E02-JEM ARM 300CF
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Zupeng
Chen
,
Evgeniya
Vorobyeva
,
Sharon
Mitchell
,
Edvin
Fako
,
Manuel A.
Ortuño
,
Núria
López
,
Sean M.
Collins
,
Paul A.
Midgley
,
Sylvia
Richard
,
Gianvito
Vilé
,
Javier
Pérez-ramírez
Diamond Proposal Number(s):
[16967]
Abstract: Palladium-catalysed cross-coupling reactions, central tools in fine-chemical synthesis, predominantly employ soluble metal complexes despite recognized challenges with product purification and catalyst reusability. Attempts to tether these homogeneous catalysts on insoluble carriers have been thwarted by suboptimal stability, which leads to a progressively worsening performance due to metal leaching or clustering4. The alternative application of supported Pd nanoparticles has faced limitations because of insufficient activity under the mild conditions required to avoid thermal degradation of the substrates or products. Single-atom heterogeneous catalysts lie at the frontier. Here, we show that the Pd atoms anchored on exfoliated graphitic carbon nitride (Pd-ECN) capture the advantages of both worlds, as they comprise a solid catalyst that matches the high chemoselectivity and broad functional group tolerance of state-of-the-art homogeneous catalysts for Suzuki couplings, and also demonstrate a robust stability in flow. The adaptive coordination environment within the macroheterocycles of ECN facilitates each catalytic step. The findings illustrate the exciting opportunities presented by nanostructuring single atoms in solid hosts for catalytic processes that remain difficult to heterogenize.
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Jun 2018
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E02-JEM ARM 300CF
I15-1-X-ray Pair Distribution Function (XPDF)
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Shichun
Li
,
Shuwen
Yu
,
Sean M.
Collins
,
Duncan N.
Johnstone
,
Christopher W.
Ashling
,
Adam F.
Sapnik
,
Philip A.
Chater
,
Dean S.
Keeble
,
Lauren N.
Mchugh
,
Paul A.
Midgley
,
David A.
Keen
,
Thomas D.
Bennett
Diamond Proposal Number(s):
[20038, 22632, 21979]
Open Access
Abstract: Metal–organic framework crystal–glass composite (MOF CGC) materials consist of a crystalline MOF embedded within a MOF–glass matrix. In this work, a new synthetic route to these materials is demonstrated through the preparation of two ZIF-62 glass-based CGCs, one with crystalline ZIF-67 and the other with crystalline UiO-66. Previous attempts to form these CGCs failed due to the high processing temperatures involved in heating above the melting point of ZIF-62. Annealing of the ZIF-62 glass above the glass transition with each MOF however leads to stable CGC formation at lower temperatures. The reduction in processing temperatures will enable the formation of a greatly expanded range of MOF CGCs.
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Sep 2020
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E02-JEM ARM 300CF
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Diamond Proposal Number(s):
[21980]
Abstract: Plasmonic structures have attracted much interest in science and engineering disciplines, exploring a myriad of potential applications owing to their strong light-matter interactions. Recently, the plasmonic concentration of energy in subwavelength volumes has been used to initiate chemical reactions, for instance by combining plasmonic materials with catalytic metals. In this work, we demonstrate that plasmonic nanoparticles of earth-abundant Mg can undergo galvanic replacement in a nonaqueous solvent to produce decorated structures. This method yields bimetallic architectures where partially oxidized 200–300 nm Mg nanoplates and nanorods support many smaller Au, Ag, Pd, or Fe nanoparticles, with potential for a stepwise process introducing multiple decoration compositions on a single Mg particle. We investigated this mechanism by electron-beam imaging and local composition mapping with energy-dispersive X-ray spectroscopy as well as, at the ensemble level, by inductively coupled plasma mass spectrometry. High-resolution scanning transmission electron microscopy further supported the bimetallic nature of the particles and provided details of the interface geometry, which includes a Mg oxide separation layer between Mg and the other metal. Depending on the composition of the metallic decorations, strong plasmonic optical signals characteristic of plasmon resonances were observed in the bulk with ultraviolet-visible spectrometry and at the single particle level with darkfield scattering. These novel bimetallic and multimetallic designs open up an exciting array of applications where one or multiple plasmonic structures could interact in the near-field of earth-abundant Mg and couple with catalytic nanoparticles for applications in sensing and plasmon-assisted catalysis.
