B22-Multimode InfraRed imaging And Microspectroscopy
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Gemma L.
Smith
,
Jennifer E.
Eyley
,
Xue
Han
,
Xinran
Zhang
,
Jiangnan
Li
,
Nicholas M.
Jacques
,
Harry G. W.
Godfrey
,
Stephen P.
Argent
,
Laura J.
Mccormick Mcpherson
,
Simon J.
Teat
,
Yongqiang
Cheng
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Sarah
Day
,
Chiu C.
Tang
,
Timothy L.
Easun
,
Svemir
Rudic
,
Anibal J.
Ramirez-cuesta
,
Sihai
Yang
,
Martin
Schroeder
Abstract: Emissions of SO2 from flue gas and marine transport have detrimental impacts on the environment and human health, but SO2 is also an important industrial feedstock if it can be recovered, stored and transported efficiently. Here we report the exceptional adsorption and separation of SO2 in a porous material, [Cu2(L)] (H4L = 4′,4‴-(pyridine-3,5-diyl)bis([1,1′-biphenyl]-3,5-dicarboxylic acid)), MFM-170. MFM-170 exhibits fully reversible SO2 uptake of 17.5 mmol g−1 at 298 K and 1.0 bar, and the SO2 binding domains for trapped molecules within MFM-170 have been determined. We report the reversible coordination of SO2 to open Cu(ii) sites, which contributes to excellent adsorption thermodynamics and selectivities for SO2 binding and facile regeneration of MFM-170 after desorption. MFM-170 is stable to water, acid and base and shows great promise for the dynamic separation of SO2 from simulated flue gas mixtures, as confirmed by breakthrough experiments.
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Oct 2019
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B22-Multimode InfraRed imaging And Microspectroscopy
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Xinchen
Kang
,
Kai
Lyu
,
Lili
Li
,
Jiangnan
Li
,
Louis
Kimberley
,
Bin
Wang
,
Lifei
Liu
,
Yongqiang
Cheng
,
Mark D.
Frogley
,
Svemir
Rudic
,
Anibal J.
Ramirez-cuesta
,
Robert A. W.
Dryfe
,
Buxing
Han
,
Sihai
Yang
,
Martin
Schroder
Diamond Proposal Number(s):
[19171]
Open Access
Abstract: Incorporation of mesopores and active sites into metal-organic framework (MOF) materials to uncover new efficient catalysts is a highly desirable but challenging task. We report the first example of a mesoporous MOF obtained by templated electrosynthesis using an ionic liquid as both electrolyte and template. The mesoporous Cu(II)-MOF MFM-100 has been synthesised in 100 seconds at room temperature, and this material incorporates crystal defects with uncoupled Cu(II) centres as evidenced by confocal fluorescence microscopy and electron paramagnetic resonance spectroscopy. MFM-100 prepared in this way shows exceptional catalytic activity for the aerobic oxidation of alcohols to produce aldehydes in near quantitative yield and selectivity under mild conditions, as well as having excellent stability and reusability over repeated cycles. The catalyst-substrate binding interactions have been probed by inelastic neutron scattering. This study offers a simple strategy to create mesopores and active sites simultaneously via electrochemical formation of crystal defects to promote efficient catalysis using MOFs.
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Oct 2019
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I11-High Resolution Powder Diffraction
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Xinran
Zhang
,
Ivan
Da Silva
,
Rodrigo
Fazzi
,
Alena M.
Sheveleva
,
Xue
Han
,
Ben F.
Spencer
,
Sergey A.
Sapchenko
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Ming
Li
,
Sihai
Yang
,
Martin
Schroder
Diamond Proposal Number(s):
[21079]
Abstract: We report a comparative study of the binding of I2 (iodine) in a pair of redox-active metal–organic framework (MOF) materials, MFM-300(VIII) and its oxidized, deprotonated analogue, MFM-300(VIV). Adsorption of I2 in MFM-300(VIII) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the VIII centers in the host framework and formation of I3– species residing in the MOF channels. Importantly, this charge-transfer induces a significant enhancement in the electrical conductivity (Δσ = 700000) of I2@MFM-300(VIII/IV) in comparison to MFM-300(VIII). In contrast, no host–guest charge-transfer or apparent change in the conductivity was observed upon adsorption of I2 in MFM-300(VIV). High-resolution synchrotron X-ray diffraction of I2@MFM-300(VIII/IV) confirms the first example of self-aggregation of adsorbed iodine species (I2 and I3–) into infinite helical chains within a MOF.
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Sep 2019
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I19-Small Molecule Single Crystal Diffraction
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Peter
Rought
,
Christopher
Marsh
,
Simona
Pili
,
Ian P.
Silverwood
,
Victoria
Garcia Sakai
,
Ming
Li
,
Martyn
Brown
,
Stephen P.
Argent
,
Inigo
Vitorica-yrezabal
,
George
Whitehead
,
Mark R.
