I19-Small Molecule Single Crystal Diffraction
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Mei-Yan
Gao
,
Andrey A.
Bezrukov
,
Bai-Qiao
Song
,
Meng
He
,
Sousa Javan
Nikkhah
,
Shi-Qiang
Wang
,
Naveen
Kumar
,
Shaza
Darwish
,
Debobroto
Sensharma
,
Chenghua
Deng
,
Jiangnan
Li
,
Lunjie
Liu
,
Rajamani
Krishna
,
Matthias
Vandichel
,
Sihai
Yang
,
Michael J.
Zaworotko
Open Access
Abstract: Ultramicroporous materials can be highly effective at trace gas separations when they offer a high density of selective binding sites. Herein, we report that sql-NbOFFIVE-bpe-Cu, a new variant of a previously reported ultramicroporous square lattice, sql, topology material, sql-SIFSIX-bpe-Zn, can exist in two polymorphs. These polymorphs, sql-NbOFFIVE-bpe-Cu-AA (AA) and sql-NbOFFIVE-bpe-Cu-AB (AB), exhibit AAAA and ABAB packing of the sql layers, respectively. Whereas NbOFFIVE-bpe-Cu-AA (AA) is isostructural with sql-SIFSIX-bpe-Zn, each exhibiting intrinsic 1D channels, sql-NbOFFIVE-bpe-Cu-AB (AB) has two types of channels, the intrinsic channels and extrinsic channels between the sql networks. Gas and temperature induced transformations of the two polymorphs of sql-NbOFFIVE-bpe-Cu were investigated by pure gas sorption, single-crystal X-ray diffraction (SCXRD), variable temperature powder X-ray diffraction (VT-PXRD), and synchrotron PXRD. We observed that the extrinsic pore structure of AB resulted in properties with potential for selective C3H4/C3H6 separation. Subsequent dynamic gas breakthrough measurements revealed exceptional experimental C3H4/C3H6 selectivity (270) and a new benchmark for productivity (118 mmol g–1) of polymer grade C3H6 (purity >99.99%) from a 1:99 C3H4/C3H6 mixture. Structural analysis, gas sorption studies, and gas adsorption kinetics enabled us to determine that a binding “sweet spot” for C3H4 in the extrinsic pores is behind the benchmark separation performance. Density-functional theory (DFT) calculations and Canonical Monte Carlo (CMC) simulations provided further insight into the binding sites of C3H4 and C3H6 molecules within these two hybrid ultramicroporous materials, HUMs. These results highlight, to our knowledge for the first time, how pore engineering through the study of packing polymorphism in layered materials can dramatically change the separation performance of a physisorbent.
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May 2023
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I11-High Resolution Powder Diffraction
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Zi
Wang
,
Alena M.
Sheveleva
,
Daniel
Lee
,
Yinlin
Chen
,
Dinu
Iuga
,
W. Trent
Franks
,
Yujie
Ma
,
Jiangnan
Li
,
Lei
Li
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Sarah J.
Day
,
Anibal J.
Ramirez-Cuesta
,
Bing
Han
,
Alexander S.
Eggeman
,
Eric J. L.
Mcinnes
,
Floriana
Tuna
,
Sihai
Yang
,
Martin
Schroeder
Abstract: We report the modulation of reactivity of nitrogen dioxide (NO2) in a charged metal-organic framework (MOF) material, MFM-305-CH3 in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl− ions in the pores. Uptake of NO2 into MFM-305-CH3 leads to reaction between NO2 and Cl– to give nitrosyl chloride (NOCl) and NO3− anions. A high dynamic uptake of 6.58 mmol g−1 at 298 K is observed for MFM-305-CH3 as measured using a flow of 500 ppm NO2 in He. In contrast, the analogous neutral material, MFM-305, shows a much lower uptake of 2.38 mmol g−1. The binding domains and reactivity of adsorbed NO2 molecules within MFM-305-CH3 and MFM-305 have been probed using in situ synchrotron X-ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high-field solid-state nuclear magnetic resonance and UV-vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.
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Apr 2023
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B22-Multimode InfraRed imaging And Microspectroscopy
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Lixia
Guo
,
Joseph
Hurd
,
Meng
He
,
Wanpeng
Lu
,
Jiangnan
Li
,
Danielle
Crawshaw
,
Mengtian
Fan
,
Sergey A.
Sapchenko
,
Yinlin
Chen
,
Xiangdi
Zeng
,
Meredydd
Kippax-Jones
,
Wenyuan
Huang
,
Zhaodong
Zhu
,
Pascal
Manuel
,
Mark D.
