B18-Core EXAFS
I11-High Resolution Powder Diffraction
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Pu
Zhao
,
Lin
Ye
,
Guangchao
Li
,
Chen
Huang
,
Simson
Wu
,
Ping-luen
Ho
,
Haokun
Wang
,
Tatchamapan
Yoskamtorn
,
Denis
Sheptyakov
,
Giannantonio
Cibin
,
Angus I.
Kirkland
,
Chiu C.
Tang
,
Anmin
Zheng
,
Wenjuan
Xue
,
Donghai
Mei
,
Kongkiat
Suriye
,
Shik Chi Edman
Tsang
Abstract: Synthesizing atomically dispersed synergistic active pairs is crucial yet challenging in developing highly active heterogeneous catalysts for various industrially important reactions. Here, a single molecular Re species is immobilized on the inner surface of a Y zeolite with Brønsted acid sites (BASs) within atomic proximity to form Re OMS–BAS active pairs for the efficient catalysis of olefin metathesis reactions (OMS: olefin metathesis site). The synergy within the active pairs is revealed by studying the coadsorption geometry of the olefin substrates over the active pairs by synchrotron X-ray and neutron powder diffraction. It is shown that the BAS not only facilitates olefin adsorption but also aligns the olefin molecule to the Re OMS for efficient intermediate formation. Consequently, for the cross-metathesis of ethene and trans-2-butene to propene, this catalyst shows high activity under mild reaction conditions without observable deactivation. The catalyst outperforms not only traditional ReOx-based catalysts but also the best industrially applicable WOx-based catalyst thus far that we discovered previously. The concept of using two isolated active sites of different functionalities within atomic proximity in a confined cavity can provide opportunities for designing synergistically catalytic materials.
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Mar 2021
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B18-Core EXAFS
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Diamond Proposal Number(s):
[16478]
Abstract: Electron paramagnetic resonance (EPR) and X-ray absorption fine structure measurements were combined with first principles calculations to investigate the substitutional behavior of Mn ions in perovskite CaTiO3 ceramics. While transition-metal dopants in perovskite-structured oxides often act as aliovalent defects, Mn in CaTiO3 is amphoteric and regardless of processing conditions concurrently occupies both Ca and Ti sites as Mn2+ and Mn4+, respectively. Contrary to the behavior of Mn in SrTiO3 and BaTiO3, which exhibit larger geometric perovskite tolerance factors, in CaTiO3, it is determined that Mn2+ prefers A-site substitution. Density functional theory (DFT) calculations provide insight to the unique defect chemistry of Mn-doped CaTiO3 compared to SrTiO3 and BaTiO3, highlighting the role of octahedral rotations which accommodate ionic size mismatch between the larger host and smaller dopant cations on the cuboctahedral sites without significant dopant-ion displacements. Superposition models of the EPR zero-field splitting parameters for multiple types of Mn defect centers were considered based on the structural parameters of DFT calculations, and these results, combined with the EPR, DFT, and X-ray absorption analysis, were used to determine the point defect substitution mechanisms of Mn-CaTiO3.
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Jan 2021
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B18-Core EXAFS
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Giovanni
Baccolo
,
Barbara
Delmonte
,
Paul B.
Niles
,
Giannantonio
Cibin
,
Elena
Di Stefano
,
Dariush
Hampai
,
Lindsay
Keller
,
Valter
Maggi
,
Augusto
Marcelli
,
Joseph
Michalski
,
Christopher
Snead
,
Massimo
Frezzotti
Diamond Proposal Number(s):
[7314, 8372, 9050]
Open Access
Abstract: Many interpretations have been proposed to explain the presence of jarosite within Martian surficial sediments, including the possibility that it precipitated within paleo-ice deposits owing to englacial weathering of dust. However, until now a similar geochemical process was not observed on Earth nor in other planetary settings. We report a multi-analytical indication of jarosite formation within deep ice. Below 1000 m depth, jarosite crystals adhering on residual silica-rich particles have been identified in the Talos Dome ice core (East Antarctica) and interpreted as products of weathering involving aeolian dust and acidic atmospheric aerosols. The progressive increase of ice metamorphism and re-crystallization with depth, favours the relocation and concentration of dust and the formation of acidic brines in isolated environments, allowing chemical reactions and mineral neo-formation to occur. This is the first described englacial diagenetic mechanism occurring in deep Antarctic ice and supports the ice-weathering model for jarosite formation on Mars, highlighting the geologic importance of paleo ice-related processes on this planet. Additional implications concern the preservation of dust-related signals in deep ice cores with respect to paleoclimatic reconstructions and the englacial history of meteorites from Antarctic blue ice fields.
