B18-Core EXAFS
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Diamond Proposal Number(s):
[29271]
Open Access
Abstract: Bioethanol upgrading to n-butanol is catalysed by homogeneous catalysts under mild solventless liquid phase conditions, at which heterogeneous catalysts have poor performance. Here a heterogeneous catalyst, initially comprised of a Ru(bipy) complex incorporated into a polyphenylene support, gave a catalytic performance (TON of 3565 Ru-1 and 82% n-butanol selectivity) that exceeded contemporary homogeneous and heterogeneous catalysts. Catalyst deactivation by water byproduct inhibition was improved by removal of water, via recharging the reactor with fresh ethanol, or by the co-addition of molecular sieve. The Ru polyphenylene catalyst showed greater stability in the presence of molecular sieve compared to the homogeneous catalyst, enabling high butanol yields. Characterisation showed a structural transformation of the single atom Ru(bipy) into 2.6 nm Ru(0) nanoparticles after 16 h reaction. While the Ru(0) had moderate recyclability (TON of 1000 Ru-1) the initial highly active species seen in the fresh catalyst are not stable.
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Jan 2025
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B18-Core EXAFS
E01-JEM ARM 200CF
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Ruoyu
Xu
,
Liqun
Kang
,
Konstantinos G.
Papanikolaou
,
Bolun
Wang
,
Sushila
Marlow
,
Qian
He
,
Peng
Zhang
,
Jianfang
Wang
,
Dan J. I.
Brett
,
Michail
Stamatakis
,
Feng Ryan
Wang
Diamond Proposal Number(s):
[20643, 19318, 19246, 19072, 20629]
Open Access
Abstract: Proton exchange membrane fuel cells require oxygen reduction catalysts with high activity and stability. Pt based alloy materials are most widely applied ORR catalyst due to its high intrinsic activity, but usually suffer from rapid deactivation as a result of particle agglomeration, detachment, Ostwald ripening and/or Pt dissolution. Here we investigate the degradation of the PdPt alloys via in situ X-ray absorption fine structure, Δμ analysis, identical location-electron microscopy and DFT calculations. We conclude that the origin of high activity and stability of the PdPt catalyst stems from the oxidation resistance of metallic Pt, forming mainly surface adsorbed O species at high potentials. Two stage degradation process are observed, showing an evolution of dynamic surface dependent ORR performance along with the deactivation process. The careful design of Pt alloy structure leads to controlled surface oxygen behaviours. This opens a new way to increase the lifespan of fuel cells and improve the Pt utilization efficiency.
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Nov 2022
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I06-Nanoscience (XPEEM)
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Dong
Li
,
Bonan
Zhu
,
Dirk
Backes
,
Larissa S. I.
Veiga
,
Tien-Lin
Lee
,
Hongguang
Wang
,
Qian
He
,
Pinku
Roy
,
Jiaye
Zhang
,
Jueli
Shi
,
Aiping
Chen
,
Peter A.
Van Aken
,
Quanxi
Jia
,
Sarnjeet S.
Dhesi
,
David O.
Scanlon
,
Kelvin H. L.
Zhang
,
Weiwei
Li
Diamond Proposal Number(s):
[25425, 26901, 29616]
Abstract: Strain engineering of epitaxial transition metal oxide heterostructures offers an intriguing opportunity to control electronic structures by modifying the interplay between spin, charge, orbital, and lattice degrees of freedom. Here, we demonstrate that the electronic structure, magnetic and transport properties of
La
0.9
Ba
0.1
MnO
3
thin films can be effectively controlled by epitaxial strain. Spectroscopic studies and first-principles calculations reveal that the orbital occupancy in Mn
e
g
orbitals can be switched from the
d
3
z
2
−
r
2
orbital to the
d
x
2
−
y
2
orbital by varying the strain from compressive to tensile. The change of orbital occupancy associated with Mn
3
d
-O
2
p
hybridization leads to dramatic modulation of the magnetic and electronic properties of strained
La
0.9
Ba
0.1
MnO
3
thin films. Under moderate tensile strain, an emergent ferromagnetic insulating state with an enhanced ferromagnetic Curie temperature of 215 K is achieved. These findings not only deepen our understanding of electronic structures, magnetic and transport properties in the
La
0.9
Ba
0.1
MnO
3
system, but also demonstrate the use of epitaxial strain as an effective knob to tune the electronic structures and related physical properties for potential spintronic device applications.
