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65 items found (0 items not approved), displaying 1 to 10.[First/Prev] 1, 2, 3, 4, 5, 6, 7 [Next/Last]

Instruments / Technical Area	Publication Details	Published
I11-High Resolution Powder Diffraction	Construction of C-C bonds via photoreductive coupling of ketones and aldehydes in the metal-organic-framework MFM-300(Cr) Tian Luo , Lili Li , Yinlin Chen , Jie An , Chengcheng Liu , Zheng Yan , Joseph H. Carter , Xue Han , Alena M. Sheveleva , Floriana Tuna , Eric J. L. Mcinnes , Chiu C. Tang , Martin Schroeder , Sihai Yang Nature Communications 12 DOI: 10.1038/s41467-021-23302-w Diamond Proposal Number(s): [15972] Open Access Show Abstract ▼ Abstract: Construction of C-C bonds via reductive coupling of aldehydes and ketones is hindered by the highly negative reduction potential of these carbonyl substrates, particularly ketones, and this renders the formation of ketyl radicals extremely endergonic. Here, we report the efficient activation of carbonyl compounds by the formation of specific host-guest interactions in a hydroxyl-decorated porous photocatalyst. MFM-300(Cr) exhibits a band gap of 1.75 eV and shows excellent catalytic activity and stability towards the photoreductive coupling of 30 different aldehydes and ketones to the corresponding 1,2-diols at room temperature. Synchrotron X-ray diffraction and electron paramagnetic resonance spectroscopy confirm the generation of ketyl radicals via confinement within MFM-300(Cr). This protocol removes simultaneously the need for a precious metal-based photocatalyst or for amine-based sacrificial agents for the photochemical synthesis.	Jun 2021
I11-High Resolution Powder Diffraction	The origin of catalytic benzylic C‐H oxidation over a redox‐active metal‐organic framework Martin Schroeder , Louis Kimberley , Alena M. Sheveleva , Jiangnan Li , Joseph H. Carter , Xinchen Kang , Gemma L. Smith , Xue Han , Sarah J. Day , Chiu C. Tang , Floriana Tuna , Eric J. L. Mcinnes , Sihai Yang Angewandte Chemie International Edition DOI: 10.1002/anie.202102313 Show Abstract ▼ Abstract: Selective oxidation of benzylic C‐H compounds to ketones is important for the production of a wide range of fine chemicals, and is often achieved using toxic or precious metals catalysts. Here, we report the efficient oxidation of benzylic C‐H groups in a broad range of substrates under mild conditions over a robust metal‐organic framework material, MFM‐170, incorporating redox‐active [Cu2II(O2CR)4] paddlewheel nodes. A comprehensive investigation employing electron paramagnetic resonance (EPR) spectroscopy and synchrotron X‐ray diffraction has identified the critical role of the paddlewheel moiety in activating the oxidant tBuOOH (t‐butyl hydroperoxide) via partial reduction to [CuIICuI(O2CR)4] species.	Apr 2021
I11-High Resolution Powder Diffraction I19-Small Molecule Single Crystal Diffraction	Exceptional packing density of ammonia in a dual-functionalized metal–organic framework Christopher Marsh , Xue Han , Jiangnan Li , Zhenzhong Lu , Stephen Argent , Ivan Da Silva , Yongqiang Cheng , Luke L. Daemen , Anibal J. Ramirez-Cuesta , Stephen P. Thompson , Alexander J. Blake , Sihai Yang , Martin Schroeder Journal Of The American Chemical Society 361 DOI: 10.1021/jacs.1c01749 Diamond Proposal Number(s): [23483, 11622] Open Access Show Abstract ▼ Abstract: We report the reversible adsorption of ammonia (NH3) up to 9.9 mmol g–1 in a robust Al-based metal–organic framework, MFM-303(Al), which is functionalized with free carboxylic acid and hydroxyl groups. The unique pore environment decorated with these acidic sites results in an exceptional packing density of NH3 at 293 K (0.801 g cm–3) comparable to that of solid NH3 at 193 K (0.817 g cm–3). In situ synchrotron X-ray diffraction and inelastic neutron scattering reveal the critical role of free −COOH and −OH groups in immobilizing NH3 molecules. Breakthrough experiments confirm the excellent performance of MFM-303(Al) for the capture of NH3 at low concentrations under both dry and wet conditions.	Apr 2021