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Dec 2019
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E02-JEM ARM 300CF
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Diamond Proposal Number(s):
[20195, 21979, 20198]
Abstract: Defect engineering can enhance key properties of metal-organic frameworks (MOFs). Tailoring the distribution of de-fects, for example in correlated nanodomains, requires characterization across length scales. However, a critical na-noscale characterization gap has emerged between the bulk diffraction techniques used to detect defect nanodomains and the sub-nanometer imaging used to observe individual defects. Here, we demonstrate that the emerging technique of scanning electron diffraction (SED) can bridge this gap uniquely enabling both nanoscale crystallographic analysis and the low-dose formation of multiple diffraction contrast images for defect analysis in MOFs. We directly image defect nanodomains in the MOF UiO-66(Hf) over an area of ca. 1 000 nm and with a spatial resolution ca. 5 nm to reveal domain morphology and distribution. Based on these observations, we suggest possible crystal growth processes underpinning synthetic control of defect nanodomains. We also identify likely dislocations and small angle grain boundaries, illustrating that SED could be a key technique in developing the potential for engineering the distribution of defects, or “microstruc-ture”, in functional MOF design.
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Jul 2020
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E02-JEM ARM 300CF
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Diamond Proposal Number(s):
[21980]
Abstract: Advances in the production of two-dimensional (2D) materials such as graphene and MoS2 during the past two decades have spurred the search for other van der Waals materials with distinct functional properties. However, reducing the dimensionality of bulk van der Waals materials can lead to structural rearrangement and chemical degradation, especially in the presence of air. These challenges have slowed the progress of the discovery and analysis of chemically diverse 2D materials. Here, we provide a case study on the shear exfoliation of a class of wide band gap van der Waals materials termed II–VI layered hybrids (II–VI LHs) and show how reducing their dimension influences their structural and chemical stabilities. ZnSe(butylamine) and ZnSe(octylamine) are exfoliated, yielding shear-thinned material whose resistance toward degradation via oxidation is studied in depth by a variety of macro- and microscopic characterization techniques. Mechanical energy input, solvent–ligand interaction, and exposure to ambient conditions all play important roles in the stability of these materials. Our findings suggest that moderately coordinating alkylamine layers stabilize 2D materials that would otherwise degrade during exfoliation and exposure to air.
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Mar 2020
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I22-Small angle scattering & Diffraction
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Louis
Longley
,
Sean M.
Collins
,
Shichun
Li
,
Glen J.
Smales
,
Ilknur
Erucar
,
Ang
Qiao
,
Jingwei
Hou
,
Cara M.
Doherty
,
Aaron W.
Thornton
,
Anita J.
Hill
,
Xiao
Yu
,
Nicholas J.
Terrill
,
Andrew J.
Smith
,
Seth M.
Cohen
,
Paul A.
Midgley
,
David A.
Keen
,
Shane G.
Telfer
,
Thomas
Bennett
Diamond Proposal Number(s):
[18236]
Open Access
Abstract: Recent demonstrations of melting in the metal–organic framework (MOF) family have created interest in the interfacial domain between inorganic glasses and amorphous organic polymers. The chemical and physical behaviour of porous hybrid liquids and glasses is of particular interest, though opportunities are limited by the inaccessible melting temperatures of many MOFs. Here, we show that the processing technique of flux melting, ‘borrowed’ from the inorganic domain, may be applied in order to melt ZIF-8, a material which does not possess an accessible liquid state in the pure form. Effectively, we employ the high-temperature liquid state of one MOF as a solvent for a secondary, non-melting MOF component. Differential scanning calorimetry, small- and wide-angle X-ray scattering, electron microscopy and X-ray total scattering techniques are used to show the flux melting of the crystalline component within the liquid. Gas adsorption and positron annihilation lifetime spectroscopy measurements show that this results in enhanced, accessible porosity to a range of guest molecules in the resultant flux melted MOF glass.
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Feb 2019
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I15-1-X-ray Pair Distribution Function (XPDF)
I22-Small angle scattering & Diffraction
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Louis
Longley
,
Sean
Collins
,
Chao
Zhou
,
Glen J.
Smales
,
Sarah E.
Norman
,
Nick J.
Brownbill
,
Christopher W.
Ashling
,
Philip A.
