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26 items found (0 items not approved), displaying 1 to 10.[First/Prev] 1, 2, 3 [Next/Last]

Instruments / Technical Area	Publication Details	Published
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
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
	Investigations of carbon nitride-supported MN3O4 oxide nanoparticles for ORR Alexander I. Large , Sebastian Wahl , Salvatore Abate , Ivan Da Silva , Juan Jose Delgado Jaen , Nicola Pinna , Georg Held , Rosa Arrigo Catalysts 10 DOI: 10.3390/catal10111289 Open Access Show Abstract ▼ Abstract: Earth-abundant Mn-based oxide nanoparticles are supported on carbon nitride using two different immobilization methods and tested for the oxygen reduction reaction. Compared to the metal free CN, the immobilization of Mn oxide enhances not only the electrocatalytic activity but also the selectivity towards the 4e- reduction reaction of O2 to H2O. The XPS analysis reveals the interaction of the pyridine N species with Mn3O4 nanoparticles being particularly beneficial. This interaction is realized—although to a limited extent—when preparing the catalysts via impregnation; via the oleic acid route it is not observed. Whilst this work shows the potential of these systems to catalyze the ORR, the main limiting factor is still the poor conductivity of the support which leads to overpotential.	Nov 2020
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
B22-Multimode InfraRed imaging And Microspectroscopy I11-High Resolution Powder Diffraction	Refinement of pore size at sub-angstrom precision in robust metal–organic frameworks for separation of xylenes Xiaolin Li , Juehua Wang , Xinran Zhang , Xue Han , Ivan Da Silva , Christopher G. Morris , Shaojun Xu , Damian M. Wilary , Yinyong Sun , Yongqiang Cheng , Claire A. Murray , Chiu C. Tang , Mark D. Frogley , Gianfelice Cinque , Tristan Lowe , Haifei Zhang , Anibal J. Ramirez-cuesta , K. Mark Thomas , Leslie W. Bolton , Sihai Yang , Martin Schroeder , Nannan Bai Nature Communications 11 DOI: 10.1038/s41467-020-17640-4 Diamond Proposal Number(s): [13247] Open Access Show Abstract ▼ Abstract: The demand for xylenes is projected to increase over the coming decades. The separation of xylene isomers, particularly p- and m-xylenes, is vital for the production of numerous polymers and materials. However, current state-of-the-art separation is based upon fractional crystallisation at 220 K which is highly energy intensive. Here, we report the discrimination of xylene isomers via refinement of the pore size in a series of porous metal–organic frameworks, MFM-300, at sub-angstrom precision leading to the optimal kinetic separation of all three xylene isomers at room temperature. The exceptional performance of MFM-300 for xylene separation is confirmed by dynamic ternary breakthrough experiments. In-depth structural and vibrational investigations using synchrotron X-ray diffraction and terahertz spectroscopy define the underlying host–guest interactions that give rise to the observed selectivity (p-xylene < o-xylene < m-xylene) and separation factors of 4.6–18 for p- and m-xylenes.	Aug 2020
B22-Multimode InfraRed imaging And Microspectroscopy	Observation of binding of carbon dioxide to nitro-decorated metal–organic frameworks Thien D. Duong , Sergey A. Sapchenko , Ivan Da Silva , Harry G. W. Godfrey , Yongqiang Cheng , Luke L. Daemen , Pascal Manuel , Mark D. Frogley , Gianfelice Cinque , Anibal J. Ramirez-cuesta , Sihai Yang , Martin Schroeder Chemical Science 325 DOI: 10.1039/C9SC04294F Diamond Proposal Number(s): [14938] Open Access Show Abstract ▼ Abstract: Metal–organic frameworks (MOFs) functionalised with amine, amide and hydroxyl groups show great promise for CO2 binding due to their ability to form hydrogen bonds to CO2. Herein we report the adsorption and selectivity of CO2 in four iso-reticular MOFs adopting the NbO topology. Functionalisation of the parent MOF, MFM-102, with –NO2, –NH2 and alkyl groups leads to an enhancement of CO2 adsorption of up to 36% for the NO2-decorated MOF and with raised selectivity. MFM-102-NO2 shows the highest adsorption capacity for CO2 (184 cm3 g−1 at 273 K and 1.0 bar) within this series, comparable to the best-behaving iso-reticular MOFs. At 298 K and 1.0 bar, MFM-102-NO2 shows a CO2/CH4 selectivity of 5.0. In situ inelastic neutron scattering and synchrotron FT-IR micro-spectroscopy were employed to elucidate the host–guest interaction dynamics within CO2-loaded MFM-102-NO2. Neutron powder diffraction enabled the direct observation of the preferred binding domains in MFM-102-NO2, and, to the best of our knowledge, we report the first example of CO2 binding to a –NO2 group in a porous MOF. Synergistic effects between the –NO2 group and the open metal sites lead to optimal binding of CO2 molecules within MFM-102-NO2 via hydrogen bonding to C–H groups.	May 2020
