I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[30280]
Open Access
Abstract: A new metal–organic framework (MOF) comprising copper and 2,3-dihydroxyterephthalate (2,3-dhtp) has been prepared using solvothermal synthesis. The solid (chemical formula of the as-made material): Cu12(dhtp)4(H2dhtp)3(CH3CO2)2 2DMF·10H2O is flexible in that its pore size adapts to match the size of guest molecules that are adsorbed. Carboxylate-containing molecules of different sizes (acetate, benzoic acid and ibuprofen) can be accommodated within the pores of the material and are coordinated to a dimeric copper unit. The localisation of the adsorbate guest molecule, the mode of binding and relatively low symmetry of the MOF allows the system to be used as a crystalline sponge. The crystal structure determination of the as-synthesised acetate-bound MOF was accomplished using single-crystal X-ray diffraction using a synchrotron source, while the benzoate- and ibuprofen-bound structures were solved using electron diffraction. A more practical adsorbent can be formulated by growing the MOF on a cotton fabric substrate, and this is shown to adsorb ibuprofen in a similar manner to the powdered MOF.
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Nov 2025
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I19-Small Molecule Single Crystal Diffraction
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Russell M.
Main
,
Romy
Ettlinger
,
Tia K.
Tajnšek
,
Deborah A.
Brako-Amoafo
,
Maximillian G.
Stanzione
,
Morven J.
Duncan
,
Philip
Ettlinger
,
Gaynor B.
Lawrence
,
Mark R.
Warren
,
Christopher J.
Heard
,
Russell E.
Morris
Diamond Proposal Number(s):
[32865, 35900]
Open Access
Abstract: Metal–organic frameworks (MOFs), with their high porosities and surface areas, show great utility in the field of gas adsorption. To unlock this porosity, MOFs are generally fully activated by removing all adsorbed guests using high temperatures and low pressures. However, this is energy intensive and can be unfeasible if the MOF is part of a composite, where the maximum temperature of the composite is below the activation temperature. To investigate the effect of activation temperature on adsorption, a series of in situ single-crystal X-ray diffraction (scXRD) studies were performed on Ni-MOF-74 loaded with the gas nitric oxide (NO) under different conditions. These experiments uncovered anomalous adsorption results where partially activated samples adsorb ∼14% more NO per framework material than did the fully activated sample. The scXRD experiments revealed a new NO binding site that is only present if the open metal sites are partially occupied by water molecules. To shed more light on the respective binding of the two different NO sites in Ni-MOF-74, these were studied in situ under different treatment conditions, such as the exposure to vacuum at different temperatures. This study yields insights into the nature of binding sites in MOFs, how these are affected by activation, and helps to pave the way for the improved design of processing conditions.
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Aug 2025
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I19-Small Molecule Single Crystal Diffraction
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Russell M.
Main
,
Simon M.
Vornholt
,
Romy
Ettlinger
,
Philip
Netzsch
,
Maximillian G.
Stanzione
,
Cameron M.
Rice
,
Caroline
Elliott
,
Samantha E.
Russell
,
Mark R.
Warren
,
Sharon E.
Ashbrook
,
Russell E.
Morris
Diamond Proposal Number(s):
[29217, 32865]
Open Access
Abstract: Living on an increasingly polluted planet, the removal of toxic pollutants such as sulfur dioxide (SO2) from the troposphere and power station flue gas is becoming more and more important. The CPO-27/MOF-74 family of metal–organic frameworks (MOFs) with their high densities of open metal sites is well suited for the selective adsorption of gases that, like SO2, bind well to metals and have been extensively researched both practically and through computer simulations. However, until now, focus has centered upon the binding of SO2 to the open metal sites in this MOF (called chemisorption, where the adsorbent–adsorbate interaction is through a chemical bond). The possibility of physisorption (where the adsorbent–adsorbate interaction is only through weak intermolecular forces) has not been identified experimentally. This work presents an in situ single-crystal X-ray diffraction (scXRD) study that identifies discrete adsorption sites within Ni-MOF-74/Ni-CPO-27, where SO2 is both chemisorbed and physisorbed while also probing competitive adsorption of SO2 of these sites when water is present. Further features of this site have been confirmed by variable SO2 pressure scXRD studies, DFT calculations, and IR studies.
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Jan 2024
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I19-Small Molecule Single Crystal Diffraction
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Alexander J. R.
Thom
,
Gemma F.
Turner
,
Zachary H.
Davis
,
Martin R.
Ward
,
Ignas
Pakamore
,
Claire L.
Hobday
,
David R.
