I11-High Resolution Powder Diffraction
I19-Small Molecule Single Crystal Diffraction
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Open Access
Abstract: The selective separation of enantiomers is important for industrial technologies such as pharmaceuticals, biotechnology, and agrochemicals. Chiral porous materials have been used as the stationary phase for the chromatographic separation of enantiomers; however, they lack synthetic and performance designability. Here we present a new chiral metal-organic framework with excellent chromatographic enantioseparation performance for a family of aromatic chiral molecules. This material has been developed by diversifying the amino acid sidechains appended to an underlying common structural framework. The structure of the framework places the bulky isopropyl sidechain of L-valine in the one-dimensional pore channels characteristic of the materials family, modulating the accessible space to emphasize the helical shape of the channels. The dimensions of the pores are adapted to those of guests, through conformational flexibility directed by the sidechain, creating appropriate adsorption sites for functionalized aromatic guests. This porous framework affords superior enantioseparation performance compared to the same underlying framework decorated with the shorter methyl sidechain. These results demonstrate that the structure and porosity of dynamic chiral metal-organic frameworks can be tailored using amino acid-derived linkers and enhance the enantiomeric separations through stimulation of conformational flexibility.
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Oct 2026
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B07-B1-Versatile Soft X-ray beamline: High Throughput ES1
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Jinhwan
Byeon
,
Nick
Gys
,
Jorid
Smets
,
Ali
Azimi
,
Lukas
Nulens
,
João
Fernandes
,
Leen
Boullart
,
Dowon
Kim
,
Kevin M.
Dorney
,
Jesus
Gandara-Loe
,
Juhyung
Park
,
Min Jong
Jeong
,
Sangjin
Kim
,
Sukwon
Hong
,
Tomasz
Sobol
,
Barbara
Wolanin
,
Tom
Hauffman
,
Joris Van De
Vondel
,
Rob
Ameloot
Diamond Proposal Number(s):
[41436]
Abstract: Dry-deposited metal–organic resists are key enablers for advanced patterning processes in next-generation semiconductor manufacturing. Here, we report halogenated amorphous zeolitic imidazolate framework (a-ZIF) resists deposited entirely by a dry process, which exhibit a pronounced irradiation-source-dependent tone conversion. Smooth a-ZIF films were grown by chemical vapor deposition (CVD) using 4,5-diiodoimidazole (DI-Im) precursors. Partial in situ thermal decomposition of DI-Im produces a ternary linker mixture (DI-Im, 4-iodoimidazole, imidazole), promoting the growth of uniform, amorphous films. Under electron-beam (e-beam) exposure, the resist operates in a positive-tone mode with high sensitivity (D50 = 0.15 mC cm–2, comparable to commercial PMMA resists) and resolves 100 nm line-and-space and 80 nm contact-hole patterns. In contrast, EUV exposure yields high sensitivity in negative-tone development (D50 = 65 mJ cm–2) and exhibits a nonmonotonic dose–thickness response in positive-tone development. We demonstrate positive-tone EUV patterning of 90 nm line-and-space features. X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopy trace the tone conversion to distinct reaction pathways: high-energy primary electrons under e-beam exposure drive imidazole ring decomposition into soluble polar fragments, giving rise to the positive-tone response, whereas the low-energy electrons generated under EUV cleave C–I bonds while retaining the ring, and the resulting poorly soluble recombination products account for both the negative-tone behavior and the nonmonotonic positive-tone response. Identifying the electron-energy regimes and reaction pathways responsible for each behavior provides a basis for engineering the resist response through linker design. These results illustrate that electron-beam exposure cannot serve as a universal chemical proxy for EUV lithography.