Frogley
,
Daniel
Lee
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[30398]
Open Access
Abstract: The development of stable sorbent materials to deliver reversible adsorption of ammonia (NH3) is a challenging task. Here, we report the efficient capture and storage of NH3 in a series of robust microporous aluminium-based metal-organic framework materials, namely MIL-160, CAU-10-H, Al-fum, and MIL-53(Al). In particular, MIL-160 shows high uptakes of NH3 of 4.8 and 12.8 mmol g−1 at both low and high pressure (0.001 and 1.0 bar, respectively) at 298 K. The combination of in situ neutron powder diffraction, synchrotron infrared micro-spectroscopy and solid-state nuclear magnetic resonance spectroscopy reveals the preferred adsorption domains of NH3 molecules in MIL-160, with H/D site-exchange between the host and guest and an unusual distortion of the local structure of [AlO6] moieties being observed. Dynamic breakthrough experiments confirm the excellent ability of MIL-160 to capture of NH3 with a dynamic uptake of 4.2 mmol g−1 at 1000 ppm. The combination of high porosity, pore aperture size and multiple binding sites promotes the significant binding affinity and capacity for NH3, which makes it a promising candidate for practical applications.
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Mar 2023
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I11-High Resolution Powder Diffraction
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Jiangnan
Li
,
Zi
Wang
,
Yinlin
Chen
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Sarah J.
Day
,
Anibal J.
Ramirez-Cuesta
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[31365]
Open Access
Abstract: Increasing levels of air pollution are driving the need for the development of new processes that take “waste-to-chemicals”. Herein, we report the capture and conversion under ambient conditions of a major air pollutant, NO2, using a robust metal-organic framework (MOF) material, Zr-bptc (H4bptc = 3,3′,5,5′-biphenyltetracarboxylic acid), comprising {Zr6(μ3-O)4(μ3-OH)4(COO)12} clusters linked by 4-connected bptc4– ligands in an ftw topology. At 298 K, Zr-bptc shows exceptional stability and adsorption of NO2 at both low (4.9 mmol g–1 at 10 mbar) and high pressures (13.8 mmol g–1 at 1.0 bar), as measured by isotherm experiments. Dynamic breakthrough experiments have confirmed the selective retention of NO2 by Zr-bptc at low concentrations under both dry and wet conditions. The immobilized NO2 can be readily transformed into valuable nitro compounds relevant to construction, agrochemical, and pharmaceutical industries. In situ crystallographic and spectroscopic studies reveal strong binding interactions of NO2 to the {Zr6(μ3-O)4(μ3-OH)4(COO)12} cluster node. This study paves a circular pathway to enable the integration of nitrogen-based air pollutants into the production of fine chemicals.
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Oct 2022
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B22-Multimode InfraRed imaging And Microspectroscopy
I19-Small Molecule Single Crystal Diffraction
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Weiyao
Li
,
Jiangnan
Li
,
Thien D.
Duong
,
Sergey A.
Sapchenko
,
Xue
Han
,
Jack D.
Humby
,
George F. S.
Whitehead
,
Inigo J.
Vitórica-Yrezábal
,
Ivan
Da Silva
,
Pascal
Manuel
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[28479, 23480]
Open Access
Abstract: The development of efficient sorbent materials for sulfur dioxide (SO2) is of key industrial interest. However, due to the corrosive nature of SO2, conventional porous materials often exhibit poor reversibility and limited uptake toward SO2 sorption. Here, we report high adsorption of SO2 in a series of Cu(II)-carboxylate-based metal–organic framework materials. We describe the impact of ligand functionalization and open metal sites on the uptake and reversibility of SO2 adsorption. Specifically, MFM-101 and MFM-190(F) show fully reversible SO2 adsorption with remarkable capacities of 18.7 and 18.3 mmol g–1, respectively, at 298 K and 1 bar; the former represents the highest reversible uptake of SO2 under ambient conditions among all porous solids reported to date. In situ neutron powder diffraction and synchrotron infrared microspectroscopy enable the direct visualization of binding domains of adsorbed SO2 molecules as well as host–guest binding dynamics. We have found that the combination of open Cu(II) sites and ligand functionalization, together with the size and geometry of metal–ligand cages, plays an integral role in the enhancement of SO2 binding.
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Jul 2022
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I11-High Resolution Powder Diffraction
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Shanshan
Liu
,
Yinlin
Chen
,
Bin
Yue
,
Chang
Wang
,
Bin
Qin
,
Yuchao
Chai
,
Guangjun
Wu
,
Jiangnan
Li
,
Xue
Han
,
Ivan
Da Silva
,
Pascal
Manuel
,
Sarah J.
Day
,
Naijia
Guan
,
Stephen P.
Thompson
,
Sihai
Yang
,
Landong
Li
Diamond Proposal Number(s):
[29649]
Abstract: The development of cost-effective sorbents for direct capture of trace CO 2 (<1%) from the atmosphere is an important and challenging task. Natural or commercial zeolites are promising sorbents, but their performance in adsorption of trace CO 2 has been poorly explored to date. Herein, we report a systematic study on capture of trace CO 2 by commercial faujasite zeolites, where we found that the extra-framework cations played a key role on their performance. Under dry conditions, Ba-X displays high dynamic uptake of 1.79 and 0.69 mmol g -1 at CO 2 concentrations of 10000 and 1000 ppm, respectively, and shows excellent recyclability in the temperature-swing adsorption processes. K-X exhibits perfect moisture resistance, and >95 % dry CO 2 uptake can be preserved under relative humidity of 74%. In situ solid-state NMR spectroscopy, synchrotron X-ray diffraction and neutron diffraction reveal two binding sites for CO 2 in these zeolites, namely the basic framework oxygen atoms and the divalent alkaline earth metal ions. This study unlocks the potential of low-cost natural zeolites for applications in direct air capture.
