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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B22-Multimode InfraRed imaging And Microspectroscopy
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Wenling
Zhao
,
Jiangnan
Li
,
Ke
Li
,
Jiapeng
Jiao
,
Shiqiang
Liu
,
Jiahao
Yang
,
Mark D.
Frogley
,
Yaguang
Peng
,
Yiyong
Wang
,
Hengan
Wang
,
Shipeng
Zhang
,
Lihong
Jing
,
Chengcheng
Liu
,
Sihai
Yang
,
Xinchen
Kang
,
Buxing
Han
Abstract: Photoreduction of CO2 is often hindered by the sluggish kinetics for its activation. Refinement of host–guest interactions is an effective strategy to overcome this barrier. Here, we report the immobilization of active Co(II) sites within a covalent-organic framework (COF) with a one-dimensional (1D) chain structure, Co-PyPDA-COF, which demonstrates a remarkable CO generation rate of 30.5 mmol g−1 h−1 and a high CO selectivity of 95.8% in 2 h for CO2 photoreduction at room temperature. The pore size of Co-PyPDA-COF is comparable to the diameter of CO2, which allows simultaneous interaction of a single CO2 molecule with the two Co(II) sites. The enhanced interaction result in increased local CO2 pressure, limited CO2 diffusion after adsorption, shortened distance for photoelectron transfer, and reduced energy barrier for the rate-determining step in CO2 reduction, promoting CO2 activation and conversion. This work opens a new way to design efficient catalysts by optimizing the pore size of the host.
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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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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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B22-Multimode InfraRed imaging And Microspectroscopy
I19-Small Molecule Single Crystal Diffraction
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Open Access
Abstract: The latest developments in acoustic technology and their integration of standing waves offers the potential to eject and trap tiny amounts of both liquid and solids with precision and stability in free space. This is appealing for experimenters at Light Sources who are traditionally relying on the use of containers or on the manual attachment of the samples to solid supports for analysis with X rays or IR. Here we present a brief overview of applications of acoustics and levitation for sample manipulation and delivery currently under investigation at Diamond Light source.
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May 2025
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B18-Core EXAFS
B22-Multimode InfraRed imaging And Microspectroscopy
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Wanpeng
Lu
,
Claudia E.
Tait
,
Gokay
Avci
,
Xian'E
Li
,
Agamemnon E.
Crumpton
,
Paul
Shao
,
Catherine M.
Aitchison
,
Fabien
Ceugniet
,
Yuyun
Yao
,
Mark D.
Frogley
,
Donato
Decarolis
,
Nan
Yao
,
Kim E.
Jelfs
,
Iain
Mcculloch
Open Access
Abstract: With the pressing urgency to reduce carbon footprint, photocatalytic carbon dioxide reduction has attracted growing attention as a sustainable mitigating option. Considering the important role of catalytic active sites (CASs) in the catalytic processes, control and design of the density and environment of CASs could enhance the catalyst performance. Herein, we report a novel metal–covalent organic framework (MCOF), MCOF-Co-315, featuring earth-abundant Co cocatalysts and conjugation through a covalently bonded backbone. MCOF-Co-315 showed a CO production rate of 1616 μmol g–1 h–1 utilizing Ru(bpy)3Cl2 as photosensitizer and triethanolamine (TEOA) as sacrificial electron donor with a 1.5 AM filter, vis mirror module (390–740 nm), and irradiation intensity adjusted to 1 sun and an especially outstanding apparent quantum yield (AQY) of 9.13% at 450 nm. The photocatalytic reaction was studied with electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge structure (XANES), and in situ synchrotron Fourier Transform Infrared (FT-IR) spectroscopy, and an underlying mechanism is proposed.
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Mar 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
Open Access
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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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
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Diamond Proposal Number(s):
[27207]
Open Access
Abstract: There is cumulative evidence that lipid metabolism plays a key role in the pathogenesis of various neurodegenerative disorders including Alzheimer’s disease (AD). Visualising lipid content in a non-destructive label-free manner can aid in elucidating the AD phenotypes towards a better understanding of the disease. In this study, we combined multiple optical molecular-specific methods, Fourier transform infrared (FTIR) spectroscopic imaging, synchrotron radiation-infrared (SR-IR) microscopy, Raman and stimulated Raman scattering (SRS) microscopy, and optical-photothermal infrared (O-PTIR) microscopy with multivariate data analysis, to investigate the biochemistry of brain hippocampus in situ using a mouse model of tauopathy (rTg4510). We observed a significant difference in the morphology and lipid content between transgenic (TG) and wild type (WT) samples. Immunohistochemical staining revealed some degree of microglia co-localisation with elevated lipids in the brain. These results provide new evidence of tauopathy-related dysfunction in a preclinical study at a subcellular level.
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Oct 2024
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