Allan
,
Mark R.
Warren
,
Wai L. W.
Leung
,
Iain D. H.
Oswald
,
Russell E.
Morris
,
Stephen A.
Moggach
,
Sharon E.
Ashbrook
,
Ross S.
Forgan
Diamond Proposal Number(s):
[24020]
Open Access
Abstract: Postsynthetic modification of metal-organic frameworks (MOFs) has proven a hugely powerful tool to tune physical properties and introduce functionality, by exploiting reactive sites on both the MOF linkers and their inorganic secondary building units (SBUs), and so has facilitated a wide range of applications. Studies into the reactivity of MOF SBUs have focussed solely on removal of neutral coordinating solvents, or direct exchange of linkers such as carboxylates, despite the prevalence of ancillary charge-balancing oxide and hydroxide ligands found in many SBUs. Herein, we show that the µ2-OH ligands in the MIL-53 topology Sc MOF, GUF-1, are labile, and can be substituted for µ2-OCH3 units through reaction with pore-bound methanol molecules in a very rare example of pressure-induced postsynthetic modification. Using comprehensive solid-state NMR spectroscopic analysis, we show an order of magnitude increase in this cluster anion substitution process after exposing bulk samples suspended in methanol to a pressure of 0.8 GPa in a large volume press. Additionally, single crystals compressed in diamond anvil cells with methanol as the pressure-transmitting medium have enabled full structural characterisation of the process across a range of pressures, leading to a quantitative single-crystal to single-crystal conversion at 4.98 GPa. This unexpected SBU reactivity – in this case chemisorption of methanol – has implications across a range of MOF chemistry, from activation of small molecules for heterogeneous catalysis to chemical stability, and we expect cluster anion substitution to be developed into a highly convenient novel method for modifying the internal pore surface and chemistry of a range of porous materials.
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Jun 2023
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[29217]
Open Access
Abstract: Metal-organic frameworks (MOFs) are well known for their ability to adsorb various gases. The use of MOFs for the storage and release of biologically active gases, particularly nitric oxide (NO) and carbon monoxide (CO), has been a subject of interest. To elucidate the binding mechanisms and geometry of these gases, an in situ single crystal X-ray diffraction (scXRD) study using synchrotron radiation at Diamond Light Source has been performed on a set of MOFs that display promising gas adsorption properties. NO and CO, were introduced into activated Ni-CPO-27 and the related Co-4,6-dihydroxyisophthalate (Co-4,6-dhip). Both MOFs show strong binding affinity towards CO and NO, however CO suffers more from competitive co-adsorption of water. Additionally, we show that morphology can play an important role in the ease of dehydration for these two systems.
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Mar 2023
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[26990]
Open Access
Abstract: An in situ pair distribution function study assessing the reassembly of three IM-12 (UTL) intermediate materials to the corresponding fully connected materials. A greater level of atomic change is observed at higher temperatures for the reassembly of the fully disconnected intermediate, IPC-1P, compared to the two partially connected intermediates of IPC-2P and IPC-6P.
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Nov 2022
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Nuria
Tapia-Ruiz
,
A. Robert
Armstrong
,
Hande
Alptekin
,
Marco A.
Amores
,
Heather
Au
,
Jerry
Barker
,
Rebecca
Boston
,
William R
Brant
,
Jake M.
Brittain
,
Yue
Chen
,
Manish
Chhowalla
,
Yong-Seok
Choi
,
Sara I. R.
Costa
,
Maria
Crespo Ribadeneyra
,
Serena A
Cussen
,
Edmund J.
Cussen
,
William I. F.
David
,
Aamod V
Desai
,
Stewart A. M.
Dickson
,
Emmanuel I.
Eweka
,
Juan D.
Forero-Saboya
,
Clare
Grey
,
John M.
Griffin
,
Peter
Gross
,
Xiao
Hua
,
John T. S.
Irvine
,
Patrik
Johansson
,
Martin O.
Jones
,
Martin
Karlsmo
,
Emma
Kendrick
,
Eunjeong
Kim
,
Oleg V
Kolosov
,
Zhuangnan
Li
,
Stijn F L
Mertens
,
Ronnie
Mogensen
,
Laure
Monconduit
,
Russell E
Morris
,
Andrew J.
Naylor
,
Shahin
Nikman
,
Christopher A
O’keefe
,
Darren M. C.
Ould
,
Robert G.
Palgrave
,
Philippe
Poizot
,
Alexandre
Ponrouch
,
Stéven
Renault
,
Emily M.
Reynolds
,
Ashish
Rudola
,
Ruth
Sayers
,
David O.