I11-High Resolution Powder Diffraction I20-EDE-Energy Dispersive EXAFS (EDE)	Control of zeolite microenvironment for propene synthesis from methanol Longfei Lin , Mengtian Fan , Alena M. Sheveleva , Xue Han , Zhimou Tang , Joseph H. Carter , Ivan Da Silva , Christopher Parlett , Floriana Tuna , Eric J. L. Mcinnes , German Sastre , Svemir Rudic , Hamish Cavaye , Stewart F. Parker , Yongqiang Cheng , Luke L. Daemen , Anibal J. Ramirez-Cuesta , Martin P. Attfield , Yueming Liu , Chiu C. Tang , Buxing Han , Sihai Yang Nature Communications 12 DOI: 10.1038/s41467-021-21062-1 Diamond Proposal Number(s): [2359] Open Access Show Abstract ▼ Abstract: Optimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.	Feb 2021
B18-Core EXAFS B22-Multimode InfraRed imaging And Microspectroscopy I11-High Resolution Powder Diffraction	Catalytic decomposition of NO2 over a copper-decorated metal–organic framework by non-thermal plasma Shaojun Xu , Xue Han , Yujie Ma , Thien D. Duong , Longfei Lin , Emma K. Gibson , Alena Sheveleva , Sarayute Chansai , Alex Walton , Duc-The Ngo , Mark D. Frogley , Chiu C. Tang , Floriana Tuna , Eric J. L. Mcinnes , C. Richard A. Catlow , Christopher Hardacre , Sihai Yang , Martin Schroeder Cell Reports Physical Science 3 DOI: 10.1016/j.xcrp.2021.100349 Open Access Show Abstract ▼ Abstract: Efficient catalytic conversion of NO2 to non-harmful species remains an important target for research. State-of-the-art deNOx processes are based upon ammonia (NH3)-assisted selective catalytic reduction (NH3-SCR) over Cu-exchanged zeolites at elevated temperatures. Here, we describe a highly efficient non-thermal plasma (NTP) deNOx process catalyzed by a Cu-embedded metal-organic framework, Cu/MFM-300(Al), at room temperature. Under NTP activation at 25°C, Cu/MFM-300(Al) enables direct decomposition of NO2 into N2, NO, N2O, and O2 without the use of NH3 or other reducing agents. NO2 conversion of 96% with a N2 selectivity of 82% at a turnover frequency of 2.9 h−1 is achieved, comparable to leading NH3-SCR catalysts that use NH3 operating at 250°C–550°C. The mechanism for the rate-determining step (NO→N2) is elucidated by in operando diffuse reflectance infrared Fourier transform spectroscopy, and electron paramagnetic resonance spectroscopy confirms the formation of Cu2+⋯NO nitrosylic adducts on Cu/MFM-300(Al), which facilitates NO dissociation and results in the notable N2 selectivity.	Feb 2021
B22-Multimode InfraRed imaging And Microspectroscopy	High ammonia adsorption in MFM-300 materials: Dynamics and charge transfer in host–guest binding Xue Han , Wanpeng Lu , Yinlin Chen , Ivan Da Silva , Jiangnan Li , Longfei Lin , Weiyao Li , Alena M. Sheveleva , Harry G. W. Godfrey , Zhenzhong Lu , Floriana Tuna , Eric J. L. Mcinnes , Yongqiang Cheng , Luke L. Daemen , Laura J. Mccormick Mcpherson , Simon J. Teat , Mark D. Frogley , Svemir Rudic , Pascal Manuel , Anibal J. Ramirez-Cuesta , Sihai Yang , Martin Schroeder Journal Of The American Chemical Society DOI: 10.1021/jacs.0c11930 Diamond Proposal Number(s): [23782] Show Abstract ▼ Abstract: Ammonia (NH3) is a promising energy resource owing to its high hydrogen density. However, its widespread application is restricted by the lack of efficient and corrosion-resistant storage materials. Here, we report high NH3 adsorption in a series of robust metal–organic framework (MOF) materials, MFM-300(M) (M = Fe, V, Cr, In). MFM-300(M) (M = Fe, VIII, Cr) show fully reversible capacity for >20 cycles, reaching capacities of 16.1, 15.6, and 14.0 mmol g–1, respectively, at 273 K and 1 bar. Under the same conditions, MFM-300(VIV) exhibits the highest uptake among this series of MOFs of 17.3 mmol g–1. In situ neutron powder diffraction, single-crystal X-ray diffraction, and electron paramagnetic resonance spectroscopy confirm that the redox-active V center enables host–guest charge transfer, with VIV being reduced to VIII and NH3 being oxidized to hydrazine (N2H4). A combination of in situ inelastic neutron scattering and DFT modeling has revealed the binding dynamics of adsorbed NH3 within these MOFs to afford a comprehensive insight into the application of MOF materials to the adsorption and conversion of NH3.	Feb 2021
B22-Multimode InfraRed imaging And Microspectroscopy I11-High Resolution Powder Diffraction	Binding and separation of CO2, SO2 and C2H2 in homo- and hetero-metallic metal-organic framework materials Lydia Briggs , Ruth Newby , Xue Han , Christopher Morris , Mathew Savage , Cristina Perez , Timothy L. Easun , Mark Frogley , Gianfelice Cinque , Claire A. Murray , Chiu C. Tang , Sihai Yang , Junliang Sun , Martin Schroeder Journal Of Materials Chemistry A DOI: 10.1039/D1TA00687H Diamond Proposal Number(s): [22137, 22138] Open Access Show Abstract ▼ Abstract: We report the adsorption of C2H2, CO2 and SO2 in a new, ultra-stable Cr(III)-based MOF, MFM-300(Cr), {[Cr2(OH)2(L)], H4L = biphenyl-3,3',5,5'-tetracarboxylic acid}. MFM-300(Cr) shows uptakes of 7.37, 7.73 and 8.59 mmol g-1 for CO2, C2H2 and SO2, respectively, at 273 K, 1.0 bar, and shows a higher selectivity for SO2/CO2 compared with the Al(III) analogue MFM-300(Al) (selectivity of 79 vs. 45). In order to monitor the effects of changing metal centre on gas uptake and to integrate the properties of the homometallic analogues, the mixed metal MFM-300(Al0.67Cr0.33), [Al1.34Cr0.66(OH)2L] has been synthesised. In situ synchrotron micro-FTIR spectroscopy has identified distinct CO2 binding environments on Al-O(H)-Al, Cr-O(H)-Cr and Al-O(H)-Cr bridges in MFM-300(Al0.67Cr0.33), and we have determined the binding domains for these gases by in situ synchrotron X-ray diffraction in both MFM-300(Cr) and MFM-300(Al0.67Cr0.33). The capability of these materials for gas separation has been confirmed by dynamic breakthrough experiments. The incorporation of Al(III) and Cr(III) within the same framework allows tuning of the host-guest and guest-guest interactions within these functional porous materials.	Feb 2021
I19-Small Molecule Single Crystal Diffraction	Selective gas uptake and rotational dynamics in a (3,24)-connected metal–organic framework material William J. F. Trenholme , Daniil I. Kolokolov , Michelle Bound , Stephen P. Argent , Jamie A. Gould , Jiangnan Li , Sarah A. Barnett , Alexander J. Blake , Alexander G. Stepanov , Elena Besley , Timothy L. Easun , Sihai Yang , Martin Schroeder Journal Of The American Chemical Society 71 DOI: 10.1021/jacs.0c11202 Show Abstract ▼ Abstract: The desolvated (3,24)-connected metal–organic framework (MOF) material, MFM-160a, [Cu3(L)(H2O)3] [H6L = 1,3,5-triazine-2,4,6-tris(aminophenyl-4-isophthalic acid)], exhibits excellent high-pressure uptake of CO2 (110 wt% at 20 bar, 298 K) and highly selective separation of C2 hydrocarbons from CH4 at 1 bar pressure. Henry’s law selectivities of 79:1 for C2H2:CH4 and 70:1 for C2H4:CH4 at 298 K are observed, consistent with ideal adsorption solution theory (IAST) predictions. Significantly, MFM-160a shows a selectivity of 16:1 for C2H2:CO2. Solid-state 2H NMR spectroscopic studies on partially deuterated MFM-160-d12 confirm an ultra-low barrier (∼2 kJ mol–1) to