I11-High Resolution Powder Diffraction
I19-Small Molecule Single Crystal Diffraction
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Stephen P.
Argent
,
Ivan
Da Silva
,
Alex
Greenaway
,
Mathew
Savage
,
Jack
Humby
,
Andrew J.
Davies
,
Harriott
Nowell
,
William
Lewis
,
Pascal
Manuel
,
Chiu C.
Tang
,
Alexander J.
Blake
,
Michael W.
George
,
Alexander V.
Markevich
,
Elena
Besley
,
Sihai
Yang
,
Neil R.
Champness
,
Martin
Schroeder
Open Access
Abstract: Designing porous materials which can selectively adsorb CO2 or CH4 is an important environmental and industrial goal which requires an understanding of the host–guest interactions involved at the atomic scale. Metal–organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family of MOPs (Cu-1a, Cu-1b, Cu-2), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra. Thus, for Cu-1a, the void fraction outside the cages totals 56% with only 2% within. The relative stabilities of these MOP structures are rationalized by considering their weak nondirectional packing interactions using Hirshfeld surface analyses. The exceptional stability of Cu-1a enables a detailed structural investigation into the adsorption of CO2 and CH4 using in situ X-ray and neutron diffraction, coupled with DFT calculations. The primary binding sites for adsorbed CO2 and CH4 in Cu-1a are found to be the open metal sites and pockets defined by the faces of phenyl rings. More importantly, the structural analysis of a hydrated sample of Cu-1a reveals a strong hydrogen bond between the adsorbed CO2 molecule and the Cu(II)-bound water molecule, shedding light on previous empirical and theoretical observations that partial hydration of metal−organic framework (MOF) materials containing open metal sites increases their uptake of CO2. The results of the crystallographic study on MOP–gas binding have been rationalized using DFT calculations, yielding individual binding energies for the various pore environments of Cu-1a.
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Oct 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
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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
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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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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[14555]
Open Access
Abstract: Temperature or pressure-swing sorption in porous metal-organic framework (MOF) materials has been proposed for new gas separation technologies. The high tuneability of MOFs toward particular adsorbates and the relatively low energy penalty for system regeneration means that reversible physisorption in MOFs has the potential to create economic and environmental benefits compared with state-of-the-art chemisorption systems. However, for MOF-based sorbents to be commercialised they have to show long-term stability under the conditions imposed by the application. Here, we demonstrate the structural stability of MFM-300(Al) to the presence of a series of industrially-relevant toxic and corrosive gases, including SO2, NO2 and NH3, over four years using long duration synchrotron X-ray powder diffraction. Full structural analysis of gas-loaded MFM-300(Al) confirms the retention of these toxic gas molecules within the porous framework for up to 200 weeks, and cycling adsorption experiments verified the reusability of MFM-300(Al) for the capture of these toxic air pollutants.
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Aug 2020
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B22-Multimode InfraRed imaging And Microspectroscopy
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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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I11-High Resolution Powder Diffraction
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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
Diamond Proposal Number(s):
[23483]
Open Access
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.
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May 2020
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[22138]
Abstract: Coordination pillared-layer metal-organic frameworks (CPL-MOFs), such as CPL-2, are interesting versatile and porous materials with the potential for gas adsorption and separation. CPL-2 shows the unusual and gradual linker rotation upon the adsorption of ethylene (C2H4) and ethane (C2H6), leading to a fully reversible adsorption isotherm specifically under the conditions studied. Grand canonical Monte Carlo (GCMC) simulations showed that it is impossible to accommodate the experimentally observed loadings of C2H4 and C2H6 in CPL-2 using the crystallographic structure reported in the literature. According to the simulation findings, the pore expansion might be initiated by the clockwise 4,4′-bipyridine (bpy) pillar linker rotation. The pillar rotation leads to the enlarged pore volume, rendering additional adsorption sites, which are not present in the pristine structure. In situ synchrotron PXRD experiments for C2H4 and C2H6 adsorption on CPL-2 confirmed the occurrence of pore expansion in CPL-2 MOF. The combined experimental and simulation study shows for the first time that the linker rotation in CPL-2 can result in a adsorption isotherm without hysteresis. This work developed a real insight into the nature of pillared-layer MOFs, and the revealed structural changes could be potentially exploited to enhance alkene and alkane working capacities of such microporous materials.
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Feb 2020
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
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Longfei
Lin
,
Alena M.
