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21 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	Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site Bing An , Zhe Li , Zi Wang , Xiangdi Zeng , Xue Han , Yongqiang Chen , Alena M. Sheveleva , Zhongyue Zhang , Floriana Tuna , Eric J. L. Mcinnes , Mark D. Frogley , Anibal J. Ramirez-Cuesta , Louise S. Natrajan , Cheng Wang , Wenbin Li , Sihai Yang , Martin Schroeder Nature Materials 338 DOI: 10.1038/s41563-022-01279-1 Diamond Proposal Number(s): [23782] Show Abstract ▼ Abstract: Natural gas, consisting mainly of methane (CH4), has a relatively low energy density at ambient conditions (~36 kJ l−1). Partial oxidation of CH4 to methanol (CH3OH) lifts the energy density to ~17 MJ l−1 and drives the production of numerous chemicals. In nature, this is achieved by methane monooxygenase with di-iron sites, which is extremely challenging to mimic in artificial systems due to the high dissociation energy of the C–H bond in CH4 (439 kJ mol−1) and facile over-oxidation of CH3OH to CO and CO2. Here we report the direct photo-oxidation of CH4 over mono-iron hydroxyl sites immobilized within a metal–organic framework, PMOF-RuFe(OH). Under ambient and flow conditions in the presence of H2O and O2, CH4 is converted to CH3OH with 100% selectivity and a time yield of 8.81 ± 0.34 mmol gcat−1 h−1 (versus 5.05 mmol gcat−1 h−1 for methane monooxygenase). By using operando spectroscopic and modelling techniques, we find that confined mono-iron hydroxyl sites bind CH4 by forming an [Fe–OH···CH4] intermediate, thus lowering the barrier for C–H bond activation. The confinement of mono-iron hydroxyl sites in a porous matrix demonstrates a strategy for C–H bond activation in CH4 to drive the direct photosynthesis of CH3OH.	Jun 2022
B18-Core EXAFS B22-Multimode InfraRed imaging And Microspectroscopy	Direct observation of ammonia storage in UIO-66 incorporating Cu(II) binding sites Yujie Ma , Wanpeng Lu , Xue Han , Yinlin Chen , Ivan Da Silva , Daniel Lee , Alena M. Sheveleva , Zi Wang , Jiangnan Li , Weiyao Li , Mengtian Fan , Shaojun Xu , Floriana Tuna , Eric J. L. Mcinnes , Yongqiang Cheng , Svemir Rudic , Pascal Manuel , Mark D. Frogley , Anibal J. Ramirez-Cuesta , Martin Schroeder , Sihai Yang Journal Of The American Chemical Society DOI: 10.1021/jacs.2c00952 Diamond Proposal Number(s): [19850] Open Access Show Abstract ▼ Abstract: The presence of active sites in metal–organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111–1135 m2 g–1), decoration of the −OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g–1 in UiO-66-CuII. A 100% enhancement of dynamic adsorption of NH3 at a concentration level of 630 ppm from 2.07 mmol g–1 in UiO-66-defect to 4.15 mmol g–1 in UiO-66-CuII at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH3 uptake in UiO-66-CuII originates from a {Cu(II)···NH3} interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH3 capture and storage.	May 2022
B22-Multimode InfraRed imaging And Microspectroscopy	High capacity ammonia adsorption in a robust metal-organic framework mediated by reversible host-guest interactions Lixia Guo , Xue Han , Yujie Ma , Jiangnan Li , Wanpeng Lu , Weiyao Li , Daniel Lee , Ivan Da Silva , Yongqiang Cheng , Svemir Rudic , Pascal Manuel , Mark D. Frogley , Anibal Javier Ramirez-Cuesta , Martin Schroeder , Sihai Yang Chemical Communications DOI: 10.1039/D2CC01197B Diamond Proposal Number(s): [30398] Open Access Show Abstract ▼ Abstract: To understand the exceptional adsorption of ammonia (NH3) in MFM-300(Sc) (19.5 mmol g−1 at 273 K and 1 bar without hysteresis), we report a systematic investigation of the mechanism of adsorption by a combination of in situ neutron powder diffraction, inelastic neutron scattering, synchrotron infrared microspectroscopy, and solid-state 45Sc NMR spectroscopy. These complementary techniques reveal the formation of reversible host-guest supramolecular interactions, which explains directly the observed excellent reversibility of this material over 90 adsorption-desorption cycles.	Apr 2022
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
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
B22-Multimode InfraRed imaging And Microspectroscopy	Guest-controlled incommensurate modulation in a meta-rigid metal–organic framework material Jiangnan Li , Zhengyang Zhou , Xue Han , Xinran Zhang , Yong Yan , Weiyao Li , Gemma L. Smith , Yongqiang Cheng , Laura J. Mcormick Mpherson , Simon J. Teat , Mark D. Frogley , Svemir Rudic , Anibal J. Ramirez-Cuesta , Alexander J. Blake , Junliang Sun , Martin Schroeder , Sihai Yang Journal Of The American Chemical Society DOI: 10.1021/jacs.0c08794 Diamond Proposal Number(s): [22137] Open Access Show Abstract ▼ Abstract: Structural transitions of host systems in response to guest binding dominate many chemical processes. We report an unprecedented type of structural flexibility within a meta-rigid material, MFM-520, which exhibits a reversible periodic-to-aperiodic structural transition resulting from a drastic distortion of a [ZnO4N] node controlled by the specific host–guest interactions. The aperiodic crystal structure of MFM-520 has no three-dimensional (3D) lattice periodicity but shows translational symmetry in higher-dimensional (3 + 2)D space. We have directly visualized the aperiodic state which is induced by incommensurate modulation of the periodic framework of MFM-520·H2O upon dehydration to give MFM-520. Filling MFM-520 with CO2 and SO2 reveals that, while CO2 has a minimal structural influence, SO2 can further modulate the structure incommensurately. MFM-520 shows exceptional selectivity for SO2 under flue-gas desulfurization conditions, and the facile release of captured SO2 from MFM-520 enabled the conversion to valuable sulfonamide products. MFM-520 can thus be used as a highly efficient capture and delivery system for SO2.	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

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