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Samer
Abdulridha
,
Rongxin
Zhang
,
Shaojun
Xu
,
Aleksander
Tedstone
,
Xiaoxia
Ou
,
Jiacheng
Gong
,
Boyang
Mao
,
Mark
Frogley
,
Carlo
Bawn
,
Zhaoxia
Zhou
,
Xinran
Zhang
,
Sarayute
Chansai
,
Stuart M.
Holmes
,
Christopher
Hardacre
,
Arthur A.
Garforth
,
Sihai
Yang
,
Yilai
Jiao
,
Xiaolei
Fan
Abstract: We report a low-cost, highly energy efficient microwave-assisted chelation (MWAC) method, which enabled the post-synthetic modification of synthetic zeolites for adopting hierarchical structures within minutes. Exemplified by Zeolite Y, hierarchical Y zeolites prepared in this way showed exceptional specific external surface areas of >300 m2 g−1 and mesopore volumes of >0.46 cm3 g−1. Comparative assessments revealed that developed zeolites have shown significantly improved catalytic activities for catalysis involving large substrates, such as catalytic cracking and hydrocracking of plastics.
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Oct 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
|
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
Diamond Proposal Number(s):
[22137]
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.
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Oct 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
|
Xinchen
Kang
,
Bin
Wang
,
Kui
Hu
,
Kai
Lyu
,
Xue
Han
,
Ben F.
Spencer
,
Mark D.
Frogley
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Robert A. W.
Dryfe
,
Buxing
Han
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[19171]
Open Access
Abstract: Efficient electro-reduction of CO2 over metal–organic framework (MOF) materials is hindered by the poor contact between thermally synthesized MOF particles and the electrode surface, which leads to low Faradaic efficiency for a given product and poor electrochemical stability of the catalyst. We report a MOF-based electrode prepared via electro-synthesis of MFM-300(In) on an indium foil, and its activity for the electrochemical reduction of CO2 is assessed. The resultant MFM-300(In)-e/In electrode shows a 1 order of magnitude improvement in conductivity compared with that for MFM-300(In)/carbon-paper electrodes. MFM-300(In)-e/In exhibits a current density of 46.1 mA cm–2 at an applied potential of −2.15 V vs Ag/Ag+ for the electro-reduction of CO2 in organic electrolyte, achieving an exceptional Faradaic efficiency of 99.1% for the formation of formic acid. The facile preparation of the MFM-300(In)-e/In electrode, coupled with its excellent electrochemical stability, provides a new pathway to develop efficient electro-catalysts for CO2 reduction.
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Sep 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
|
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
Diamond Proposal Number(s):
[13247]
Open Access
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.
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Aug 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
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Diamond Proposal Number(s):
[15975, 21059]
Open Access
Abstract: Mudstone-hosted microfossils are a major component of the Proterozoic fossil record, particularly dominating the record of early eukaryotic life. Early organisms possessed no biomineralized parts to resist decay and controls on their fossilization in mudstones are poorly understood. Consequently, the Proterozoic fossil record is compromised—we do not know whether changing temporal/spatial patterns of microfossil occurrences reflect evolution or the distribution of favourable fossilization conditions. We investigated fossilization within the approximately 1000 Ma Lakhanda Group (Russia) and the approximately 800 Ma Svanbergfjellet and Wynniatt formations (Svalbard and Arctic Canada). Vertical sections of microfossils and surrounding matrices were extracted from thin sections by focused ion beam milling. Elemental mapping and synchrotron-based infrared microspectroscopy revealed that microfossils are surrounded by haloes rich in aluminium, probably hosted in kaolinite. Kaolinite has been implicated in Cambrian Burgess Shale-type (BST) fossilization and is known to slow the growth of degraders. The Neoproterozoic mudstone microfossil record may be biased to tropical settings conducive to kaolinite formation. These deposits lack metazoan fossils even though they share fossilization conditions with younger BST deposits that are capable of preserving non-mineralizing metazoans. Thus metazoans, at least those typically preserved in BST deposits, were probably absent from sedimentary environments before approximately 800 Ma.
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Jun 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
|
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
Diamond Proposal Number(s):
[14938]
Open Access
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.
