZIFs) represent a new family of glass formers, with hitherto unknown photonic functionalities. In this work, we report the discovery of broadband white light emission in ZIF-62, achieved through a vitrification-pressurization-annealing strategy. In this strategy, visible (blue) light emission was realized after the vitrification of ZIF-62, subsequently enhanced and broadened upon pressurization. Additionally, a sharp redshift (37 nm) of the emission peak occurred in pressurized ZIF-62 glass as the annealing temperature exceeded a critical annealing temperature (1.07Tg). This implies that the photoluminescence of ZIF-62 can be precisely tailored. The photoluminescence quantum yield of ZIF-62 glass reached 12.2% after annealing at 1.13Tg for 30 min. The origin of the observed phenomena was revealed by conducting structural analyses. Based on the annealed ZIF-62 glass with the best photoluminescent performance, a white light-emitting diode (LED) was fabricated, which exhibited a luminous efficacy of 4.2 lm/W and a high operational stability, i.e., retaining 36.8% of the efficacy after 72 h of operation. This work demonstrated the feasibility of the development of one-component white LEDs by utilizing the annealed ZIF-62 glass.
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Mar 2026
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