Sheveleva
,
Ivan
Da Silva
,
Christopher M. A.
Parlett
,
Zhimou
Tang
,
Yueming
Liu
,
Mengtian
Fan
,
Xue
Han
,
Joseph H.
Carter
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Svemir
Rudic
,
Anibal J.
Ramirez-cuesta
,
Chiu C.
Tang
,
Sihai
Yang
Diamond Proposal Number(s):
[15151, 24726]
Abstract: The efficient production of light olefins from renewable biomass is a vital and challenging target to achieve future sustainable chemical processes. Here we report a hetero-atomic MFI-type zeolite (NbAlS-1), over which aqueous solutions of γ-valerolactone (GVL), obtained from biomass-derived carbohydrates, can be quantitatively converted into butenes with a yield of >99% at ambient pressure under continuous flow conditions. NbAlS-1 incorporates simultaneously niobium(v) and aluminium(iii) centres into the framework and thus has a desirable distribution of Lewis and Brønsted acid sites with optimal strength. Synchrotron X-ray diffraction and absorption spectroscopy show that there is cooperativity between Nb(v) and the Brønsted acid sites on the confined adsorption of GVL, whereas the catalytic mechanism for the conversion of the confined GVL into butenes is revealed by in situ inelastic neutron scattering, coupled with modelling. This study offers a prospect for the sustainable production of butene as a platform chemical for the manufacture of renewable materials.
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Dec 2019
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B23-Circular Dichroism
I19-Small Molecule Single Crystal Diffraction
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Zongsu
Han
,
Kunyu
Wang
,
Yifan
Guo
,
Wenjie
Chen
,
Jiale
Zhang
,
Xinran
Zhang
,
Giuliano
Siligardi
,
Sihai
Yang
,
Zhen
Zhou
,
Pingchuan
Sun
,
Wei
Shi
,
Peng
Cheng
Diamond Proposal Number(s):
[20293]
Open Access
Abstract: The integration of luminescence and chirality in easy-scalable metal-organic frameworks gives rise to the development of advanced luminescent sensors. To date, the synthesis of chiral metal-organic frameworks is poorly predictable and their chirality primarily originates from components that constitute the frameworks. By contrast, the introduction of chirality into the pores of metal-organic frameworks has not been explored to the best of our knowledge. Here, we demonstrate that chirality can be introduced into an anionic Zn-based metal-organic framework via simple cation exchange, yielding dual luminescent centers comprised of the ligand and Tb3+ ions, accompanied by a chiral center in the pores. This bifunctional material shows enantioselectivity luminescent sensing for a mixture of stereoisomers, demonstrated for Cinchonine and Cinchonidine epimers and amino alcohol enantiomers, from which the quantitative determination of the stereoisomeric excess has been obtained. This study paves a pathway for the design of multifunctional metal-organic framework systems as a useful method for rapid sensing of chiral molecules.
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Nov 2019
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
I12-JEEP: Joint Engineering, Environmental and Processing
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Harry G. W.
Godfrey
,
Lydia
Briggs
,
Xue
Han
,
William J. F.
Trenholme
,
Christopher
Morris
,
Mathew
Savage
,
Louis
Kimberley
,
Oxana
Magdysyuk
,
Michael
Drakopoulos
,
Claire A.
Murray
,
Chiu C.
Tang
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[11278]
Open Access
Abstract: Understanding the mechanism of assembly and function of metal-organic frameworks (MOFs) is important for the development of practical materials. Herein, we report a time-resolved diffraction analysis of the kinetics of formation of a robust MOF, MFM-300(Fe), which shows high adsorption capacity for CO2 (9.55 mmol g−1 at 293 K and 20 bar). Applying the Avrami-Erofe’ev and the two-step kinetic Finke-Watzky models to in situ high-energy synchrotron X-ray powder diffraction data obtained during the synthesis of MFM-300(Fe) enables determination of the overall activation energy of formation (50.9 kJ mol−1), the average energy of nucleation (56.7 kJ mol−1), and the average energy of autocatalytic growth (50.7 kJ mol−1). The synthesis of MFM-300(Fe) has been scaled up 1000-fold, enabling the successful breakthrough separations of the CO2/N2 mixture in a packed-bed with a selectivity for CO2/N2 of 21.6. This study gives an overall understanding for the intrinsic behaviors of this MOF system, and we have determined directly the binding domains and dynamics for adsorbed CO2 molecules within the pores of MFM-300(Fe).
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Nov 2019
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