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May 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
Optics
|
Open Access
Abstract: Vibrational microspectroscopy via Fourier transform infrared (FTIR) faces an experimental trade-off among the signal to noise ratio (SNR), acquisition time, spatial resolution, and sample coverage. This is mainly associated with broadband source type: e.g. low brightness thermal sources with high flux for large field of view imaging at low resolution, or low ´etendue of synchrotron radiation infrared (SRIR) for diffraction-limited scanning mi- croanalysis at high magnification.1 Adaptive optics (AO), in this case deformable mirror (DM), is a potent tool in tackling the problem by modulating the intensity of high brightness structured SRIR beam toward a homo- geneous field illumination for IR imaging at high magnification. The latter is required for an efficient coupling of SRIR source to a multi-pixel detector such as focal plane array (FPA).2 Additionally, DM enables to achieve different shapes, optimized for different Cassegrain IR objective. Regardless, the quality of the generated beam relies upon the performance of the adaptive elements, i.e. actuators and their linear and reproducible response to the applied voltage. Moreover, the beam shaping capability of a single DM in controlling light beam position and angle is limited by its actuators influence function. In this work, we implemented two DMs for intensity shaping for the complex SRIR beam. A variation of multi-conjugate AO is implemented to characterize the performance of DMs and their actuators transfer function at multiple locations. An IR sensitive microbolometer array has been optically conjugated to the focal plane of individual actuators and the far-field of DM, in order to probe the corresponding actuating response. By analysing each actuator’s response individually, a measure of linear independence, uniformity in response, and cross-coupling can be obtained in a spectral range, from visible to near and mid IR. Additionally, by assembling the vectorized version of each actuator response, the transfer matrix can be formed. This matrix describes the relationship between the actuation effect on the beam and the response of the IR microbolometer, at the given conjugate planes. Based on such discussion, we assess the stability of the deformable mirror for open-loop (i.e. without feedback) operation.
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May 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
|
Diamond Proposal Number(s):
[21061]
Abstract: Synchrotron resonance-enhanced infrared-atomic force microscopy (RE-AFM-IR) is a near-field photothermal vibrational nanoprobe developed at the Diamond Light Source (DLS), capable of measuring mid-infrared absorption spectra with spatial resolution around 100 nm. The present study reports a first application of synchrotron RE-AFM-IR to interrogate biological soft matter at subcellular level, in this case on a cellular model of drug-induced phospholipidosis (DIPL). J774A-1 macrophages were exposed to amiodarone (10 µM) or medium for 24 hours and chemically fixed. AFM topography maps revealed amiodarone-treated cells with enlarged cytoplasm and very thin regions corresponding to collapsed vesicles. IR maps of the whole cell were analysed by exploiting the RE-AFM-IR overall signal, i.e. the integrated RE-AFM-IR signal amplitude versus AFM-derived cell thickness, also on lateral resolution around 100 nm. Results shown that vibrational band assignment was possible and all characteristic peaks for lipids, proteins and DNA/RNA were identified. Both peak ratio and unsupervised chemometric analysis of RE-AFM-IR nanospectra generated from the nuclear and perinuclear regions of untreated and amiodarone-treated cells showed that the perinuclear region (i.e. cytoplasm) of amiodarone-treated cells had significantly elevated band intensities in the regions corresponding to phosphate and carbonyl groups, indicating detection of phospholipid-rich inclusion bodies typical for cells with DIPL. The results of this study are of importance to demonstrate not only the applicability of Synchrotron RE-AFM-IR to soft biological matters with subcellular spatial resolution, but also that the spectral information gathered from an individual sub-micron sample volume enables chemometric identification of treatment and biochemical differences between mammalian cells.
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May 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
|
Diamond Proposal Number(s):
[13725, 16257, 18680, 20906]
Abstract: Operando synchrotron infrared microspectroscopy (OIMS) was used to study the conversion of methanol over coffin-shaped HZSM-5 crystals of different sizes: large (∼250 × 80 × 85 μm3), medium (∼160 × 60 × 60 μm3) and small (∼55 × 30 × 30 μm3). The induction period, for direct alkene formation by deprotonation of surface methoxy groups, was found to decrease with decreasing crystal size and with increasing reaction temperature. Experiments with a continuous flow of dimethylether showed that evolution of the hydrocarbon pool and indirect alkene formation is also strongly dependent on crystal size. These measurements suggest that the hydrocarbon pool formation and indirect alkene generation should be almost instantaneous at reaction temperatures used in practical catalysis with crystal sizes typically ∼1 μm3.
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Mar 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
|
Open Access
Abstract: Broadband infrared nanospectroscopy with Synchrotron Radiation, via the atomic force microscope detection of photothermal expansion, was first demonstrated at the MIRIAM beamline of Diamond in 2016. Since then, the system has undergone significant developments and has been available to users in collaboration since January 2018. Continuous nano-FTIR spectra are so-far achieved with useful signal-to-noise in the 4000 – 800 wavenumber region and at around 100 nm spatial resolution (depending on sample geometry and thermal diffusion at the modulation frequency of the IR beam), for soft materials like single biological cells and polymers. Here we briefly describe the nanospectroscopy system and evaluate the performances through comparison of measured data for typical samples with theoretical expectations. Noise levels are shown to be cantilever thermal-noise limited at the first contact resonance currently employed, whilst signal levels are consistent with expectations for the focussed IR power density available from the IR beamline and using sinusoidal modulation of the beam tuned to the contact resonance frequency. Finally, planned enhancements of the performance, including access to higher cantilever contact resonances to reduce noise and increase spatial resolution, are discussed.
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Feb 2020
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