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Oct 2026
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B18-Core EXAFS
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Diamond Proposal Number(s):
[40080]
Open Access
Abstract: Metal–organic frameworks (MOFs) offer tunable platforms for water purification, yet the disposal of contaminant-loaded frameworks creates secondary waste and limits their sustainable use. Here, a circular adsorbent-to-catalyst strategy is demonstrated using a freeze-dried two-dimensional Cu–imidazolate framework (FD-BNMG-1). Prepared through scalable aqueous synthesis and lyophilization, FD-BNMG-1 removes more than 95% of Mn(II) from water within 24 h and reaches a maximum adsorption capacity of 370 mg g−1, the highest reported for an unmodified MOF adsorbent toward Mn(II). Cu and Mn K-edge X-ray absorption spectroscopy, supported by powder X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy with energy-dispersive X-ray spectroscopy, and nitrogen sorption analysis, reveals that Mn sequestration drives substantial structural and electronic reconstruction. The Cu coordination number increases from 4.0 to 5.7, long-range Cu order is disrupted, and an open, redox-heterogeneous Mn-integrated Cu coordination nanonetwork is formed. Rather than being discarded, the resulting spent material, Mn@FDB, is directly repurposed as a heterogeneous catalyst for oxidative C–O cross-coupling reactions, affording aryl ester products in yields up to 84% and retaining activity over multiple cycles. This transformation demonstrates how adsorption can program a functional second life for contaminant-loaded MOFs. The approach integrates pollutant capture, material transformation, and efficient catalytic valorization.
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Sep 2026
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I20-Scanning-X-ray spectroscopy (XAS/XES)
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Filip J. R.
Meysman
,
Bent
Smets
,
Silvia
Hidalgo-Martinez
,
Nathalie
Claes
,
Bob C.
Schroeder
,
Jeanine S.
Geelhoed
,
Yun
Liu
,
Jiji
Alingapoyil Choyikutty
,
Tamazouzt
Chennit
,
Thijs
Bodson
,
Alberto
Collauto
,
Maxie M.
Roessler
,
Dmitry
Karpov
,
Sylvain
Bohic
,
Matteo
Aramini
,
Shusaku
Hayama
,
Maxwell
Wetherington
,
Martijn A.
Zwijnenburg
,
Galina
Pankratova
,
Isabel
Pintelon
,
Jean-Pierre
Timmermans
,
Gert
Nuyts
,
Karolien
De Wael
,
Sara
Bals
,
Jo
Verbeeck
,
Han
Remaut
,
Henricus T. S.
Boschker
Diamond Proposal Number(s):
[31284, 36538, 38275]
Open Access
Abstract: Biobased electronics aims for disruptive innovation in sustainable electronics but is obstructed by the low intrinsic conductivity of biomaterials. Recently, fibres were discovered within the cell envelope of multi-cellular cable bacteria, which display an exceptional conductivity for a biomaterial. Yet, the molecular structure and electron transport mechanism remain unresolved, thus precluding a detailed structure-function understanding and the development of biomimetic analogues. Here, we demonstrate that each fibre embeds an extended nickel-organic framework, which consists of a bundle of intertwined nanoribbons, each built from stacked repeat units in which multiple nickel centres are linked by organic dithiolene ligands. This metal-organic supramolecular architecture provides extensive conjugation and electron delocalization, thus enabling exceptional conductance over macroscale distances. This suggests a novel design principle for bio-based electronic materials and opens possibilities for biosynthesis of metal-organic frameworks.
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Sep 2026
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I11-High Resolution Powder Diffraction
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Yukun
Ye
,
Lixia
Guo
,
Jiarui
Fan
,
Zhixin
Wang
,
Zhaozhao
Hu
,
Ruohan
Li
,
Siyu
Zhou
,
Lifei
Lin
,
Yiheng
Wang
,
Mark R.
Warren
,
Ben
Coulson
,
Pascal
Manuel
,
Sarah
Day
,
Eamonn T.
