B22-Multimode InfraRed imaging And Microspectroscopy
|
Bing
An
,
Zhe
Li
,
Zi
Wang
,
Xiangdi
Zeng
,
Xue
Han
,
Yongqiang
Chen
,
Alena M.
Sheveleva
,
Zhongyue
Zhang
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Mark D.
Frogley
,
Anibal J.
Ramirez-Cuesta
,
Louise S.
Natrajan
,
Cheng
Wang
,
Wenbin
Li
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[23782]
Abstract: Natural gas, consisting mainly of methane (CH4), has a relatively low energy density at ambient conditions (~36 kJ l−1). Partial oxidation of CH4 to methanol (CH3OH) lifts the energy density to ~17 MJ l−1 and drives the production of numerous chemicals. In nature, this is achieved by methane monooxygenase with di-iron sites, which is extremely challenging to mimic in artificial systems due to the high dissociation energy of the C–H bond in CH4 (439 kJ mol−1) and facile over-oxidation of CH3OH to CO and CO2. Here we report the direct photo-oxidation of CH4 over mono-iron hydroxyl sites immobilized within a metal–organic framework, PMOF-RuFe(OH). Under ambient and flow conditions in the presence of H2O and O2, CH4 is converted to CH3OH with 100% selectivity and a time yield of 8.81 ± 0.34 mmol gcat−1 h−1 (versus 5.05 mmol gcat−1 h−1 for methane monooxygenase). By using operando spectroscopic and modelling techniques, we find that confined mono-iron hydroxyl sites bind CH4 by forming an [Fe–OH···CH4] intermediate, thus lowering the barrier for C–H bond activation. The confinement of mono-iron hydroxyl sites in a porous matrix demonstrates a strategy for C–H bond activation in CH4 to drive the direct photosynthesis of CH3OH.
|
Jun 2022
|
|
I12-JEEP: Joint Engineering, Environmental and Processing
|
Yongqiang
Chen
,
Holger
Steeb
,
Hamidreza
Erfani
,
Nikolaos K.
Karadimitriou
,
Monika
Walczak
,
Matthias
Ruf
,
Dongwon
Lee
,
Senyou
An
,
Sharul
Hasan
,
Thomas
Connolley
,
Nghia T.
Vo
,
Vahid
Niasar
Diamond Proposal Number(s):
[20072]
Open Access
Abstract: Experimental and field studies reported a significant discrepancy between the cleanup and contamination time scales, while its cause is not yet addressed. Using high-resolution fast synchrotron x-ray computed tomography, we characterized the solute transport in a fully saturated sand packing for both contamination and cleanup processes at similar hydrodynamic conditions. The discrepancy in the time scales has been demonstrated by the nonuniqueness of hydrodynamic dispersion coefficient versus injection rate (Péclet number). Observations show that in the mixed advection-diffusion regime, the hydrodynamic dispersion coefficient of cleanup is significantly larger than that of the contamination process. This nonuniqueness has been attributed to the concentration-dependent diffusion coefficient during the cocurrent and countercurrent advection and diffusion, present in contamination and cleanup processes. The new findings enhance our fundamental understanding of transport processes and improve our capability to estimate the transport time scales of chemicals or pollution in geological and engineering systems.
|
Dec 2021
|
|
I11-High Resolution Powder Diffraction
I19-Small Molecule Single Crystal Diffraction
|
Christopher
Marsh
,
Xue
Han
,
Jiangnan
Li
,
Zhenzhong
Lu
,
Stephen
Argent
,
Ivan
Da Silva
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Anibal J.
Ramirez-Cuesta
,
Stephen P.
Thompson
,
Alexander J.
Blake
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[23483, 11622]
Open Access
Abstract: We report the reversible adsorption of ammonia (NH3) up to 9.9 mmol g–1 in a robust Al-based metal–organic framework, MFM-303(Al), which is functionalized with free carboxylic acid and hydroxyl groups. The unique pore environment decorated with these acidic sites results in an exceptional packing density of NH3 at 293 K (0.801 g cm–3) comparable to that of solid NH3 at 193 K (0.817 g cm–3). In situ synchrotron X-ray diffraction and inelastic neutron scattering reveal the critical role of free −COOH and −OH groups in immobilizing NH3 molecules. Breakthrough experiments confirm the excellent performance of MFM-303(Al) for the capture of NH3 at low concentrations under both dry and wet conditions.
|
Apr 2021
|
|
B22-Multimode InfraRed imaging And Microspectroscopy
|
Xue
Han
,
Wanpeng
Lu
,
Yinlin
Chen
,
Ivan
Da Silva
,
Jiangnan
Li
,
Longfei
Lin
,
Weiyao
Li
,
Alena M.
