The Oxford-Diamond <i>In Situ</i> Cell for studying chemical reactions using time-resolved X-ray diffraction

Moorhouse, Saul J.; Vranješ, N.; Jupe, Andrew C.; Drakopoulos, Michael; O’Hare, Dermot

doi:10.1063/1.4746382

Cited by 42 publications

(34 citation statements)

References 18 publications

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“…Experiments were performed in the Oxford-Diamond In Situ Cell (ODISC), the details of which have been reported elsewhere. 36 In brief, ODISC comprises an IR-heated furnace system with a stirrer attachment, similar to the Oxford-Daresbury cell but with more rapid heating and cooling cycles possible. Reactions were performed using the same amounts of materials as for those on DORIS, but with glassy carbon tubes used in place of borosilicate glass (in order to ensure effective heat transfer).…”

Section: Methodsmentioning

confidence: 99%

A kinetic and mechanistic study into the formation of the Cu–Cr layered double hydroxide

Williams

Clout

Burley

2013

Phys. Chem. Chem. Phys.

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The formation of the layered double hydroxide [Cu 2 Cr(OH) 6 ]ClÁyH 2 O from the reaction between CuO and aqueous CrCl 3 Á6H 2 O was explored using synchrotron X-ray diffraction and ex situ analyses. The use of hard X-rays permitted time-resolved in situ studies to be performed as the reaction proceeded under a range of conditions. Additional information was obtained from ex situ experiments in which aliquots of the reaction mixture were removed, quenched, and subsequently analysed by laboratory X-ray diffraction, IR, UV-visible, and atomic emission spectroscopies. On the basis of these data, it is proposed that the reaction involves three steps. First, the solid CuO starting material is hydrolysed to give Cu(OH) 2 chains, releasing Cu 2+ ions into solution. The Cu hydroxide chains subsequently condense with aqueous Cr 3+ species, Cl À ions and water molecules to give a hydrated form of the LDH. This material then extrudes some water to form a phase with a reduced interlayer spacing.

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Section: Methodsmentioning

confidence: 99%

A kinetic and mechanistic study into the formation of the Cu–Cr layered double hydroxide

Williams

Clout

Burley

2013

Phys. Chem. Chem. Phys.

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“…The reaction was stirred rapidly with a Tefloncoated magnetic follower to aid heat transfer and to ensure that uniform solid product was present in the X-ray beam throughout the experiment. The cells were heated within the ODISC infra-red furnace, 24 with a glassy carbon sheath around the sample tube to allow heat transfer to the reaction mixture. A wavelength of 0.2242 Å was used and 2D diffraction patterns collected every minute using a Pixium image plate detector (430 × 430 mm 2 ) with an exposure time of 4000 ms.…”

Section: -19mentioning

confidence: 99%

Structural variety in ytterbium dicarboxylate frameworks and in situ study diffraction of their solvothermal crystallisation

et al. 2017

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aThe ytterbium 1,4-benzenedicarboxylate (BDC) framework [Yb 2 ĲBDC) 3 ĲDMF) 2 ]·H 2 O (1) crystallises from a N, N-dimethylformamide (DMF)-rich solution at 80-120°C. (1) is constructed from infinite chains of dicarboxylate-bridged seven-coordinate Yb atoms, cross-linked in two directions by BDC to yield diamond-shaped channels (sra topology) lined by coordinated DMF molecules and occluded water. Increasing the water content in the synthesis solution yields a material with more crystal water (2), in which the Yb centres are eight-coordinate and form dimers bridged by BDC to give two interpenetrating networks of pcu (α-Po) topology. Upon extended reaction in this water-rich solvent mixture, an alternative phase is formed: an anhydrous mixed BDC-formate, YbĲBDC)ĲHCO 2 ), (3), which has a pillared, layered structure, with formate produced by hydrolysis of the DMF. An isoreticular version of (2) can also be formed under similar conditions using 2,6-naphthalene-dicarboxylate (NDC) as linker: [Yb 2 ĲNDC) 3 ĲH 2 O) 4 ]·2DMF (4). Despite their different structures, (1) and (2) are calcined to a common porous, desolvated phase Yb 2 ĲBDC) 3 at 300°C. Using high energy X-rays at Diamond Light Source we are able to penetrate the solvothermal reaction vessels and to follow the formation of (1) and (2) in real time.This allows accurate crystallisation curves to be obtained from which qualitative kinetic information is extracted. Importantly, the high angular resolution of the in situ powder XRD patterns allows refinement of crystal structure: this permits the temporal evolution of unit cell parameters to be followed, which are ascribed to changes in coordinated solvent composition within the materials during their formation, while analysis of phase fraction allows kinetic parameters to be quantified using the nucleation-growth model of Gualtieri.

