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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I19-Small Molecule Single Crystal Diffraction
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Thien D.
Duong
,
Jiangnan
Li
,
Ruohan
Li
,
Xin
Lian
,
Yinlin
Chen
,
Jiarui
Fan
,
Joseph
Hurd
,
Lixia
Guo
,
Daniel
Lee
,
Mark
Warren
,
Sihai
Yang
Diamond Proposal Number(s):
[41123]
Abstract: The capture of xenon (Xe) and krypton (Kr) from the off-gas of used nuclear fuel is of great importance to the treatment of radioactive wastes and production of high purity Xe. Solid sorbents, in particular metal–organic frameworks (MOFs), show promise in gas capture. However, the unknown radiation resistance of MOFs has limited their development. Herein, the efficient capture and separation of Xe/Kr by MFM-520, which strikes a remarkable stability toward 1750 kilogray (kGy) γ-irradiation, is reported. Under ambient conditions, dynamic breakthrough experiments confirm the efficient separation performance, yielding a Xe capacity of 66 and 0.2 mg g−1 from a by-product of air separation (Xe/Kr: 20/80; v/v) and off-gas (Xe/Kr: 400/40 ppm balance in air), respectively. In situ synchrotron X-ray single crystal diffraction and solid-state nuclear magnetic resonance (ssNMR) studies reveal that the optimal micropore of MFM-520 underpins specific host-guest interactions to Xe, resulting in selective Xe capture.
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Oct 2025
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B18-Core EXAFS
I20-EDE-Energy Dispersive EXAFS (EDE)
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Wenyuan
Huang
,
Bing
An
,
Zeyu
Chen
,
Yu
Han
,
Yinlin
Chen
,
Jiangnan
Li
,
Xue
Han
,
Shaojun
Xu
,
Danielle
Crawshaw
,
Evan
Tillotson
,
Sarah J.
Haigh
,
Bing
Han
,
Christopher M. A.
Parlett
,
Luke
Keenan
,
Svemir
Rudic
,
Yongqiang
Cheng
,
Ben F.
Spencer
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[28575, 31729]
Open Access
Abstract: The development of earth-abundant metal-based catalysts is an important goal for the synthesis of fine chemicals. Here, an active nickel catalyst supported on a robust metal–organic framework, MFM-300(Cr), is reported which shows an exceptional performance for reductive amination, a reaction that has long been dominated by noble metals. Ni/MFM-300(Cr) promotes the synthesis of 38 primary amines via reductive amination of their parent carbonyl compounds, including biomass-derived aldehydes and ketones, using NH3 in the presence of H2 operating under relatively mild conditions (5 bar and 160 °C). X-ray absorption spectroscopy confirms the formation of mixtures of metallic Ni0 and Nin+ active sites, while in situ inelastic neutron scattering, coupled with modeling, reveals details of the mechanism of catalysis involving the formation of N-benzyl-1-phenylmethanediamine (BPDI) as an intermediate species in the generation of benzylamine. Cooperativity between Ni sites and MFM-300(Cr) creates an optimal microenvironment for the efficient activation of carbonyl compounds and the selective production of primary amines using a non-precious metal-based catalyst.
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Oct 2025
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B18-Core EXAFS
B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Boya
Tang
,
David
Brooks
,
Meng
He
,
Yinlin
Chen
,
Zhaozhao
Hu
,
Xue
Han
,
Jiangnan
Li
,
Siyu
Zhao
,
Jiarui
Fan
,
Yukun
Ye
,
Ivan
Da Silva
,
Cheng
Li
,
Zi
Wang
,
Lutong
Shan
,
Bing
Han
,
Weiyao
Li
,
Daniil
Polyukhov
,
Bing
An
,
Catherine
Dejoie
,
Martin
Wilding
,
Shaojun
Xu
,
Meredydd
Kippax-Jones
,
Zhaodong
Zhu
,
Yujie
Ma
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Sarah J.
Day
,
Stephen P.
Thompson
,
Mark D.
Frogley
,
Louise S.