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Jan 2021
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B18-Core EXAFS
I21-Resonant Inelastic X-ray Scattering (RIXS)
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Diamond Proposal Number(s):
[20363, 23889]
Open Access
Abstract: In the search for high energy density cathodes for next-generation lithium-ion batteries, the disordered rocksalt oxyfluorides are receiving significant attention due to their high capacity and lower voltage hysteresis compared with ordered Li-rich layered compounds. However, a deep understanding of these phenomena and their redox chemistry remains incomplete. Using the archetypal oxyfluoride, Li2MnO2F, we show that the oxygen redox process in such materials involves the formation of molecular O2 trapped in the bulk structure of the charged cathode, which is reduced on discharge. The molecular O2 is trapped rigidly within vacancy clusters and exhibits minimal mobility unlike free gaseous O2, making it more characteristic of a solid-like environment. The Mn redox process occurs between octahedral Mn3+ and Mn4+ with no evidence of tetrahedral Mn5+ or Mn7+. We furthermore derive the relationship between local coordination environment and redox potential; this gives rise to the observed overlap in Mn and O redox couples and reveals that the onset potential of oxide ion oxidation is determined by the degree of ionicity around oxygen, which extends models based on linear Li–O–Li configurations. This study advances our fundamental understanding of redox mechanisms in disordered rocksalt oxyfluorides, highlighting their promise as high capacity cathodes.
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Dec 2020
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B18-Core EXAFS
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Diamond Proposal Number(s):
[18561]
Abstract: Pine biomass (Pine), pine gasification biochar (PG) and pine biomass loaded with TiO2 (Pine/TiO2) were used as sorbent materials to remove Cr(III) or Cr(VI) ions from aqueous solutions. Our results showed that Pine/TiO2 had an improved adsorption capacity respect to Pine being the adsorption capacity for Cr(VI), 12.8 mg/g, much larger than for Cr(III), 1.23 mg/g. On the other hand, PG showed much higher adsorption for Cr(III), 12.4 mg/g, than Pine/TiO2, and negligible adsorption for Cr(VI). To understand this species-dependent adsorption behavior, the adsorption mechanisms, sorbents morphology and functional sites were characterized using a multi-technique approach. The chemical state and local coordination structure of the adsorbed Cr species was studied by X-ray absorption spectroscopy (XAS). Our results show that the adsorption of Cr(III) occurred mainly through cation exchange with mineral elements in PG biochar, whereas the Cr(III) adsorption by functional groups (carboxyl and hydroxyl groups) dominate in the biomass sorbent. The enhancement of Cr(VI) adsorption in Pine/TiO2 can be explained by the presence of TiOH2+ groups present in the surface of theTiO2 microparticles. X-ray absorption spectroscopy (XAS) results reveal that Cr(VI) reduces to Cr(III) after being adsorbed by the sorbent materials.