Connolly
,
Jiangnan
Li
,
Sihai
Yang
Diamond Proposal Number(s):
[45967]
Abstract: We report the exceptional propyne (C3H4) storage and propylene (C3H6) purification in a metal-organic framework, PKU-101, controlled via regulation of aromaticity. The pyrene-fused pore interior of PKU-101 provides multiple C─H···π interactions for alkyne, resulting in a record C3H4 adsorption of 250 cm3 cm−3 at 298 K and 1 bar, representing a benchmark sorbent for C3H4. Additionally, the supramolecular interactions enable fine thermodynamic discrimination for alkenes, resulting in excellent separation of C2H4/C3H6 (v/v = 1/1), delivering simultaneously high productivities of C3H6 and C2H4 (267 and 174 L kg−1, respectively; C2H4 purity > 99.9 %). Effective separation of C3H6/C3H8 (v/v = 1/1) and C3H4/C3H6 (v/v = 1/99) with a high C3H6 productivity of 532 L kg−1 (purity of 99.99 %) has also been achieved by PKU-101. In situ crystallographic and spectroscopic studies confirmed the key role of enhanced aromaticity on the discrimination of alkanes/alkenes/alkynes. Importantly, these weak supramolecular interactions enable complete regeneration at only 318 K.
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Sep 2026
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[40309]
Open Access
Abstract: Barocaloric (BC) effects at liquid–vapor transitions in hydrofluorocarbons drive most commercial technologies used for heating and cooling in the heating, ventilation and air-conditioning sector. However, these fluids suffer from huge global warming potential and alternative gases are less efficient, toxic or flammable. Solid–solid and solid–liquid BC materials have zero global warming potential and could even improve on current device efficiencies. Whilst solid–liquid BCs typically outperform solid–solid BCs, the latter are advantageous as they avoid leaks and present easier handling and recyclability thus facilitating waste management. Here we confine the solid–liquid BC stearic acid inside the nanopores of a functionalized metal-organic framework (MOF) and demonstrate that the colossal BC properties are retained in a solid-state material. Moreover, the enhanced interactions between the pore surface and the BC material allow a level of active control over the thermal response, as opposed to passive encapsulation. Our results open novel avenues to exploit and tune colossal BC effects in a wide range of combinations of solid–liquid BC materials embedded within functionalized MOFs, without the associated engineering drawbacks.
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Sep 2026
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B18-Core EXAFS
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Diamond Proposal Number(s):
[37421]
Abstract: This study maps the thermal conversion pathways of ZIF-67 and ZIF-8 under oxidative and reducing atmospheres. Identical sodalite ZIFs were tracked in situ by temperature-resolved synchrotron XRD and Co K-edge XAS, and characterized by TG, FTIR, N2 physisorption and electron microscopy. Under reducing conditions, ZIF-67 maintains tetrahedral Co-N coordination up to ≈523-673 K, collapses between ≈703 and 723 K, and converts at higher temperatures to a mixture of orthorhombic Co2C and metallic Co0. XAS indicates loss of the Co-N pre-edge and growth of low-coordination Co-Co scattering consistent with sub-nanometer, undercoordinated Co clusters embedded in a carbonaceous matrix. Oxidative calcination of ZIF-67 produces crystalline spinel Co3O4, which reduces stepwise (Co3O4 → CoO → Co0) under H2. ZIF-8 decomposes at lower temperatures (onset ≈623 K) and yields stable wurtzite ZnO under oxidative conditions or Zn(CN)2 at high temperature under reducing flow, consistent with imidazolate fragmentation and cyanide capture by zinc. Thermal treatment causes pronounced loss of surface area and pore structure for both ZIFs. These findings clarify atmosphere- and temperature-dependent routes from ZIF precursors to oxide, metallic and carbidic products and offer guidance for tailoring ZIF-derived catalysts and functional nanomaterials via controlled thermal programs.
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Sep 2026
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
I19-Small Molecule Single Crystal Diffraction
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Xu
Chen
,
Lik Hong
Wee
,
Mohammad Reza
Alizadeh Kiapi
,
Christos
Tampaxis
,
Jiarui
Fan
,
Hamish W.
Macleod
,
Yan
Zheng
,
Benjamin J.
Moore
,
Pascal
Manuel
,
Fabio
Orlandi
,
Luke L.
