I11-High Resolution Powder Diffraction
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Abstract: The adsorbate interactions of furans as probe molecules in H-ZSM-5 and H-USY with and without metal ion modification have been revealed by synchrotron X-ray powder diffraction (SXRD). The Rietveld refinements give both qualitatively and quantitatively the spatial arrangements and adsorption geometries of furan and 2,5-dimethylfuran (DMF) on the Brønsted acid sites (BAS) and metal Lewis acid sites (LAS). The bonding information between the adsorbate-framework can also be correlated with thermogravimetric findings. The use of probe molecule-SXRD can be used as a new characterisation tool which can spatially interrogate the acidity of crystalline porous catalysts, leading to molecular engineering of new catalytic systems.
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Apr 2020
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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
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Simson
Wu
,
Yung-kang
Peng
,
Tianyi
Chen
,
Jiaying
Mo
,
Alex
Large
,
Ian
Mcpherson
,
Hung-lung
Chou
,
Ian
Wilkinson
,
Federica
Venturini
,
David
Grinter
,
Pilar
Ferrer Escorihuela
,
Georg
Held
,
Shik Chi Edman
Tsang
Abstract: The increasing availability of low-cost and low pressure, renewable H2 from wind and solar means has triggered tremendous interest in developing low pressure ammonia synthesis with N2 as energy carrier as well as green fertilizer. As such Cs-promoted Ru/MgO catalysts used in Kellogg process show superiority to Fe-based catalysts at milder conditions, however, as known, the surface poisoning of Ru sites by competitive strong H2 dissociative adsorption limits the overall rate. It is demonstrated for the first time that the use of simple polar MgO(111) to replace non-polar MgO as support can significantly alleviate the hydrogen poisoning and facilitate an unprecedented ammonia production rate by its high intrinsic proton capture ability.
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Apr 2020
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[23230]
Abstract: We report the first crystallographic observation of stereospecific bindings of L‐ and D‐lysine in achiral MFI zeolites. The MFI structure has offered inherent geometric and internal confinement effects for the enantiomeric difference in L‐ and D‐lysine adsorption. Notable difference over the sorption properties has been observed by circular dichroism (CD) spectroscopy and thermogravimetric analysis (TGA). Distinct L‐ and D‐lysine adsorption behaviours on the H‐ZSM‐5 framework have been revealed by the Rietveld refinement of high‐resolution synchrotron X‐ray powder diffraction (SXRD) data and the density functional theory (DFT) calculation. Despite only demonstrated in L‐ and D‐lysine over MFI zeolites, the differential adsorption study sheds light towards the rational engineering of molecular interactions(s) with achiral microporous materials for chiral separation purposes.
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Nov 2019
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I11-High Resolution Powder Diffraction
I15-1-X-ray Pair Distribution Function (XPDF)
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Tianyi
Chen
,
Ieuan
Ellis
,
Thomas
Hooper
,
Emanuela
Liberti
,
Lin
Ye
,
Tsz Woon Benedict
Lo
,
Colum
O'leary
,
Alexandra A.
Sheader
,
Gerardo T.
Martinez
,
Lewys
Jones
,
Ping-luen
Ho
,
Pu
Zhao
,
James
Cookson
,
Peter T
Bishop
,
Philip A.
Chater
,
John V.
Hanna
,
Peter D.
Nellist
,
Shik Chi Edman
Tsang
Diamond Proposal Number(s):
[15452]
Abstract: It is well established that the inclusion of small atomic species such as boron (B) in powder metal catalysts can subtly modify catalytic properties, and the associated changes in the metal lattice implies that the B atoms are located in the interstitial sites. However, there is no compelling evidence for the occurrence of interstitial B atoms, and there is a concomitant lack of detailed structural information describing the nature of this occupancy and its effects on the metal host. In this work, we use an innovative combination of high-resolution 11B magic-angle-spinning (MAS) and 105Pd static solid state NMR nuclear magnetic resonance (NMR), synchrotron X-ray diffraction (SXRD), in-situ X-ray pair distribution function (XPDF), scanning transmission electron microscopy-annular dark field imaging (STEM-ADF), electron ptychography and electron energy loss spectroscopy (EELS) to investigate the B atom positions, properties and structural modifications to the palladium lattice of an industrial type interstitial boron doped palladium nanoparticle catalyst system (Pd-intB/C NPs). In this study we report that upon B incorporation into the Pd lattice, the overall face centered cubic (FCC) lattice is maintained, however short range disorder is introduced. The 105Pd static solid-state NMR illustrates how different types (and levels) of structural strain and disorder are introduced in the nanoparticle history. These structural distortions can lead to the appearance of small amounts of local hexagonal close packed (HCP) structured material in localized regions. The short range lattice tailoring of the Pd framework to accommodate interstitial B dopants in the octahedral sites of the distorted FCC structure can be imaged by electron ptychography. This study describes new toolsets that enables the characterization of industrial metal nanocatalysts across length scales from macro-analysis to micro-analysis, which gives important guidance to structure-activity relationship of the system.