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Nov 2020
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B18-Core EXAFS
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Diamond Proposal Number(s):
[15151, 18431]
Open Access
Abstract: The technique of inelastic neutron scattering (INS) is used to investigate how hydrogen is partitioned within a series of Na and S promoted iron-based Fischer-Tropsch-to-olefin catalysts. Two reaction test regimes are examined. First, reaction testing at elevated temperature and pressure demonstrate how Na/S additions enhance short chain olefin selectivity and reduce methane formation under industrially relevant reaction conditions. For a fixed level of Na incorporation (2000 ppm), sulfur concentrations of ≤ 100 ppm result in only a modest improvement in olefin selectivity. However, for sulfur values of ≥ 100 ppm there is a noticeable and systematic increase in C2-C4 olefin selectivity; rising from ∼30.0 % to 35.2% at 250 ppm. Second, using ambient pressure CO hydrogenation as a test reaction in INS and micro-reactor configurations, catalyst samples are further analysed by TPR, TPO, XRD and S K-edge XANES. INS shows the formation of a hydrocarbonaceous overlayer to be significantly attenuated by the presence of the promoters, with increasing S levels significantly reducing the intensity of the sp2 and sp3 hybridised ν(C-H) modes of the overlayer, albeit to differing degrees. A probable role for how this combination of promoters is perturbing the form of the hydrocarbonaceous overlayer to subsequently moderate the product distribution is considered.
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Oct 2020
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B18-Core EXAFS
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P.
Ghigna
,
L.
Airoldi
,
M.
Fracchia
,
D.
Callegari
,
U.
Anselmi-tamburini
,
P.
D’angelo
,
N.
Pianta
,
R.
Ruffo
,
G.
Cibin
,
Danilo Oliveira
De Souza
,
E.
Quartarone
Diamond Proposal Number(s):
[17198]
Abstract: High-entropy oxides based on transition metals, such as Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O (TM-HEO), have recently drawn special attention as potential anodes in lithium-ion batteries due to high specific capacity and cycling reversibility. However, the lithiation/delithiation mechanism of such systems is still controversial and not clearly addressed. Here, we report on an operando XAS investigation into TM-HEO-based anodes for lithium-ion cells during the first lithiation/delithiation cycle. This material showed a high specific capacity exceeding 600 mAh g–1 at 0.1 C and Coulombic efficiency very close to unity. The combination of functional and advanced spectroscopic studies revealed complex charging mechanisms, developing through the reduction of transition-metal (TM) cations, which triggers the conversion reaction below 1.0 V. The conversion is irreversible and incomplete, leading to the final collapse of the HEO rock-salt structure. Other redox processes are therefore discussed and called to account for the observed cycling behavior of the TM-HEO-based anode. Despite the irreversible phenomena, the HEO cubic structure remains intact for ∼60% of lithiation capacity, so proving the beneficial role of the configuration entropy in enhancing the stability of the HEO rock-salt structure during the redox phenomena.
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Oct 2020
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B18-Core EXAFS
I15-Extreme Conditions
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Diamond Proposal Number(s):
[22856, 22930]
Abstract: For magnesium ion batteries (MIBs) to be used commercially, new cathodes must be developed that show stable reversible Mg intercalation. VS4 is one such promising material, with vanadium and disulfide anions [S2]2– forming one-dimensional linear chains, with a large interchain spacing (5.83 Å) enabling reversible Mg insertion. However, little is known about the details of the redox processes and structural transformations that occur upon Mg intercalation and deintercalation. Here, employing a suite of local structure characterization methods including X-ray photoelectron spectroscopy (XPS), V and S X-ray absorption near-edge spectroscopy (XANES), and 51V Hahn echo and magic-angle turning with phase-adjusted sideband separation (MATPASS) NMR, we show that the reaction proceeds via internal electron transfer from V4+ to [S2]2–, resulting in the simultaneous and coupled oxidation of V4+ to V5+ and reduction of [S2]2– to S2–. We report the formation of a previously unknown intermediate in the Mg–V–S compositional space, Mg3V2S8, comprising [VS4]3– tetrahedral units, identified by using density functional theory coupled with an evolutionary structure-predicting algorithm. The structure is verified experimentally via X-ray pair distribution function analysis. The voltage associated with the competing conversion reaction to form MgS plus V metal directly is similar to that of intermediate formation, resulting in two competing reaction pathways. Partial reversibility is seen to re-form the V5+ and S2– containing intermediate on charging instead of VS4. This work showcases the possibility of developing a family of transition metal polychalcogenides functioning via coupled cationic–anionic redox processes as a potential way of achieving higher capacities for MIBs.