Natrajan
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[37900, 37887, 36450]
Abstract: Photocatalytic synthesis of hydrogen peroxide (H2O2) from oxygen (O2) is a challenging process. Metal–organic framework (MOF) materials are emerging photocatalysts with potential tunable light absorption properties. Herein, we report a rhenium (Re) modified Zr-based MOF, Re10-MFM-67, in which active Re sites are incorporated into MFM-67 by partial replacement of 9,9′-bianthracene-10,10′-dicarboxylic acid (H2L1) with a [(H2L2)ReI(CO)3Cl] (H2L2 = 2,2′-bipyridine-5,5′-dicarboxylic acid) moiety. Re10-MFM-67 (10 refers to the molar percentage content of Re complex within the material) exhibits broadband light absorption with an exceptional rate of formation of H2O2 from O2 of 8.50 mmol gcat–1 h–1 and a record turnover frequency (TOF) of 28.7 h–1 under visible light irradiation (λ > 400 nm). Synchrotron powder X-ray diffraction (SPXRD) and neutron powder diffraction (NPD) confirm the structure of Re10-MFM-67, and together with extended X-ray absorption fine structure (EXAFS) analysis establish the coordination environment and binding of the [ReI(CO)3Cl] moiety within the framework structure. In situ electron paramagnetic resonance (EPR) spectroscopy suggests that photocatalytic H2O2 generation on Re10-MFM-67 occurs via a two-step oxygen reduction reaction (ORR) pathway with the superoxide anion formed as an intermediate. This study promotes the design of MOF-based photocatalysts with conjugated ligands for efficient photosynthesis.
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Jul 2025
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B18-Core EXAFS
B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Zhaodong
Zhu
,
Mengtian
Fan
,
Meng
He
,
Bing
An
,
Yinlin
Chen
,
Shaojun
Xu
,
Tianze
Zhou
,
Alena M.
Sheveleva
,
Meredydd
Kippax-Jones
,
Lutong
Shan
,
Yongqiang
Chen
,
Hamish
Cavaye
,
Jeff
Armstrong
,
Svemir
Rudic
,
Stewart F.
Parker
,
William
Thornley
,
Evan
Tillotson
,
Matthew
Lindley
,
Shenglong
Tian
,
Daniel
Lee
,
Shiyu
Fu
,
Mark D.
Frogley
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Sarah J.
Haigh
,
Sihai
Yang
Abstract: The methanol-to-olefins (MTO) process has the potential to bridge future gaps in the supply of sustainable lower olefins. Promoting the selectivity of propylene and ethylene and revealing the catalytic role of active sites are challenging goals in MTO reactions. Here, we report a novel heteroatomic silicoaluminophosphate (SAPO) zeolite, SAPO-34-Ta, which incorporates active tantalum(V) sites within the framework to afford an optimal distribution of acidity. SAPO-34-Ta exhibits a remarkable total selectivity of 85.8% for propylene and ethylene with a high selectivity of 54.9% for propylene on full conversion of methanol at 400 oC. In situ and operando synchrotron powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy and inelastic neutron scattering, coupled with theoretical calculations, reveal trimethyloxonium as the key reaction intermediate, promoting the formation of first carbon-carbon bonds in olefins. The tacit cooperation between tantalum(V) and Brønsted acid sites within SAPO-34 provides an efficient platform for selective production of lower olefins from methanol.
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Jan 2025
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I11-High Resolution Powder Diffraction
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Xinchen
Kang
,
Lili
Li
,
Hengan
Wang
,
Tian
Luo
,
Shaojun
Xu
,
Yinlin
Chen
,
Joseph H.
Carter
,
Zi
Wang
,
Alena M.
Sheveleva
,
Kai
Lyu
,
Xue
Han
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Chiu C.
Tang
,
Lifei
Liu
,
Buxing
Han
,
Emma K.