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Nov 2019
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E01-JEM ARM 200CF
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Haohong
Duan
,
Jin-cheng
Liu
,
Ming
Xu
,
Yufei
Zhao
,
Xue-lu
Ma
,
Juncai
Dong
,
Xusheng
Zheng
,
Jianwei
Zheng
,
Christopher
Allen
,
Mohsen
Danaie
,
Yung-kang
Peng
,
Titipong
Issariyakul
,
Dongliang
Chen
,
Angus
Kirkland
,
Jean-charles
Buffet
,
Jun
Li
,
Shik Chi Edman
Tsang
,
Dermot
O'hare
Diamond Proposal Number(s):
[16969, 17397]
Abstract: Although molecular dinitrogen (N2) is widely used as a carrier or inert gas for many catalytic reactions, it is rarely considered as a catalytic promoter. Here, we report that N2 could be used to reduce the activation energy for catalytic hydrodeoxygenation over ruthenium-based catalysts. Specifically, we report a 4.3-fold activity increase in the catalytic hydrodeoxygenation of p-cresol to toluene over a titanium oxide supported ruthenium catalyst (Ru/TiO2) by simply introducing 6 bar N2 under batch conditions at 160 °C and 1 bar hydrogen. Detailed investigations indicate that N2 can be adsorbed and activated on the metallic ruthenium surface to form hydrogenated nitrogen species, which offer protic hydrogen to lower the activation energy of direct carbonaromatic–oxygen bond scission and the hydrogenation of hydroxy groups. Thus, by employing different ruthenium catalysts, including Ru/TiO2, Ru/Al2O3, Ru/ZrO2 and Ru/C, we demonstrate that N2 promotion of hydrodeoxygenation can be regarded as a general strategy.
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Oct 2019
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I11-High Resolution Powder Diffraction
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Zhenping
Cai
,
Jinxing
Long
,
Yingwen
Li
,
Lin
Ye
,
Biaolin
Yin
,
Liam John
France
,
Juncai
Dong
,
Lirong
Zheng
,
Hongyan
He
,
Sijie
Liu
,
Shik Chi Edman
Tsang
,
Xuehui
Li
Abstract: Green production of bulk chemicals traditionally obtained from fossil resources is of great importance. One potential route toward realizing this goal is through the utilization of renewable lignin; however, current techniques generally lead to low product specificity because of the structural diversity of this recalcitrant biopolymer. Herein, we devised a new catalytic system to promote selectively oxidative lignin in air, and diethyl maleate was formed at impressively high yield of 404.8 mg g−1 and selectivity of 72.7% over the polyoxometalate ionic liquid of [BSmim]CuPW12O40. This high catalytic activity is ascribed to a five-coordinated Cu+ species, which, through the formation of end-on dioxygen species in vacant orbitals, facilitates the selective oxidation of basic lignin aromatic units (phenylpropane C9 units). Therefore, these results represent significant progress toward the realization of an industrially applicable and highly selective lignin oxidation process for the generation of value-added and bulk chemicals.
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Jun 2019
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E01-JEM ARM 200CF
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Lin
Ye
,
A. A. Hanif
Mahadi
,
Chalathan
Saengruengrit
,
Jin
Qu
,
Feng
Xu
,
Simon
Fairclough
,
Neil
Young
,
Ping-luen
Ho
,
Junjun
Shan
,
Luan
Nguyen
,
Franklin F.