Scanlon
,
S.
Sen
,
Valerie R.
Seymour
,
Begoña
Silván
,
Moulay Tahar
Sougrati
,
Lorenzo
Stievano
,
Grant S.
Stone
,
Chris I.
Thomas
,
Maria-Magdalena
Titirici
,
Jincheng
Tong
,
Thomas J.
Wood
,
Dominic S
Wright
,
Reza
Younesi
Open Access
Abstract: Increasing concerns regarding the sustainability of lithium sources, due to their limited availability and consequent expected price increase, have raised awareness of the importance of developing alternative energy-storage candidates that can sustain the ever-growing energy demand. Furthermore, limitations on the availability of the transition metals used in the manufacturing of cathode materials, together with questionable mining practices, are driving development towards more sustainable elements. Given the uniformly high abundance and cost-effectiveness of sodium, as well as its very suitable redox potential (close to that of lithium), sodium-ion battery technology offers tremendous potential to be a counterpart to lithium-ion batteries (LIBs) in different application scenarios, such as stationary energy storage and low-cost vehicles. This potential is reflected by the major investments that are being made by industry in a wide variety of markets and in diverse material combinations. Despite the associated advantages of being a drop-in replacement for LIBs, there are remarkable differences in the physicochemical properties between sodium and lithium that give rise to different behaviours, for example, different coordination preferences in compounds, desolvation energies, or solubility of the solid–electrolyte interphase inorganic salt components. This demands a more detailed study of the underlying physical and chemical processes occurring in sodium-ion batteries and allows great scope for groundbreaking advances in the field, from lab-scale to scale-up. This roadmap provides an extensive review by experts in academia and industry of the current state of the art in 2021 and the different research directions and strategies currently underway to improve the performance of sodium-ion batteries. The aim is to provide an opinion with respect to the current challenges and opportunities, from the fundamental properties to the practical applications of this technology.
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Jul 2021
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[24028]
Open Access
Abstract: The size of single crystals of the metal-organic framework CPO-27-Ni was incrementally increased through a series of modulated syntheses. A novel linker modulated synthesis using 2,5-dihydroxyterephthalic acid and the isomeric ligand 4,6-dihydroxyisophthalic acid yielded large single crystals of CPO-27-Ni (~70 µm). All materials proved high crystallinity and phase pure through powder X-ray diffraction, electron microscopy methods, thermogravimetric, and compositional analysis. For the first time single crystal structure analyses were carried out on CPO-27-Ni. High BET surface areas and nitric oxide (NO) release efficiencies were recorded for all materials. Large single crystals of CPO-27-Ni showed a prolonged NO release and proved suitable for in situ single crystal diffraction experiments to follow the NO adsorption. An efficient activation protocol was developed, leading to a dehydrated structure after just 4 h, which subsequently was NO-loaded, giving a first NO loaded single crystal structural model of CPO-27-Ni.
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Mar 2021
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[14567]
Abstract: The conjugated dicarboxylate, sodium naphthalene‐2,6‐dicarboxylate (Na2NDC), has been prepared by a low energy consumption reflux method and its performance as a negative electrode for sodium‐ion batteries evaluated in electrochemical cells. The structure of Na2NDC was solved for the first time (monoclinic P21/c) from powder X‐ray diffraction data and consists of π‐stacked naphthalene units separated by sodium‐oxygen layers. Through an appropriate choice of binder and conducting carbon additive Na2NDC exhibits a reversible two electron sodium insertion at around 0.4 V vs. Na+/Na with remarkably stable capacities of ca. 200 mA h g‐1 at a rate of C/2 and good rate capability (~133 mA h g‐1 at 5C). In parallel the high thermal stability of the material is demonstrated by HT‐X‐ray diffraction, the framework remaining intact to above 500 °C.
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Aug 2019
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I15-Extreme Conditions
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Abstract: A study into the disassembly and organisation steps of the ADOR process has been undertaken through in situ Pair Distribution Function (PDF) analysis. Three aqueous systems (water, 6 M HCl and 12 M HCl) were introduced to a parent zeolite germanosilicate UTL in a cell. Hydrolysis could be clearly seen when UTL was exposed to water over a period of 8 hr, forming the disorded layered material, IPC-1P. In hydrochloric acid, the hydrolysis step is too quick to observe and a Ge-Cl containing species could be seen. In 6 M HCl, the rearrangement of the interlayer region began after an induction period of 8 hr, with the process still occuring after 15 hr. In 12 M HCl, the rearrangement appears to have come to an end after only 6 hr.
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Aug 2018
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