Sheveleva
,
Harry G. W.
Godfrey
,
Zhenzhong
Lu
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Laura J.
Mccormick Mcpherson
,
Simon J.
Teat
,
Mark D.
Frogley
,
Svemir
Rudic
,
Pascal
Manuel
,
Anibal J.
Ramirez-Cuesta
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[23782]
Abstract: Ammonia (NH3) is a promising energy resource owing to its high hydrogen density. However, its widespread application is restricted by the lack of efficient and corrosion-resistant storage materials. Here, we report high NH3 adsorption in a series of robust metal–organic framework (MOF) materials, MFM-300(M) (M = Fe, V, Cr, In). MFM-300(M) (M = Fe, VIII, Cr) show fully reversible capacity for >20 cycles, reaching capacities of 16.1, 15.6, and 14.0 mmol g–1, respectively, at 273 K and 1 bar. Under the same conditions, MFM-300(VIV) exhibits the highest uptake among this series of MOFs of 17.3 mmol g–1. In situ neutron powder diffraction, single-crystal X-ray diffraction, and electron paramagnetic resonance spectroscopy confirm that the redox-active V center enables host–guest charge transfer, with VIV being reduced to VIII and NH3 being oxidized to hydrazine (N2H4). A combination of in situ inelastic neutron scattering and DFT modeling has revealed the binding dynamics of adsorbed NH3 within these MOFs to afford a comprehensive insight into the application of MOF materials to the adsorption and conversion of NH3.
|
Feb 2021
|
|
I11-High Resolution Powder Diffraction
I20-EDE-Energy Dispersive EXAFS (EDE)
|
Longfei
Lin
,
Mengtian
Fan
,
Alena M.
Sheveleva
,
Xue
Han
,
Zhimou
Tang
,
Joseph H.
Carter
,
Ivan
Da Silva
,
Christopher
Parlett
,
Floriana
Tuna
,
Eric J. L.
Mcinnes
,
German
Sastre
,
Svemir
Rudic
,
Hamish
Cavaye
,
Stewart F.
Parker
,
Yongqiang
Cheng
,
Luke L.
Daemen
,
Anibal J.
Ramirez-Cuesta
,
Martin P.
Attfield
,
Yueming
Liu
,
Chiu C.
Tang
,
Buxing
Han
,
Sihai
Yang
Diamond Proposal Number(s):
[2359]
Open Access
Abstract: Optimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.
|
Feb 2021
|
|
B22-Multimode InfraRed imaging And Microspectroscopy
|
Jiangnan
Li
,
Zhengyang
Zhou
,
Xue
Han
,
Xinran
Zhang
,
Yong
Yan
,
Weiyao
Li
,
Gemma L.
Smith
,
Yongqiang
Cheng
,
Laura J.
Mcormick Mpherson
,
Simon J.
Teat
,
Mark D.
Frogley
,
Svemir
Rudic
,
Anibal J.
Ramirez-Cuesta
,
Alexander J.
Blake
,
Junliang
Sun
,
Martin
Schroeder
,
Sihai
Yang
Diamond Proposal Number(s):
[22137]
Open Access
Abstract: Structural transitions of host systems in response to guest binding dominate many chemical processes. We report an unprecedented type of structural flexibility within a meta-rigid material, MFM-520, which exhibits a reversible periodic-to-aperiodic structural transition resulting from a drastic distortion of a [ZnO4N] node controlled by the specific host–guest interactions. The aperiodic crystal structure of MFM-520 has no three-dimensional (3D) lattice periodicity but shows translational symmetry in higher-dimensional (3 + 2)D space. We have directly visualized the aperiodic state which is induced by incommensurate modulation of the periodic framework of MFM-520·H2O upon dehydration to give MFM-520. Filling MFM-520 with CO2 and SO2 reveals that, while CO2 has a minimal structural influence, SO2 can further modulate the structure incommensurately. MFM-520 shows exceptional selectivity for SO2 under flue-gas desulfurization conditions, and the facile release of captured SO2 from MFM-520 enabled the conversion to valuable sulfonamide products. MFM-520 can thus be used as a highly efficient capture and delivery system for SO2.
|
Oct 2020
|
|
B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
|
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.
|
Aug 2020
|
|
B22-Multimode InfraRed imaging And Microspectroscopy
|
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.
|
May 2020
|
|
I11-High Resolution Powder Diffraction
|
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.
|
May 2020
|
|
B18-Core EXAFS
I11-High Resolution Powder Diffraction
|
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.
|
Dec 2019
|
|
