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
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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
,
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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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[26090]
Open Access
Abstract: Reorientational dynamics in solid electrolytes can significantly enhance the ionic conductivity, and understanding these dynamics can facilitate the rational design of improved solid electrolytes. Additionally, recent investigations on metal hydridoborate-based solid electrolytes have shown that the addition of a neutral ligand can also have a positive effect on the ionic conductivity. In this study, we investigate the dynamics in monomethylamine magnesium borohydride (Mg(BH4)2·CH3NH2) with quasielastic and inelastic neutron scattering, density functional theory calculations, and molecular dynamics simulations. The results suggest that the addition of methylamine significantly speeds up the reorientational frequency of the BH4– anion compared to Mg(BH4)2. This is likely part of the explanation for the high Mg-ion transport observed for Mg(BH4)2·CH3NH2. Furthermore, while the dynamics of both the BH4– anion and the CH3 group of the methylamine ligand is rapid, the NH2 group of the methylamine ligand exhibits much slower reorientations, as confirmed by both experimental and computational investigations. Notably, molecular dynamics calculations reveal mean square displacements of 0.387 Å2 for NH2, 1.503 Å2 for CH3, and 1.856 Å2 for BH4– using a trajectory of 10 ps. This study confirms the simultaneous presence of fast dynamics and high ionic conductivity in a metal borohydride-based system and can function as an experimental foundation for future studies on dynamics in hydrogen-rich solid electrolytes.
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Sep 2024
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
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Lutong
Shan
,
Yujie
Ma
,
Shaojun
Xu
,
Meng
Zhou
,
Meng
He
,
Alena M.
Sheveleva
,
Rongsheng
Cai
,
Daniel
Lee
,
Yongqiang
Chen
,
Boya
Tang
,
Bing
Han
,
Yinlin
Chen
,
Lan
An
,
Tianze
Zhou
,
Martin
Wilding
,
Alexander S.
Eggeman
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Sarah J.
Day
,
Stephen P.
Thompson
,
Sarah J.
Haigh
,
Xinchen
Kang
,
Buxing
Han
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[33115, 31729]
Open Access
Abstract: The design and preparation of efficient catalysts for ammonia production under mild conditions is a desirable but highly challenging target. Here, we report a series of single-atom catalysts [M-SACs, M = Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Mo(II)] derived from UiO-66 containing structural defects and their application to electrochemical reduction of nitrate (NO3-) to ammonia (NH3). Cu-SAC and Fe-SAC exhibit remarkable yield rates for NH3 production of 30.0 and 29.0 mg h−1 cm−2, respectively, with a high Faradaic efficiency (FENH3) of over 96% at −1.0 V versus the reversible hydrogen electrode. Importantly, their catalytic performance can be retained in various simulated wastewaters. Complementary experiments confirmed the nature of single-atom sites within these catalysts and the binding domains of NO3- in UiO-66-Cu. In situ spectroscopic techniques, coupled with density functional theory calculations confirm the strong binding of NO3- and the formation of reaction intermediates, thus facilitating the catalytic conversion to NH3.
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Jun 2024
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B22-Multimode InfraRed imaging And Microspectroscopy
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Xiangbing
Zeng
,
Jiangnan
Li
,
Meng
He
,
Wanpeng
Lu
,
Danielle
Crawshaw
,
Lixia
Guo
,
Yujie
Ma
,
Meredydd
Kippax-Jones
,
Yongqiang
Cheng
,
Pascal
Manuel
,
Svemir
Rudic
,
Mark D.
Frogley
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[30398]
Open Access
Abstract: We report the high adsorption of NH3 in the titanium-based metal-organic framework, MFM-300(Ti), comprising extended [TiO6]∞ chains linked by biphenyl-3,3’,5,5’-tetracarboxylate ligands. At 273 K and 1 bar, MFM-300(Ti) shows an exceptional NH3 uptake of 23.4 mmol g–1 with a record-high packing density of 0.84 g cm–3. Dynamic breakthrough experiments confirm the excellent uptake and separation of NH3 at low concentration (1000 ppm). The combination of in situ neutron powder diffraction and spectroscopic studies reveal strong, yet reversible binding interactions of NH3 to the framework oxygen sites.
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Apr 2024
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I11-High Resolution Powder Diffraction
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Martin
Schroeder
,
Christopher
Marsh
,
Xue
Han
,
Zhenzhong
Lu
,
Ivan
Da Silva
,
Yongqiang
Chen
,
Luke L.
Daemen
,
Sarah J.
Day
,
Stephen P.
Thompson
,
Anibal Javier
Ramirez-Cuesta
,
Sihai
Yang
Open Access
Abstract: The functionalisation of organic linkers in metal-organic frameworks (MOFs) to improve gas uptake is well-documented. Although the positive role of free carboxylic acid sites in MOFs for binding gas molecules has been proposed in computational studies, relatively little experimental evidence has been reported in support of this. Primarily this is because of the inherent synthetic difficulty to prepare MOF materials bearing free, accessible –COOH moieties which would normally bind to metal ions within the framework structure. Here, we describe the direct binding of CO2 and C2H2 molecules to the free -COOH sites within the pores of MFM-303(Al). MFM-303(Al) exhibits highly selective adsorption of CO2 and C2H2 with a high selectivity for C2H2 over C2H4. In situ synchrotron X-ray diffraction and inelastic neutron scattering, coupled with modelling, highlight the cooperative interactions of adsorbed CO2 and C2H2 molecules with free -COOH and -OH sites within MFM-303(Al), thus rationalising the observed high selectivity for gas separation.