Chater
,
Robert
Tovey
,
Carola-bibiane
Schönlieb
,
Thomas F.
Headen
,
Nicholas J.
Terrill
,
Yuanzheng
Yue
,
Andrew J.
Smith
,
Frédéric
Blanc
,
David
Keen
,
Paul A.
Midgley
,
Thomas
Bennett
Diamond Proposal Number(s):
[171151, 18236]
Open Access
Abstract: The liquid and glass states of metal–organic frameworks (MOFs) have recently become of interest due to the potential for liquid-phase separations and ion transport, alongside the fundamental nature of the latter as a new, fourth category of melt-quenched glass. Here we show that the MOF liquid state can be blended with another MOF component, resulting in a domain structured MOF glass with a single, tailorable glass transition. Intra-domain connectivity and short range order is confirmed by nuclear magnetic resonance spectroscopy and pair distribution function measurements. The interfacial binding between MOF domains in the glass state is evidenced by electron tomography, and the relationship between domain size and Tg investigated. Nanoindentation experiments are also performed to place this new class of MOF materials into context with organic blends and inorganic alloys.
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Jun 2018
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E02-JEM ARM 300CF
|
Diamond Proposal Number(s):
[16983, 19130, 20195, 21979]
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Aug 2019
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E02-JEM ARM 300CF
I15-1-X-ray Pair Distribution Function (XPDF)
|
Jingwei
Hou
,
Christopher W.
Ashling
,
Sean M.
Collins
,
Andraž
Krajnc
,
Chao
Zhou
,
Louis
Longley
,
Duncan N.
Johnstone
,
Philip
Chater
,
Shichun
Li
,
Marie-vanessa
Coulet
,
Philip L.
Llewellyn
,
François-xavier
Coudert
,
David
Keen
,
Paul A.
Midgley
,
Gregor
Mali
,
Vicki
Chen
,
Thomas D.
Bennett
Diamond Proposal Number(s):
[171151, 19130, 16983]
Open Access
Abstract: The majority of research into metal-organic frameworks (MOFs) focuses on their crystalline nature. Recent research has revealed solid-liquid transitions within the family, which we use here to create a class of functional, stable and porous composite materials. Described herein is the design, synthesis, and characterisation of MOF crystal-glass composites, formed by dispersing crystalline MOFs within a MOF-glass matrix. The coordinative bonding and chemical structure of a MIL-53 crystalline phase are preserved within the ZIF-62 glass matrix. Whilst separated phases, the interfacial interactions between the closely contacted microdomains improve the mechanical properties of the composite glass. More significantly, the high temperature open pore phase of MIL-53, which spontaneously transforms to a narrow pore upon cooling in the presence of water, is stabilised at room temperature in the crystal-glass composite. This leads to a significant improvement of CO2 adsorption capacity.
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Jun 2019
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I11-High Resolution Powder Diffraction
I12-JEEP: Joint Engineering, Environmental and Processing
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Kieran W. P.
Orr
,
Sean M.
Collins
,
Emily M.
Reynolds
,
Frank
Nightingale
,
Hanna L. B.
Bostroem
,
Simon J.
Cassidy
,
Daniel M.
Dawson
,
Sharon E.
Ashbrook
,
Oxana
Magdysyuk
,
Paul A.
Midgley
,
Andrew L.
Goodwin
,
Hamish H.-m.
Yeung
Diamond Proposal Number(s):
[20946, 18786]
Open Access
Abstract: Control over the spatial distribution of components in metal–organic frameworks has potential to unlock improved performance and new behaviour in separations, sensing and catalysis. We report an unprecedented single-step synthesis of multi-component metal–organic framework (MOF) nanoparticles based on the canonical ZIF-8 (Zn) system and its Cd analogue, which form with a core–shell structure whose internal interface can be systematically tuned. We use scanning transmission electron microscopy, X-ray energy dispersive spectroscopy and a new composition gradient model to fit high-resolution X-ray diffraction data to show how core–shell composition and interface characteristics are intricately controlled by synthesis temperature and reaction composition. Particle formation is investigated by in situ X-ray diffraction, which reveals that the spatial distribution of components evolves with time and is determined by the interplay of phase stability, crystallisation kinetics and diffusion. This work opens up new possibilities for the control and characterisation of functionality, component distribution and interfaces in MOF-based materials.
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Feb 2021
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