Warren
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[13650, 12517]
Open Access
Abstract: Three multi-carboxylic acid functionalised ligands have been designed, synthesised and utilised to synthesise the new barium-based MOFs, MFM-510, -511, and -512, which show excellent stability to water-vapour. MFM-510 and MFM-511 show moderate proton conductivities (2.1 x10-5 and 5.1 x10-5 S cm-1, respectively) at 99RH% and 298 K, attributed to the lack of free protons or hindered proton diffusion within the framework structures. In contrast, MFM-512, which incorporates a pendant carboxylic acid group directed into the pore of the framework, shows a two orders of magnitude enhancement in proton conductivity (2.9 x10-3 S cm-1). Quasi-elastic neutron scattering (QENS) suggests that the proton dynamics of MFM-512 are mediated by “free diffusion inside a sphere” confirming that incorporation of free carboxylic acid groups within the pores of MOFs is an efficient albeit a synthetically challenging strategy to improve proton conductivity.
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Nov 2018
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[14341]
Abstract: We report a record-high SO2 adsorption capacity of 12.3 mmol g–1 in a robust porous material, MFM-601, at 298 K and 1.0 bar. SO2 adsorption in MFM-601 is fully reversible and highly selective over CO2 and N2. The binding domains for adsorbed SO2 and CO2 molecules in MFM-601 have been determined by in situ synchrotron X-ray diffraction experiments, giving insights at the molecular level to the basis of the observed high selectivity.
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Nov 2018
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B22-Multimode InfraRed imaging And Microspectroscopy
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Jack
Humby
,
Oguarabau
Benson
,
Gemma L.
Smith
,
Stephen P.
Argent
,
Ivan
Da Silva
,
Yongqiang
Cheng
,
Svemir
Rudic
,
Pascal
Manuel
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Lucy K.
Saunders
,
Inigo
Vitorica-yrezabal
,
George F. S.
Whitehead
,
Timothy L.
Easun
,
William
Lewis
,
Alexander J.
Blake
,
Anibal J.
Ramirez-cuesta
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[13666]
Open Access
Abstract: In order to develop new porous materials for applications in gas separations such as natural gas upgrading, landfill gas processing and acetylene purification it is vital to gain understanding of host-substrate interactions at a molecular level. Herein we report a series of six isoreticular metal-organic frameworks (MOFs) for selective gas adsorption. These materials do not incorporate open metal sites and thus provide an excellent platform to investigate the effect of the incorporation of ligand functionality via amide and alkyne groups on substrate binding. By reducing the linker length of our previously reported MFM-136, we report much improved CO2/CH4 (50:50) and CO2/N¬2 (15:85) selectivity values of 20.2 and 65.4, respectively (1 bar and 273 K), in the new amide-decorated MOF, MFM-126. The CO2 separation performance of MFM-126 has been confirmed by dynamic breakthrough experiments. In situ inelastic neutron scattering and synchrotron FT-IR microspectroscopy were employed to elucidate dynamic interactions of adsorbed CO2 molecules within MFM-126. Upon changing the functionality to an alkyne group in MFM-127, the CO2 uptake decreases but the C2H2 uptake increases by 68%, leading to excellent C2H2/CO2 and C2H2/CH4 selectivities of 3.7 and 21.2, respectively. Neutron powder diffraction enabled the direct observation of the preferred binding domains in MFM-126 and MFM-127, and, to the best of our knowledge, we report the first example of acetylene binding to an alkyne moiety in a porous material, with over 50% of the acetylene observed within MFM-127 displaying interactions (<4 Å) with the alkyne functionality of the framework.
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Oct 2018
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Lei
Li
,
Ivan
Da Silva
,
Daniil I.
Kolokolov
,
Xue
Han
,
Jiangnan
Li
,
Gemma
Smith
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Christopher G.
Morris
,
Harry G. W.
Godfrey
,
Nicholas
Jacques
,
Xinran
Zhang
,
Pascal
Manuel
,
Mark D.
Frogley
,
Claire A.
Murray
,
Anibal J.
Ramirez-cuesta
,
Gianfelice
Cinque
,
Chiu C.
Tang
,
Alexander G.