Gibson
,
C. Richard A.
Catlow
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[33115]
Open Access
Abstract: Catalytic cleavage of β-O-4 linkages is an essential but challenging step in the depolymerisation of lignin. Here, we report the templated electrosynthesis of a hydrophobic metal-organic polyhedral catalyst (Cu-MOP-e), which exhibits excellent hydrothermal stability and exceptional activity for this reaction. The oxidative cleavage of 2-phenoxyacetophenone, 1, a lignin model compound, over Cu-MOP-e at 90 oC for 1 h affords full conversion with yields of the monomer products phenol and benzoic acid of 99%. The reusability of Cu-MOP-e has been confirmed by carrying out ten cycles of reaction. The mechanism of catalyst-substrate binding has been investigated by high resolution synchrotron X-ray powder diffraction, in situ X-ray absorption spectroscopy, electron paramagnetic resonance spectroscopy and density functional theory calculations. The combination of optimal porosity and active Cu(II) sites provides confined binding of 2-phenoxyacetophenone, thus promoting the cleavage of β-O-4 linkage under relatively mild conditions.
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Dec 2024
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B22-Multimode InfraRed imaging And Microspectroscopy
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Dukula
De Alwis Jayasinghe
,
Yinlin
Chen
,
Jiangnan
Li
,
Justyna M.
Rogacka
,
Meredydd
Kippax-Jones
,
Wanpeng
Lu
,
Sergey
Sapchenko
,
Jinyue
Yang
,
Sarayute
Chansai
,
Tianze
Zhou
,
Lixia
Guo
,
Yujie
Ma
,
Longzhang
Dong
,
Daniil
Polyukhov
,
Lutong
Shan
,
Yu
Han
,
Danielle
Crawshaw
,
Xiangdi
Zeng
,
Zhaodong
Zhu
,
Lewis
Hughes
,
Mark D.
Frogley
,
Pascal
Manuel
,
Svemir
Rudic
,
Yongqiang
Chen
,
Christopher
Hardacre
,
Martin
Schroeder
,
Sihai
Yang
Open Access
Abstract: Ammonia (NH3) production in 2023 reached 150 million tons and is associated with potential concomitant production of up to 500 million tons of CO2 each year. Efforts to produce green NH3 are compromised since it is difficult to separate using conventional condensation chillers, but in situ separation with minimal cooling is challenging. While metal–organic framework materials offer some potential, they are often unstable and decompose in the presence of caustic and corrosive NH3. Here, we address these challenges by developing a pore-expansion strategy utilizing the flexible phosphonate framework, STA-12(Ni), which shows exceptional stability and capture of NH3 at ppm levels at elevated temperatures (100–220 °C) even under humid conditions. A remarkable NH3 uptake of 4.76 mmol g–1 at 100 μbar (equivalent to 100 ppm) is observed, and in situ neutron powder diffraction, inelastic neutron scattering, and infrared microspectroscopy, coupled with modeling, reveal a pore expansion from triclinic to a rhombohedral structure on cooperative binding of NH3 to unsaturated Ni(II) sites and phosphonate groups. STA-12(Ni) can be readily engineered into pellets or monoliths without losing adsorption capacity, underscoring its practical potential.
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Nov 2024
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Yu
Han
,
Wenyuan
Huang
,
Meng
He
,
Bing
An
,
Yinlin
Chen
,
Xue
Han
,
Lan
An
,
Meredydd
Kippax-Jones
,
Jiangnan
Li
,
Yuhang
Yang
,
Mark D.
Frogley
,
Cheng
Li
,
Danielle
Crawshaw
,
Pascal
Manuel
,
Svemir
Rudic
,
Yongqiang
Chen
,
Ian
Silverwood
,
Luke L.
Daemen
,
Anibal J.
Ramirez-Cuesta
,
Sarah J.
Day
,
Stephen P.
Thompson
,
Ben F.