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“…An internal thermocouple,t hreaded through the lid of the reaction tube allowed continuous monitoring of temperature during reactions.The reaction was stirred rapidly with asmaller Te flon-coatedm agnetic followert oa id heat transfer and to ensure that uniform solid product was present in the X-ray beam throughout the experiment. Thet ube was heated within the ODISC infra-red furnace, [17] with ag lassy carbon sheath around the sample to allow heat transfer to the reaction vessel. Aw avelength of 0.2242 w as used and 2D diffraction patterns collected every minute using aP ixium image plate detector( 430 430 mm 2 )w ith an exposure time of 4000 ms.T he system was calibrated with ac rystalline CeO 2 reference and the 2D image plate data were integratedusing the fit2d software to give 1D diffraction patterns.…”

Section: Zuschriftenmentioning

confidence: 99%

Exchange of Coordinated Solvent During Crystallization of a Metal–Organic Framework Observed by In Situ High‐Energy X‐ray Diffraction

Breeze

Clarkson

et al. 2016

Angewandte Chemie

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Using time-resolved monochromatic high energy X-ray diffraction, we present an in situ study of the solvothermal crystallisation of an ew MOF [Yb 2 (BDC) 3 (DMF) 2 ]·H 2 O (BDC = benzene-1,4-dicarboxylate and DMF = N,N-dimethylformamide) under solvothermal conditions,f rom mixed water/DMF solvent. Analysis of high resolution powder patterns obtained reveals an evolution of lattice parameters and electron density during the crystallisation process and Rietveld analysis shows that this is due to ag radual topochemical replacement of coordinated solvent molecules.T he water initially coordinated to Yb 3+ is replaced by DMF as the reaction progresses.The synthesis of metal-organic frameworks (MOFs) has,t o date,b een ap rocess fraught with assumptions,d ue to the difficulty of obtaining high quality structural data in situ during their formation that would provide detailed information about their crystallisation mechanism.[1] Although studies of kinetic vs.thermodynamic control in the synthesis of MOFs have been reported by screening products of reactions isolated as af unction of time,u sing both experimental and theoretical approaches, [2] an understanding of the early stages of MOF crystallisation processes remains poor.One untested assumption is that after aM OF nucleates,i tc rystallises without undergoing further structural changes.T he functionality of many metal-organic framework materials derives from their ability to interact with guest molecules.InMOFs in which the metal coordination sphere is not fully saturated with structural ligands,t he interaction between metal and coordinated molecules tends to be particularly strong, and this may give rise to favorable adsorption and catalysis properties.[3] Any interaction between guest and material must necessarily result in some level of change to the observed electron density distribution and unit cell size. This effect is prominent in several of the most widely studied MOFs:f or example,t he dehydroxylated UiO-66 framework loses hydroxyl and it unit cell contracts by ca. 0.05 , [4] while the difference between the guest-bound and bare MOF-74/ CPO-27 frameworks is on the order of 0.1 for both axes of the hexagonal cell.[5] These changes are well within the range that can be clearly resolved using high-resolution powder diffraction, and indeed this method has been used extensively in structural studies of the effect of adsorbed molecules on MOFs under gas atmospheres. [6] In many cases of MOF synthesis using solvothermal methods,i ti su nclear whether the framework is initially formed with coordinated solvent that is then exchanged with another ligand to reach the final product, or if the final product is formed from the start as the only species.T his knowledge would be valuable to the large scale deployment of MOFs,a llowing the optimization of syntheses to reduce or eliminate the need for certain types of post-synthetic processing,s uch as the high-temperature dehydroxylation of UiO-66.Energy-dispersive X-ray diffraction (EDXRD) has been used to g...

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The Oxford-Diamond In Situ Cell for studying chemical reactions using time-resolved X-ray diffraction

Cited by 42 publications

References 18 publications

A kinetic and mechanistic study into the formation of the Cu–Cr layered double hydroxide

A kinetic and mechanistic study into the formation of the Cu–Cr layered double hydroxide

Structural variety in ytterbium dicarboxylate frameworks and in situ study diffraction of their solvothermal crystallisation

Exchange of Coordinated Solvent During Crystallization of a Metal–Organic Framework Observed by In Situ High‐Energy X‐ray Diffraction

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