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Apr 2022
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B18-Core EXAFS
E01-JEM ARM 200CF
|
Open Access
Abstract: Pt/Sn-containing MFI zeolites prepared by one-pot hydrothermal methods are highly active and selective catalysts for propane dehydrogenation. An alternative preparation method is reported alongside an in-depth characterization of Pt and Sn before and after reaction. Pt species dispersed on highly-defective Silicalite-1 show a significantly long catalytic lifetime with an improved coke resistance, but increased Pt-Sn alloying and the (eventual) build-up of carbon leads to deactivation.
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Jan 2022
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E01-JEM ARM 200CF
|
Xiaoyang
Huang
,
Ouardia
Akdim
,
Mark
Douthwaite
,
Kai
Wang
,
Liang
Zhao
,
Richard J.
Lewis
,
Samuel
Pattisson
,
Isaac T.
Daniel
,
Peter J.
Miedziak
,
Greg
Shaw
,
David J.
Morgan
,
Sultan M.
Althahban
,
Thomas E.
Davies
,
Qian
He
,
Fei
Wang
,
Jile
Fu
,
Donald
Bethell
,
Steven
Mcintosh
,
Christopher J.
Kiely
,
Graham J.
Hutchings
Diamond Proposal Number(s):
[18909]
Abstract: In oxidation reactions catalysed by supported metal nanoparticles with oxygen as the terminal oxidant, the rate of the oxygen reduction can be a limiting factor. This is exemplified by the oxidative dehydrogenation of alcohols, an important class of reactions with modern commercial applications1–3. Supported gold nanoparticles are highly active for the dehydrogenation of the alcohol to an aldehyde4 but are less effective for oxygen reduction5,6. In contrast, supported palladium nanoparticles are less active than gold for dehydrogenation but offer high efficacy for oxygen reduction5,6. This imbalance can be overcome by alloying gold with palladium which gives enhanced activity to both reactions7,8; however, the electrochemical potential of the alloy is a compromise between that of the two metals meaning that although the oxygen reduction is improved in the alloy, the dehydrogenation activity is poorer. Here we show that by separating the gold and palladium components in bimetallic carbon-supported catalysts we can almost double the reaction rate beyond that achieved with a corresponding alloy catalyst. We demonstrate this using physical mixtures of carbon-supported monometallic gold and palladium and a bimetallic catalyst comprising separated gold and palladium regions. Furthermore, we demonstrate electrochemically that this enhancement is attributable to the coupling of separate redox processes occurring at isolated gold and palladium sites. The discovery of this novel catalytic effect, a cooperative redox enhancement (CORE), offers a new approach to the design of multi-component heterogeneous catalysts.
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Jan 2022
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Liqun
Kang
,
Bolun
Wang
,
Andreas T.
Güntner
,
Siyuan
Xu
,
Xuhao
Wan
,
Yiyun
Liu
,
Sushila
Marlow
,
Yifei
Ren
,
Diego
Gianolio
,
Chiu C.
Tang
,
Vadim
Murzin
,
Hiroyuki
Asakura
,
Qian
He
,
Shaoliang
Guan
,
Juan J.
Velasco-Vélez
,
Sotiris E.