Keenan
,
Enci
Zhang
,
Mehrdad
Asgari
,
Dhruv
Menon
,
Georgia
Charalambopoulou
,
Tom
Willhammar
,
Sihai
Yang
,
William
Shepard
,
Yong
Cui
,
Theodore
Steriotis
,
David
Fairen-Jimenez
Diamond Proposal Number(s):
[37562, 44352, 42292]
Open Access
Abstract: The construction of highly porous metal–organic frameworks with complex topologies requires precise matching between linker conformation and node connectivity. Here we report the reticular design and synthesis of CU-6-M (M = Fe or Cr), assembled from conformationally adaptive diphenylethynyl linkers and six-connected trinuclear oxo-centred clusters. The ability of the linker to adopt multiple out-of-plane conformations satisfies the geometric requirements of a red topology, resulting in a highly interconnected hierarchical pore architecture. CU-6-Fe and CU-6-Cr exhibit an interconnected hierarchical pore system with Brunauer–Emmett–Teller surface areas up to 7,145 m2 g−1. This architecture enables total H2 uptakes of up to 17.5 wt% and 45.4 g l−1 at 100 bar and 77 K. Under temperature–pressure swing conditions, CU-6-Fe and CU-6-Cr deliver up to 16.9 wt% and 44.1 g l−1 and also show record gravimetric CH4 storage at ambient temperature. These results establish linker flexibility as a key design parameter for the realization of complex, highly porous topologies for high-capacity storage of clean-energy fuel gases.
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Sep 2026
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I15-1-X-ray Pair Distribution Function (XPDF)
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Jan-Benedikt
Weiss
,
Lorena
Fritsch
,
Michele
Tricarico
,
Anke
Schoch
,
Soma
Salamon
,
Wen-Long
Xue
,
Chinmoy
Das
,
Pascal
Kolodzeiski
,
Heiko
Wende
,
Jin-Chong
Tan
,
Matthias
Bauer
,
Sebastian
Henke
Diamond Proposal Number(s):
[31642]
Open Access
Abstract: Melt-quenched glasses derived from metal–organic frameworks (MOFs) combine the processability of glasses with the modularity and microporosity of MOFs, yet remain structurally and functionally less diverse than crystalline analogues. Here we show that the chelating ligand 1,10-phenanthroline acts as an organic flux that lowers the glass transition temperature of selected MOFs and induces ligand exchange during melting, thereby enabling control over local coordination and global topology in MOF glasses. In Co2+-based systems, phenanthroline coordinates to the metal nodes, increases the coordination number and reduces network connectivity by forming terminal ligands. This coordination sphere engineering affords a level of structural control not readily achievable in conventional inorganic or organic glasses. Crucially, the lower processing temperature suppresses thermal decomposition, enabling the synthesis of Co2+-based MOF glasses free of magnetic impurities. These glasses exhibit antiferromagnetic coupling and represent unique examples of magnetic MOF glasses formed by melt quenching. Finally, we extend the strategy to otherwise non-meltable carboxylate-based MOFs, establishing flux-mediated ligand exchange as a versatile route to hybrid glasses with tailored connectivity and properties.
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Aug 2026
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[39531]
Open Access
Abstract: Estrogenic hormones are potent endocrine-disrupting contaminants that are inefficiently removed by conventional wastewater treatment processes. Herein, we evaluate a family of isoreticular amino-acid–derived metal–organic frameworks (MOFs), including multivariate variants, for the simultaneous capture of estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethinylestradiol (EE2) from water. Using a solid-phase extraction configuration, a leucine-based oxamidato MOF emerges as a highly efficient sorbent, achieving >90%–95% removal of all four hormones within 30 s in a single loading step, representing one of the fastest simultaneous estrogen capture systems reported to date under SPE conditions. This material exhibits exceptional regenerability, enabling near-quantitative desorption under mild conditions with minimal solvent consumption (1 mL methanol), and stable performance over at least ten reuse cycles. Notably, comparable capture efficiencies are maintained in real river-water samples, demonstrating robustness toward complex aqueous matrices. The crystal structure of a host–guest aggregate confirms estrogen encapsulation within the flexible framework, providing direct structural insight into the origin of the high capture efficiency. These results identify amino-acid–based MOFs as a highly competitive platform for rapid, regenerable, and selective estrogen capture, combining excellent performance with valuable structural insight into host–guest interactions.
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Aug 2026
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