Tao
,
Karaked
Tedsree
,
Shik Chi Edman
Tsang
Abstract: Ceria has been widely used as support in electrocatalysis for its high degree of oxygen storage, fast oxygen mobility and reduction and oxidation properties at mild conditions. However, it is unclear what are the underlying principles and the nature of surface involved. By controlling the growth of various morphologies of ceria nanoparticles, it is demonstrated that the cubic-form of ceria, predominantly covered with higher energy polar surface (100), as support for Pd gives much higher activity in the electrocatalytic oxidation of formic acid than ceria of other morphologies (rods and spheres) with low indexed facets ((110) and (111)). High resolution TEM confirms the alternating layer-to-layer of cations and anions in (100) surface, the electrostatic repulsion of oxygen anions within the same layers gives intrinsically higher oxygen vacancies on this redox active surface in order to reduce surface polarity. DFT calculations suggest that the properties of fast oxygen mobility to re-oxidize the CO-poisoned Pd may arise from the overdosed oxygens on these ceria surface layers during electro-oxidation hence sustaining higher activity.
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Apr 2019
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I11-High Resolution Powder Diffraction
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Open Access
Abstract: Stimuli-responsive behaviors of flexible metal–organic frameworks (MOFs) make these materials promising in a wide variety of applications such as gas separation, drug delivery, and molecular sensing. Considerable efforts have been made over the last decade to understand the structural changes of flexible MOFs in response to external stimuli. Uniform pore deformation has been used as the general description. However, recent advances in synthesizing MOFs with non-uniform porous structures, i.e. with multiple types of pores which vary in size, shape, and environment, challenge the adequacy of this description. Here, we demonstrate that the CO2-adsorption-stimulated structural change of a flexible MOF, ZIF-7, is induced by CO2 migration in its non-uniform porous structure rather than by the proactive opening of one type of its guest-hosting pores. Structural dynamics induced by guest migration in non-uniform porous structures is rare among the enormous number of MOFs discovered and detailed characterization is very limited in the literature. The concept presented in this work provides new insights into MOF flexibility.
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Mar 2019
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B18-Core EXAFS
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Abstract: The direct hydrogenation of CO2 to methanol has become a very active research field because CO2 can be prospectively recycled to mitigate greenhouse effect and store clean synthetic fuels. This reaction can be catalyzed by supported Cu catalysts and the catalysts display strong support or promoter effects. Sintering of Cu species accelerates the separation of Cu–oxide interfaces, reduces the active component, and diminishes the methanol selectivity. In this work, we report a Cu catalyst supported on La-modified SBA-15, where the Cu–LaOx interface is generated through the interaction of highly dispersed Cu nanoparticles with LaOx species bedded into the SBA-15 pore wall. The optimized Cu1La0.2/SBA-15 catalyst can achieve methanol selectivity up to 81.2% with no deterioration in activity over 100 h on stream compared with the La-free catalyst. A thorough study reveals that La species not only significantly improve the CO2 adsorption but also enhance Cu dispersion to produce well-dispersed active sites. The H/D exchange experiments show that the methanol synthesis displays a strong thermodynamic isotope effect and the Cu–LaOx interface plays a crucial role for the methanol synthesis rate in CO2/D2 feed. In situ DRIFTS studies reveal that *HCOO and *OCH3 species are the key intermediates formed during the activation of CO2 and methanol synthesis over the Cu1La0.2/SBA-15 catalyst.
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Mar 2019
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I11-High Resolution Powder Diffraction
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Lin
Ye
,
Xinping
Duan
,
Simson
Wu
,
Tai-sing
Wu
,
Yuxin
Zhao
,
Alex W.
Robertson
,
Hung-lung
Chou
,
Jianwei
Zheng
,
Tugce
Ayvali
,
Sarah
Day
,
Chiu
Tang
,
Yun-liang
Soo
,
Youzhu
Yuan
,
Shik Chi Edman
Tsang
Open Access
Abstract: Replacement of Hg with non-toxic Au based catalysts for industrial hydrochlorination of acetylene to vinyl chloride is urgently required. However Au catalysts suffer from progressive deactivation caused by auto-reduction of Au(I) and Au(III) active sites and irreversible aggregation of Au(0) inactive sites. Here we show from synchrotron X-ray absorption, STEM imaging and DFT modelling that the availability of ceria(110) surface renders Au(0)/Au(I) as active pairs. Thus, Au(0) is directly involved in the catalysis. Owing to the strong mediating properties of Ce(IV)/Ce(III) with one electron complementary redox coupling reactions, the ceria promotion to Au catalysts gives enhanced activity and stability. Total pre-reduction of Au species to inactive Au nanoparticles of Au/CeO2&AC when placed in a C2H2/HCl stream can also rapidly rejuvenate. This is dramatically achieved by re-dispersing the Au particles to Au(0) atoms and oxidising to Au(I) entities, whereas Au/AC does not recover from the deactivation.
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Feb 2019
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