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Apr 2024
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B07-B1-Versatile Soft X-ray beamline: High Throughput ES1
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Ziyu
Cen
,
Xue
Han
,
Longfei
Lin
,
Sihai
Yang
,
Wanying
Han
,
Weilong
Wen
,
Wenli
Yuan
,
Minghua
Dong
,
Zhiye
Ma
,
Fang
Li
,
Yubin
Ke
,
Juncai
Dong
,
Jin
Zhang
,
Shuhu
Liu
,
Jialiang
Li
,
Qian
Li
,
Ningning
Wu
,
Junfeng
Xiang
,
Hao
Wu
,
Lile
Cai
,
Yanbo
Hou
,
Yongqiang
Chen
,
Luke L.
Daemen
,
Anibal J.
Ramirez-Cuesta
,
Pilar
Ferrer
,
David C.
Grinter
,
Georg
Held
,
Yueming
Liu
,
Buxing
Han
Diamond Proposal Number(s):
[33962]
Open Access
Abstract: Conversion of plastic wastes to valuable carbon resources without using noble metal catalysts or external hydrogen remains a challenging task. Here we report a layered self-pillared zeolite that enables the conversion of polyethylene to gasoline with a remarkable selectivity of 99% and yields of >80% in 4 h at 240 °C. The liquid product is primarily composed of branched alkanes (selectivity of 72%), affording a high research octane number of 88.0 that is comparable to commercial gasoline (86.6). In situ inelastic neutron scattering, small-angle neutron scattering, solid-state nuclear magnetic resonance, X-ray absorption spectroscopy and isotope-labelling experiments reveal that the activation of polyethylene is promoted by the open framework tri-coordinated Al sites of the zeolite, followed by β-scission and isomerization on Brönsted acids sites, accompanied by hydride transfer over open framework tri-coordinated Al sites through a self-supplied hydrogen pathway to yield selectivity to branched alkanes. This study shows the potential of layered zeolite materials in enabling the upcycling of plastic wastes.
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Apr 2024
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B18-Core EXAFS
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Yujie
Ma
,
Xue
Han
,
Shaojun
Xu
,
Zhe
Li
,
Wanpeng
Lu
,
Bing
An
,
Daniel
Lee
,
Sarayute
Chansai
,
Alena M.
Sheveleva
,
Zi
Wang
,
Yinlin
Chen
,
Jiangnan
Li
,
Weiyao
Li
,
Rongsheng
Cai
,
Ivan
Da Silva
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Lewis
Hughes
,
Pascal
Manuel
,
Anibal J.
Ramirez-Cuesta
,
Sarah J.
Haigh
,
Christopher
Hardacre
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[19850]
Open Access
Abstract: Conversion of methane (CH4) to ethylene (C2H4) and/or acetylene (C2H2) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH4 controllably, and separating C2+ products from unreacted CH4 can be challenging. Here, we report the direct conversion of CH4 to C2H4 and C2H2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal–organic framework material, MFM-300(Fe). The selectivity for the formation of C2H4 and C2H2 reaches 96% with a high time yield of 334 μmol gcat–1 h–1. At a conversion of 10%, the selectivity to C2+ hydrocarbons and time yield exceed 98% and 2056 μmol gcat–1 h–1, respectively, representing a new benchmark for conversion of CH4. In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe–O(H)–Fe sites in activating CH4 and stabilizing reaction intermediates via the formation of an Fe–O(CH3)–Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C2H4 and C2H2 from unreacted CH4 for direct use. Integrating the processes of CH4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.
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Sep 2023
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I11-High Resolution Powder Diffraction
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Zi
Wang
,
Alena M.
Sheveleva
,
Daniel
Lee
,
Yinlin
Chen
,
Dinu
Iuga
,
W. Trent
Franks
,
Yujie
Ma
,
Jiangnan
Li
,
Lei
Li
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Sarah J.
Day
,
Anibal J.
Ramirez-Cuesta
,
Bing
Han
,
Alexander S.
Eggeman
,
Eric J. L.
Mcinnes
,
Floriana
Tuna
,
Sihai
Yang
,
Martin
Schroeder
Open Access
Abstract: We report the modulation of reactivity of nitrogen dioxide (NO2) in a charged metal-organic framework (MOF) material, MFM-305-CH3 in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl− ions in the pores. Uptake of NO2 into MFM-305-CH3 leads to reaction between NO2 and Cl– to give nitrosyl chloride (NOCl) and NO3− anions. A high dynamic uptake of 6.58 mmol g−1 at 298 K is observed for MFM-305-CH3 as measured using a flow of 500 ppm NO2 in He. In contrast, the analogous neutral material, MFM-305, shows a much lower uptake of 2.38 mmol g−1. The binding domains and reactivity of adsorbed NO2 molecules within MFM-305-CH3 and MFM-305 have been probed using in situ synchrotron X-ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high-field solid-state nuclear magnetic resonance and UV-vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.
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Apr 2023
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