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Jun 2022
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
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Jiangnan
Li
,
Gemma L.
Smith
,
Yinlin
Chen
,
Yujie
Ma
,
Meredydd
Kippax-Jones
,
Mengtian
Fan
,
Wanpeng
Lu
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Sarah
Day
,
Stephen P.
Thompson
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Anibal J.
Ramirez-Cuetos
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[28497, 29649]
Open Access
Abstract: We report reversible high capacity adsorption of SO2 in robust Zr-based metal-organic frameworks (MOFs). Zr-bptc (H4bptc = biphenyl-3,3’,5,5’-tetracarboxylic acid) shows a high SO2 uptake of 6.2 mmol g-1 at 0.1 bar and 298 K, reflecting excellent capture capability and removal of SO2 at low concentration (2500 ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically-dispersed Cu(II) or heteroatomic sulphur sites into the pores enhance the capture of SO2 at low concentrations. The captured SO2 can be converted quantitatively to a pharmaceutical intermediate, aryl N-aminosulfonamide, thus converting waste to chemical values. In situ X-ray diffraction, infrared micro-spectroscopic and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO2 molecules and host-guest binding dynamics in these materials at the atomic level. The refinement of pore environment plays a critical role in designing efficient sorbent materials.
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Jun 2022
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B18-Core EXAFS
B22-Multimode InfraRed imaging And Microspectroscopy
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Yujie
Ma
,
Wanpeng
Lu
,
Xue
Han
,
Yinlin
Chen
,
Ivan
Da Silva
,
Daniel
Lee
,
Alena M.
Sheveleva
,
Zi
Wang
,
Jiangnan
Li
,
Weiyao
Li
,
Mengtian
Fan
,
Shaojun
Xu
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Yongqiang
Cheng
,
Svemir
Rudic
,
Pascal
Manuel
,
Mark D.
Frogley
,
Anibal J.
Ramirez-Cuesta
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[19850]
Open Access
Abstract: The presence of active sites in metal–organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111–1135 m2 g–1), decoration of the −OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g–1 in UiO-66-CuII. A 100% enhancement of dynamic adsorption of NH3 at a concentration level of 630 ppm from 2.07 mmol g–1 in UiO-66-defect to 4.15 mmol g–1 in UiO-66-CuII at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH3 uptake in UiO-66-CuII originates from a {Cu(II)···NH3} interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH3 capture and storage.
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May 2022
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I11-High Resolution Powder Diffraction
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Shanshan
Liu
,
Yinlin
Chen
,
Bin
Yue
,
Yuanxin
Nie
,
Yuchao
Chai
,
Guangjun
Wu
,
Jiangnan
Li
,
Xue
Han
,
Sarah J.
Day
,
Stephen P.
Thompson
,
Naijia
Guan
,
Sihai
Yang
,
Landong
Li
Diamond Proposal Number(s):
[31365]
Abstract: Adsorptive separation of light hydrocarbons by porous solids provides an energy-efficient alternative to state-of-the-art cryogenic distillation. However, an optimal balance between the cost, performance and stability of the sorbent material is yet to be achieved for industrial applications. Here, we report the efficient separation of C2 and C3 hydrocarbons by a faujasite zeolite (Na-X, Si/Al=1.23). A tandem configuration of two fixed-beds packed with Na-X affords complete dynamic separation of the ternary mixture of C2H2/C2H4/C2H6 (1/49.5/49.5; v/v/v) under ambient conditions. Pressure-swing desorption on the latter fixed-bed gives ethylene (>99.50%, 1.80 mmol g-1) and ethane (>99.99%, 1.41 mmol g-1). In situ synchrotron X-ray powder diffraction revealed the binding sites for C2H2 and C2H4 in Na-X. This study highlights the potential application of commercial zeolites for challenging industrial separations.
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May 2022
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B22-Multimode InfraRed imaging And Microspectroscopy
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Lixia
Guo
,
Xue
Han
,
Yujie
Ma
,
Jiangnan
Li
,
Wanpeng
Lu
,
Weiyao
Li
,
Daniel
Lee
,
Ivan
Da Silva
,
Yongqiang
Cheng
,
Svemir
Rudic
,
Pascal
Manuel
,
Mark D.
Frogley
,
Anibal Javier
Ramirez-Cuesta
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[30398]
Open Access
Abstract: To understand the exceptional adsorption of ammonia (NH3) in MFM-300(Sc) (19.5 mmol g−1 at 273 K and 1 bar without hysteresis), we report a systematic investigation of the mechanism of adsorption by a combination of in situ neutron powder diffraction, inelastic neutron scattering, synchrotron infrared microspectroscopy, and solid-state 45Sc NMR spectroscopy. These complementary techniques reveal the formation of reversible host-guest supramolecular interactions, which explains directly the observed excellent reversibility of this material over 90 adsorption-desorption cycles.
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Apr 2022
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