Pratsinis
,
Yuzheng
Guo
,
Feng Ryan
Wang
Open Access
Abstract: Electronic metal‐support interaction (EMSI) describes the electron flow between metal sites and a metal oxide support. It is generally used to follow the mechanism of redox reactions. In the study of CuO‐CeO2 redox, an additional flow of electron from metallic Cu to surface carbon species is observed via a combination of operando X‐ray absorption spectroscopy, synchrotron X‐ray powder diffraction, near ambient pressure‐near edge X‐ray absorption fine structure, and diffuse reflectance infrared Fourier transform spectroscopy. An electronic metal‐support‐carbon interaction (EMSCI) is proposed to explain the reaction pathway of CO oxidation. The EMSCI provides a complete picture of the mass and electron flow, which will help predict and improve the catalytic performance in the selective activation of CO2 , carbonate or carbonyl species in C1 chemistry.
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Mar 2021
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B18-Core EXAFS
E01-JEM ARM 200CF
E02-JEM ARM 300CF
|
Liqun
Kang
,
Bolun
Wang
,
Adam
Thetford
,
Ke
Wu
,
Mohsen
Danaie
,
Qian
He
,
Emma
Gibson
,
Ling-Dong
Sun
,
Hiroyuki
Asakura
,
Richard
Catlow
,
Feng Ryan
Wang
Diamond Proposal Number(s):
[16966, 17559, 18909, 19246, 19318, 20643, 20847, 17377, 15151, 14239]
Open Access
Abstract: Ru(II) compounds are widely used in catalysis, photocatalysis and medical applications. They are usually obtained in reductive environment as molecular O 2 can oxidize Ru(II) to Ru(III) and Ru(IV). Here we report the design, identification and evolution of an air‐stable surface ‐[bipy‐Ru(II)(CO) 2 Cl 2 ] site that is covalently mounted onto a polyphenylene framework. Such Ru(II) site was obtained by reduction of ‐[bipy‐Ru(III)Cl 4 ] ‐ with simultaneous ligand exchange from Cl ‐ to CO. This structural evolution was witnessed by a combination of in situ X‐ray and infrared spectroscopy studies. The ‐[bipy‐Ru(II)(CO) 2 Cl 2 ] site enables oxidation of CO with a turnover frequency of 0.73 × 10 ‐2 s ‐1 at 462 K, while the Ru(III) site is completely inert. This work contributes to the studies of structure‐activity relationship by demonstrating a practical control over both geometric and electronic structures of single‐site catalysts at molecular level, which can be further applied in other single site catalyst researches.
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Sep 2020
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B18-Core EXAFS
E01-JEM ARM 200CF
E02-JEM ARM 300CF
I11-High Resolution Powder Diffraction
I20-Scanning-X-ray spectroscopy (XAS/XES)
|
Liqun
Kang
,
Bolun
Wang
,
Qiming
Bing
,
Michal
Zalibera
,
Robert
Büchel
,
Ruoyu
Xu
,
Qiming
Wang
,
Yiyun
Liu
,
Diego
Gianolio
,
Chiu C.
Tang
,
Emma K.
Gibson
,
Mohsen
Danaie
,
Christopher
Allen
,
Ke
Wu
,
Sushila
Marlow
,
Ling-Dong
Sun
,
Qian
He
,
Shaoliang
Guan
,
Anton
Savitsky
,
Juan J.
Velasco-Vélez
,
June
Callison
,
Christopher W. M.
Kay
,
Sotiris E.
Pratsinis
,
Wolfgang
Lubitz
,
Jing-Yao
Liu
,
Feng Ryan
Wang
Diamond Proposal Number(s):
[15151, 15763, 16966, 17377, 19072, 19246, 20939, 17559, 24285, 19318, 19850]
Open Access
Abstract: Supported atomic metal sites have discrete molecular orbitals. Precise control over the energies of these sites is key to achieving novel reaction pathways with superior selectivity. Here, we achieve selective oxygen (O2) activation by utilising a framework of cerium (Ce) cations to reduce the energy of 3d orbitals of isolated copper (Cu) sites. Operando X-ray absorption spectroscopy, electron paramagnetic resonance and density-functional theory simulations are used to demonstrate that a [Cu(I)O2]3− site selectively adsorbs molecular O2, forming a rarely reported electrophilic η2-O2 species at 298 K. Assisted by neighbouring Ce(III) cations, η2-O2 is finally reduced to two O2−, that create two Cu–O–Ce oxo-bridges at 453 K. The isolated Cu(I)/(II) sites are ten times more active in CO oxidation than CuO clusters, showing a turnover frequency of 0.028 ± 0.003 s−1 at 373 K and 0.01 bar PCO. The unique electronic structure of [Cu(I)O2]3− site suggests its potential in selective oxidation.