Spencer
,
Marek
Nikiel
,
Daniel
Lee
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[37155, 36474]
Open Access
Abstract: Capture of trace benzene is an important and challenging task. Metal–organic framework materials are promising sorbents for a variety of gases, but their limited capacity towards benzene at low concentration remains unresolved. Here we report the adsorption of trace benzene by decorating a structural defect in MIL-125-defect with single-atom metal centres to afford MIL-125-X (X = Mn, Fe, Co, Ni, Cu, Zn; MIL-125, Ti8O8(OH)4(BDC)6 where H2BDC is 1,4-benzenedicarboxylic acid). At 298 K, MIL-125-Zn exhibits a benzene uptake of 7.63 mmol g−1 at 1.2 mbar and 5.33 mmol g−1 at 0.12 mbar, and breakthrough experiments confirm the removal of trace benzene (from 5 to <0.5 ppm) from air (up to 111,000 min g−1 of metal–organic framework), even after exposure to moisture. The binding of benzene to the defect and open Zn(II) sites at low pressure has been visualized by diffraction, scattering and spectroscopy. This work highlights the importance of fine-tuning pore chemistry for designing adsorbents for the removal of air pollutants.
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Nov 2024
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Yu
Han
,
David
Brooks
,
Meng
He
,
Yinlin
Chen
,
Wenyuan
Huang
,
Boya
Tang
,
Bing
An
,
Xue
Han
,
Meredydd
Kippax-Jones
,
Mark D.
Frogley
,
Sarah J.
Day
,
Stephen P.
Thompson
,
Svemir
Rudic
,
Yongqiang
Chen
,
Luke L.
Daemen
,
Anibal J.
Ramirez-Cuesta
,
Catherine
Dejoie
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[33115, 30398]
Open Access
Abstract: The functionalization of metal–organic frameworks (MOFs) to enhance the adsorption of benzene at trace levels remains a significant challenge. Here, we report the exceptional adsorption of trace benzene in a series of zirconium-based MOFs functionalized with chloro groups. Notably, MFM-68-Cl2, constructed from an anthracene linker incorporating chloro groups, exhibits a remarkable benzene uptake of 4.62 mmol g–1 at 298 K and 0.12 mbar, superior to benchmark materials. In situ synchrotron X-ray diffraction, Fourier transform infrared microspectroscopy, and inelastic neutron scattering, coupled with density functional theory modeling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between chloro-groups, the optimized pore size, aromatic functionality, and the flexibility of the linkers in response to benzene uptake in MFM-68-Cl2. This study represents the first example of enhanced adsorption of trace benzene promoted by −CH···Cl and Cl···π interactions in porous materials.
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Oct 2024
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B22-Multimode InfraRed imaging And Microspectroscopy
I15-1-X-ray Pair Distribution Function (XPDF)
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Wanpeng
Lu
,
Yinlin
Chen
,
Zi
Wang
,
Jin
Chen
,
Yujie
Ma
,
Weiyao
Li
,
Jiangnan
Li
,
Meng
He
,
Mengtian
Fan
,
Alena M.
Sheveleva
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Mark D.
Frogley
,
Philip A.
Chater
,
Catherine
Dejoie
,
Martin
Schroder
,
Sihai
Yang
,
Lixia
Guo
Open Access
Abstract: The development of materials for ammonia (NH3) storage is an important and challenging task. Here, we report the high NH3 uptake in a series of copper-carboxylate materials, namely MFM-100, MFM-101, MFM-102, MFM-126, MFM-127, MFM-190(F), MFM-170, and Cu-MOP-1a. At 273 K and 1 bar, MFM-101 shows an exceptional uptake of 21.9 mmol g−1. X-ray pair distribution function analysis reveals an unusual crystalline-amorphous-crystalline phase transition for the isoreticular MFM-100, MFM-101 and MFM-102 upon adsorption and desorption of NH3 followed by regeneration in water. In situ X-ray diffraction, synchrotron infrared micro-spectroscopy, and electron paramagnetic resonance spectroscopy are employed to elucidate the presence of strong Cu(II)⋯NH3 interactions and changes in coordination at the [Cu2(O2CR)4] (R = di-, tri-, and tetra-phenyl ligands) paddlewheel.
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Sep 2024
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