I11-High Resolution Powder Diffraction	Control of zeolite pore interior for chemoselective alkyne/olefin separations Yuchao Chai , Xue Han , Weiyao Li , Shanshan Liu , Sikai Yao , Chong Wang , Wei Shi , Ivan Da Silva , Pascal Manuel , Yongqiang Cheng , Luke D. Daemen , Anibal J. Ramirez-cuesta , Chiu C. Tang , Ling Jiang , Sihai Yang , Naijia Guan , Landong Li Science 368, 1002 - 1006 DOI: 10.1126/science.aay8447 Diamond Proposal Number(s): [23483] Open Access Show Abstract ▼ Abstract: The efficient removal of alkyne impurities for the production of polymer-grade lower olefins remains an important and challenging goal for many industries. We report a strategy to control the pore interior of faujasite (FAU) zeolites by the confinement of isolated open nickel(II) sites in their six-membered rings. Under ambient conditions, Ni@FAU showed remarkable adsorption of alkynes and efficient separations of acetylene/ethylene, propyne/propylene, and butyne/1,3-butadiene mixtures, with unprecedented dynamic separation selectivities of 100, 92, and 83, respectively. In situ neutron diffraction and inelastic neutron scattering revealed that confined nickel(II) sites enabled chemoselective and reversible binding to acetylene through the formation of metastable [Ni(II)(C2H2)3] complexes. Control of the chemistry of pore interiors of easily scalable zeolites has unlocked their potential in challenging industrial separations.	May 2020
B18-Core EXAFS I11-High Resolution Powder Diffraction	Quantitative production of butenes from biomass-derived γ-valerolactone catalysed by hetero-atomic MFI zeolite Longfei Lin , Alena M. Sheveleva , Ivan Da Silva , Christopher M. A. Parlett , Zhimou Tang , Yueming Liu , Mengtian Fan , Xue Han , Joseph H. Carter , Floriana Tuna , Eric J. L. Mcinnes , Yongqiang Cheng , Luke L. Daemen , Svemir Rudic , Anibal J. Ramirez-cuesta , Chiu C. Tang , Sihai Yang Nature Materials 19, 86 - 93 DOI: 10.1038/s41563-019-0562-6 Diamond Proposal Number(s): [15151, 24726] Show Abstract ▼ Abstract: The efficient production of light olefins from renewable biomass is a vital and challenging target to achieve future sustainable chemical processes. Here we report a hetero-atomic MFI-type zeolite (NbAlS-1), over which aqueous solutions of γ-valerolactone (GVL), obtained from biomass-derived carbohydrates, can be quantitatively converted into butenes with a yield of >99% at ambient pressure under continuous flow conditions. NbAlS-1 incorporates simultaneously niobium(v) and aluminium(iii) centres into the framework and thus has a desirable distribution of Lewis and Brønsted acid sites with optimal strength. Synchrotron X-ray diffraction and absorption spectroscopy show that there is cooperativity between Nb(v) and the Brønsted acid sites on the confined adsorption of GVL, whereas the catalytic mechanism for the conversion of the confined GVL into butenes is revealed by in situ inelastic neutron scattering, coupled with modelling. This study offers a prospect for the sustainable production of butene as a platform chemical for the manufacture of renewable materials.	Dec 2019
B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS B18-Core EXAFS E01-JEM ARM 200CF	Influence of synthesis conditions on the structure of nickel nanoparticles and their reactivity in selective asymmetric hydrogenation Rosa Arrigo , Simone Gallarati , Manfred E. Schuster , Jake Seymour , Diego Gianolio , Ivan Da Silva , June Callison , Haosheng Feng , John E. Proctor , Pilar Ferrer , Federica Venturini , Dave Grinter , Georg Held Chemcatchem DOI: 10.1002/cctc.201901955 Open Access Show Abstract ▼ Abstract: Unsupported and SiO 2 ‐supported Ni nanoparticles (NPs), were synthesised via hot‐injection colloidal route using oleylamine (OAm) and trioctylphosphine (TOP) as reducing and protective agents, respectively. By adopting a multi‐length scale structural characterization, it was found that by changing equivalents of OAM and TOP not only the size of the nanoparticles is affected but also the Ni electronic structure. The synthetized NPs were modified with ( R , R )‐tartaric acid (TA) and investigated in the asymmetric hydrogenation of methyl acetoacetate to chiral methyl‐3‐hydroxy butyrate. The comparative analysis of structure and catalytic performance for the synthetized catalysts has enabled us to identify a Ni metallic active surface, whereby the activity increases with the size of the metallic domains. Conversely, at the high conversion obtained for the unsupported NPs there was no impact of particle size on the selectivity. ( R )‐selectivity was very high only on catalysts containing positively charged Ni species such as over the SiO 2 ‐supported NiO NPs. This work shows that the chiral modification of metallic Ni NPs with TA is insufficient to maintain high selectivity towards the ( R )‐enantiomer at long reaction time and provide guidance for the engineering of long‐term stable enantioselective catalysts.	Dec 2019

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