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Aug 2020
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E01-JEM ARM 200CF
|
Mark
Douthwaite
,
Natasha
Powell
,
Aoife
Taylor
,
Grayson
Ford
,
José Manuel
López
,
Benjamin
Solsona
,
Nating
Yang
,
Olga
Sanahuja‐parejo
,
Qian
He
,
David J.
Morgan
,
Tomas
Garcia
,
Stuart H.
Taylor
Diamond Proposal Number(s):
[21641, 22766]
Open Access
Abstract: A high surface area mesoporous TiO2 material (110 m2/g) was synthesised using a nanocasting methodology, utilizing SBA‐15 as a hard template. This material was subsequently used as a support to prepare a series of 1 wt.% AuPt/TiO2 catalysts, synthesised by conventional impregnation and sol‐immobilisation. Catalysts were tested for the oxidation of glycerol to lactic acid and their performance was compared with corresponding catalysts supported on TiO2−P25, TiO2‐anatase and TiO2‐rutile. Higher rates of reaction and higher selectivity to lactic acid were observed over nanocast TiO2 supported catalysts. The increased performance of these catalysts was attributed to the presence of Si on the surface of the support, which likely arose from inefficient etching of the SBA‐15 template. The presence of Si in these catalysts was confirmed by X‐ray photoelectron spectroscopy and electron energy loss spectroscopy. It was proposed that the residual Si present increases the Brønsted acidity of the TiO2 support, which can lead to the formation of Lewis acid sites under reaction conditions; both sites are known to catalyse the dehydration of a primary alcohol in glycerol. Typically, under alkaline conditions, lactic acid is formed by the nucleophilic abstraction of a hydrogen. Thus, we propose that the improved selectivity to lactic acid over the nanocast TiO2 supported catalyst is attributed to the co‐operation of heterogeneous and homogeneous dehydration reactions, as both compete directly with a direct oxidation pathway, which leads to the formation of oxidation products such as glyceric and tartronic acid.
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Jun 2020
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I06-Nanoscience (XPEEM)
|
Weiwei
Li
,
Bonan
Zhu
,
Qian
He
,
Albina Y.
Borisevich
,
Chao
Yun
,
Rui
Wu
,
Ping
Lu
,
Zhimin
Qi
,
Qiang
Wang
,
Aiping
Chen
,
Haiyan
Wang
,
Stuart A.
Cavill
,
Kelvin H. L.
Zhang
,
Judith L.
Macmanus‐driscoll
Diamond Proposal Number(s):
[17284]
Open Access
Abstract: Ultrathin epitaxial films of ferromagnetic insulators (FMIs) with Curie temperatures near room temperature are critically needed for use in dissipationless quantum computation and spintronic devices. However, such materials are extremely rare. Here, a room‐temperature FMI is achieved in ultrathin La0.9Ba0.1MnO3 films grown on SrTiO3 substrates via an interface proximity effect. Detailed scanning transmission electron microscopy images clearly demonstrate that MnO6 octahedral rotations in La0.9Ba0.1MnO3 close to the interface are strongly suppressed. As determined from in situ X‐ray photoemission spectroscopy, O K‐edge X‐ray absorption spectroscopy, and density functional theory, the realization of the FMI state arises from a reduction of Mn eg bandwidth caused by the quenched MnO6 octahedral rotations. The emerging FMI state in La0.9Ba0.1MnO3 together with necessary coherent interface achieved with the perovskite substrate gives very high potential for future high performance electronic devices.
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Nov 2019
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