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Oct 2020
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B18-Core EXAFS
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B.
Venezia
,
E.
Cao
,
Santhosh K.
Matam
,
C.
Waldron
,
G.
Cibin
,
E. K.
Gibson
,
S.
Golunski
,
P. P.
Wells
,
I.
Silverwood
,
C. R. A.
Catlow
,
G.
Sankar
,
A.
Gavriilidis
Diamond Proposal Number(s):
[19359]
Open Access
Abstract: Operando X-ray absorption spectroscopy (XAS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and mass spectrometry (MS) provide complementary information on the catalyst structure, surface reaction mechanisms and activity relationships. The powerful combination of the techniques has been the driving force to design and engineer suitable spectroscopic operando reactors that can mitigate limitations inherent to conventional reaction cells and facilitate experiments under kinetic regimes. Microreactors have recently emerged as effective spectroscopic operando cells due to their plug-flow type operation with no dead volume and negligible mass and heat transfer resistances. Here we present a novel microfabricated reactor that can be used for both operando XAS and DRIFTS studies. The reactor has a glass–silicon–glass sandwich-like structure with a reaction channel (3000 μm × 600 μm; width × depth) packed with a catalyst bed (ca. 25 mg) and placed sideways to the X-ray beam, while the infrared beam illuminates the catalyst bed from the top. The outlet of the reactor is connected to MS for continuous monitoring of the reactor effluent. The feasibility of the microreactor is demonstrated by conducting two reactions: i) combustion of methane over 2 wt% Pd/Al2O3 studied by operando XAS at the Pd K-edge and ii) CO oxidation over 1 wt% Pt/Al2O3 catalyst studied by operando DRIFTS. The former shows that palladium is in an oxidised state at all studied temperatures, 250, 300, 350, 400 °C and the latter shows the presence of linearly adsorbed CO on the platinum surface. Furthermore, temperature-resolved reduction of palladium catalyst with methane and CO oxidation over platinum catalyst are also studied. Based on these results, the catalyst structure and surface reaction dynamics are discussed, which demonstrate not only the applicability and versatility of the microreactor for combined operando XAS and DRIFTS studies, but also illustrate the unique advantages of the microreactor for high space velocity and transient response experiments.
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Oct 2020
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B18-Core EXAFS
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Wolfgang
Bensch
,
Jonas
Van Dinter
,
Kevin
Synnatschke
,
Tobias
Engesser
,
Sylvio
Indris
,
Niklas
Wolff
,
Ole
Gronenberg
,
Martin
Etter
,
Giannantonio
Cibin
,
Lorenz
Kienle
,
Claudia
Backes
Diamond Proposal Number(s):
[20060]
Abstract: The layered compound Ni2P2S6 was electrochemically characterized for application as anode material in sodium-ion batteries (SIBs). A high reversible capacity of 621 mAh g 1 at 1 A g 1 was achieved after 190 cycles. The investigation of the complex reaction mechanism of the conversion reaction was performed applying complementary techniques including X-ray powder diffraction, pair distribution function analyses, X-ray absorption spectroscopy, 19F/23Na/31P MAS NMR, TEM and nano-EDX. The results highlight that Na uptake for up to 5 Na/formula unit (f.u.) led to reduction of Ni2+ to metallic Ni nanoparticles and concomitant formation of an intermediate compound Na4P2S6. Increasing the Na content to 12 Na/f.u. generates nanocrystalline Na2S, which is accompanied by loss of the long-range order of the pristine sample. In the completely discharged state elemental Ni and Na2S are present, but in contrast to literature reports, no evidence for the formation of NaxP phases was found. During the charge process, Ni3S2 is formed upon the release of ~11.7 Na/f.u. A very high specific capacity of 621 mAh g 1 at 1.0 A g 1 is obtained after 190 cycles, and Coulombic efficiencies reach nearly 100% after the 3rd cycle.
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Oct 2020
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