Stepanov
,
Sihai
Yang
,
Martin
Schroder
Diamond Proposal Number(s):
[14564, 15970]
Open Access
Abstract: Modulation of pore environment is an effective strategy to optimize guest binding in porous materials. We report the post-synthetic modification of the charge distribution in a charged metal-organic framework, MFM-305-CH3, [Al(OH)(L)]Cl, [(H2L)Cl = 3,5-dicarboxy-1-methylpyridinium chloride] and its effect on guest binding. MFM-305-CH3 shows a distribution of cationic (methylpyridinium) and anionic (chloride) centers and can be modified to release free pyridyl N-centres by thermal demethylation of the 1-methylpyridinium moiety to give the neutral isostructural MFM-305. This leads simultaneously to enhanced adsorption capacities and selectivities (two parameters that often change in opposite directions) for CO2 and SO2 in MFM-305. The host-guest binding has been comprehensively investigated by in situ synchrotron X-ray and neutron powder diffraction, inelastic neutron scattering, synchrotron infrared and 2H NMR spectroscopy and theoretical modelling to reveal the binding domains of CO2 and SO2 in these materials. CO2 and SO2 binding in MFM-305-CH3 is shown to occur via hydrogen bonding to the methyl and aromatic-CH groups, with a long range interaction to chloride for CO2. In MFM-305 the hydroxyl, pyridyl and aromatic C-H groups bind CO2 and SO2 more effectively via hydrogen bonds and dipole interactions. Post-synthetic modification via dealkylation of the as-synthesised metal-organic framework is a powerful route to the synthesis of materials incorporating active polar groups that cannot be prepared directly.
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Oct 2018
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I11-High Resolution Powder Diffraction
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Simona
Pili
,
Peter
Rought
,
Daniil I.
Kolokolov
,
Longfei
Lin
,
Ivan
Da Silva
,
Yongqiang
Cheng
,
Christopher
Marsh
,
Ian P.
Silverwood
,
Victoria
García-sakai
,
Ming
Li
,
Jeremy J.
Titman
,
Lyndsey
Knight
,
Luke L.
Daemen
,
Anibal J.
Ramirez-cuesta
,
Chiu C.
Tang
,
Alexander G.
Stepanov
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[13247]
Abstract: Owing to their inherent pore structure, porous metal-organic frameworks (MOFs) can undergo post-synthetic modification, such as loading extra-framework proton carriers. However, strategies for improving the proton conductivity for non-porous MOFs are largely lacking, although increasing numbers of non-porous MOFs exhibit promising proton conductivities. Often, high humidity is required for non-porous MOFs to achieve high conductivities, but to date no clear mechanisms have been experimentally identified. Here we describe the new materials MFM-550(M), [M(HL1)], (H4L1 = biphenyl-4,4'-diphosphonic acid; M = La, Ce, Nd, Sm, Gd, Ho), MFM-550(Ba), [Ba(H2L1)], and MFM-555(M), [M(HL2)], (H4L2 = benzene-1,4-diphosphonic acid; M = La, Ce, Nd, Sm, Gd, Ho), and report enhanced proton conductivities in these non-porous materials by (i) replacing the metal ion to one with a lower oxidation state, (ii) reducing the length of the organic ligand, and (iii) introducing additional acidic protons on MOF surface. Increased framework proton density in these materials can lead to an enhancement in proton conductivity of up to four orders of magnitude. Additionally, we report a comprehensive investigation using in situ 2H NMR and neutron spectroscopy, coupled with molecular dynamic modelling, to elucidate the role of humidity in assembling interconnected networks for proton hopping. This study constructs a relationship between framework proton density and the corresponding proton conductivity in non-porous MOFs, and directly explains the role of both surface protons and external water in assembling the proton conducting pathways.
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Sep 2018
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Martin
Schroder
,
Harry
Godfrey
,
Ivan
Da Silva
,
Lydia
Briggs
,
Joe
Carter
,
Christopher
Morris
,
Mathew
Savage
,
Timothy
Easun
,
Pascal
Manuel
,
Claire
Murray
,
Chiu
Tang
,
Mark
Frogley
,
Gianfelice
Cinque
,
Sihai
Yang
Diamond Proposal Number(s):
[15972, 13666]
Abstract: MFM‐300(Al) shows reversible uptake of NH3 (15.7 mmol g‐1 at 273 K and 1.0 bar) over 50 cycles with an exceptional packing density of 0.62 g cm‐3 at 293 K. In situ neutron powder diffraction and synchrotron FTIR micro‐spectroscopy on ND3@MFM‐300(Al) confirms reversible H/D site exchange between the adsorbent and adsorbate, representing a new type of adsorption interaction.
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Aug 2018
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B22-Multimode InfraRed imaging And Microspectroscopy
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Nicholas M.
Jacques
,
Peter R. E.
Rought
,
Detlev
Fritsch
,
Mathew
Savage
,
Harry G. W.
Godfrey
,
Lei
Li
,
Tamoghna
Mitra
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Sihai
Yang
,
Martin
Schroder
Diamond Proposal Number(s):
[17709]
Abstract: The binding domains within a mixed matrix membrane (MMM) that is selective for CO2 comprising MFM-300(Al) and the polymer 6FDA-Durene-DABA have been established via in situ synchrotron IR microspectroscopy. The MOF crystals are fully accessible and play a critical role in the binding of CO2, creating a selective pathway to promote permeation of CO2 within and through the MMM. This study reveals directly the molecular mechanism for the overall enhanced performance of this MMM in terms of permeability, solubility and selectivity for CO2.
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Mar 2018
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