rotation of the phenyl group in the activated MOF and a rotation rate 5 orders of magnitude slower than usually observed for solid-state materials (1.4 × 106 Hz cf. 1011–1013 Hz). Upon introduction of CO2 or C2H2 into desolvated MFM-160a, this rate of rotation was found to increase with increasing gas pressure, a phenomenon attributed to the weakening of an intramolecular hydrogen bond in the triazine-containing linker upon gas binding. DFT calculations of binding energies and interactions of CO2 and C2H2 around the triazine core are entirely consistent with the 2H NMR spectroscopic observations.	Feb 2021
I11-High Resolution Powder Diffraction	Enhanced proton conductivity in a flexible metal-organic framework promoted by single-crystal-to-single-crystal transformation Xi Chen , Zhongyue Zhang , Jin Chen , Sergei Sapchenko , Xue Han , Ivan Da Silva , Ming Li , Inigo Vitorica-Yrezabal , George Whitehead , Chiu C. Tang , Kunio Awaga , Sihai Yang , Martin Schroeder Chemical Communications DOI: 10.1039/D0CC05270A Diamond Proposal Number(s): [22138] Show Abstract ▼ Abstract: MFM-722(Pb)-DMA undergoes a single-crystal-to-single-crystal (SCSC) transformation to give MFM-722(Pb)-H2O via ligand substitution upon exposure to water vapour. In situ single crystal impedance spectroscopy reveals an increase in proton conductivity due to this structural transition, with MFM-722(Pb)-H2O showing a proton conductivity of 6.61×10-4 S cm-1 at 50 °C and 98% RH. The low activation energy (Ea = 0.21 eV) indicates that the proton conduction follows a Grotthuss mechanism.	Nov 2020
I11-High Resolution Powder Diffraction I19-Small Molecule Single Crystal Diffraction	Porous metal–organic polyhedra: morphology, porosity, and guest binding Stephen P. Argent , Ivan Da Silva , Alex Greenaway , Mathew Savage , Jack Humby , Andrew J. Davies , Harriott Nowell , William Lewis , Pascal Manuel , Chiu C. Tang , Alexander J. Blake , Michael W. George , Alexander V. Markevich , Elena Besley , Sihai Yang , Neil R. Champness , Martin Schroeder Inorganic Chemistry DOI: 10.1021/acs.inorgchem.0c01935 Diamond Proposal Number(s): [861, 11622, 15833, 9443] Open Access Show Abstract ▼ Abstract: Designing porous materials which can selectively adsorb CO2 or CH4 is an important environmental and industrial goal which requires an understanding of the host–guest interactions involved at the atomic scale. Metal–organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family of MOPs (Cu-1a, Cu-1b, Cu-2), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra. Thus, for Cu-1a, the void fraction outside the cages totals 56% with only 2% within. The relative stabilities of these MOP structures are rationalized by considering their weak nondirectional packing interactions using Hirshfeld surface analyses. The exceptional stability of Cu-1a enables a detailed structural investigation into the adsorption of CO2 and CH4 using in situ X-ray and neutron diffraction, coupled with DFT calculations. The primary binding sites for adsorbed CO2 and CH4 in Cu-1a are found to be the open metal sites and pockets defined by the faces of phenyl rings. More importantly, the structural analysis of a hydrated sample of Cu-1a reveals a strong hydrogen bond between the adsorbed CO2 molecule and the Cu(II)-bound water molecule, shedding light on previous empirical and theoretical observations that partial hydration of metal−organic framework (MOF) materials containing open metal sites increases their uptake of CO2. The results of the crystallographic study on MOP–gas binding have been rationalized using DFT calculations, yielding individual binding energies for the various pore environments of Cu-1a.	Oct 2020

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