B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
B18-Core EXAFS
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Diamond Proposal Number(s):
[26554]
Open Access
Abstract: The nature and evolution of FeNxCy moieties in Fe/C/N catalysts has been studied by analysing Fe and N environments. TEM and Fe-XAS reveal the presence of FeNx moieties and Fe3C particles in the fresh catalyst. NEXAFS reveals the presence of two groups of (Fe)NxCy ensembles, namely (Fe)Nx-pyridinic and (Fe)Nx-pyrrolic. The architecture of the FeNxCy ensembles and their evolution during the ORR has been analysed by XAS, NEXAFS, and identical locations TEM. NxCy, FeNxCy and Fe3C species are partially removed during the ORR, resulting in the formation of Fe2O3 and Fe3O4 particles with different morphologies. The process is more severe in acid electrolyte than in alkaline one. (Fe)Nx-pyrrolic moieties are the main ones in the fresh catalysts, but (Fe)Nx-pyridinic groups are more stable after the ORR. The correlation between the evolution of the ORR activity and that of the FeNxCy ensembles indicates that FeNx-pyridinic ensembles are responsible for the ORR activity.
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Apr 2021
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Open Access
Abstract: Multiply‐bonded lanthanide oxo groups are rare in coordination compounds and have not previously been reported for a surface termination of a lanthanide oxide. Here we report the observation of a Ce=O terminated ceria surface in a CeO 2 (111)‐( [[EQUATION]] x [[EQUATION]] )R30° reconstruction of ~3 nm thick ceria islands prepared on Pt(111). This is evidenced by scanning tunnelling microscopy, low energy electron diffraction and high‐resolution electron energy loss spectroscopy (HREELS) measurements in conjunction with density functional theory (DFT) calculations. A Ce=O stretching frequency of 775 cm ‐1 is observed in HREELS, compared with 766 cm ‐1 calculated by DFT. The calculations also predict that the Ce=O bond is weak, with an oxygen vacancy formation energy of 0.85 eV. This could play an important role in the facile removal of lattice oxygen from CeO 2 , accompanied by the reduction of Ce IV to Ce III , which is a key attribute of ceria‐based systems in connection with their unique catalytic properties.
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Apr 2021
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Karel
Saksl
,
Ildikó
Pethes
,
Pál
Jóvári
,
Zuzana
Molčanová
,
Juraj
Durisin
,
Beáta
Ballóková
,
László
Temleitner
,
Stefan
Michalik
,
Michaela
Sulikova
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Katarína
Šuľová
,
Miloš
Fejercak
,
Dagmara
Varcholová
,
Rastislav
Motýľ
Abstract: Amorphous alloys consisting of elements present in the human body, such as magnesium, zinc and calcium, are currently extensively studied in order to utilize them as a material for biodegradable orthopaedic implants. amongst all Mg-Zn-Ca alloys investigated up to date, the Mg66Zn30Ca4 composition has the greatest potential for applications. Its critical casting thickness reaches a value of 5 mm, the compressive strength (716–854 MPa) is about 4 times the limit of human cortical bone while elastic modulus is (31 GPa) is only 3 times higher than that of human bone. During dissolution the alloy shows only marginal hydrogen evolution. Here we present a detailed, experiment-based structural investigation of Mg66Zn30Ca4. Structural and topological analysis of its atomic structure reveals a high number of predominantly icosahedral densely packed Zn-centred clusters. It is believed that the existence of these structural units is responsible for the suppression of internal diffusion and thus greatly improves glass formability.
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Apr 2021
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I15-1-X-ray Pair Distribution Function (XPDF)
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Jianwei
Zheng
,
Lilin
Lu
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Konstantin
Lebedev
,
Simson
Wu
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Pu
Zhao
,
Ian J.
Mcpherson
,
Tai-Sing
Wu
,
Ryuichi
Kato
,
Yiyang
Li
,
Ping-Luen
Ho
,
Guangchao
Li
,
Linlu
Bai
,
Jianhui
Sun
,
Dharmalingam
Prabhakaran
,
Robert A.
Taylor
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Yun-Liang
Soo
,
Kazu
Suenaga
,
Shik Chi Edman
Tsang
Abstract: Current industrial production of ammonia from the Haber-Bosch process and its transport concomitantly produces a large quantity of CO2. Herein, we successfully synthesize inorganic-structure-based catalysts with [Fe-S2-Mo] motifs with a connecting structure similar to that of FeMoco (a cofactor of nitrogenase) by placing iron atoms on a single molecular layer of MoS2 at various loadings. This type of new catalytic material functionally mimics the nitrogenase to convert N2 to ammonia and hydrogen in water without adding any sacrificial agent under visible-light illumination. Using the elevated temperature boosts the ammonia yield and the energy efficiency by one order of magnitude. The solar-to-NH3 energy-conversion efficiency can be up to 0.24% at 270°C, which is the highest efficiency among all reported photocatalytic systems. This method of ammonia production and the photocatalytic materials may open up an exciting possibility for the decentralization of ammonia production for fertilizer provision to local farmlands using solar illumination.
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Apr 2021
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I13-2-Diamond Manchester Imaging
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Abstract: Porosity is the term used to describe the voids in a rock. This porosity is made up of many pores which form a pore network. Pore scale displacement in fluid flow is relevant to a number of industrial and environmental applications. The characteristics of the pore network control the way in which fluid flow occurs throughout the network. Carbonate rocks have particularly complex pore networks due a range of post-depositional processes that modify pore size, shape and connectivity. Although the contributions of factors such as pore throat size and pore network connectivity on fluid flow are reasonably well understood, there is a limited understanding of the effect of pore topology. This research aims to provide a pore-scale picture of the dynamics of fluid flow in both single and multiphase immiscible flow through the use of digital image analysis of fluid flow experiments. The dynamics and patterns of interface displacement as well as the size distribution of trapped oil ganglia were visualised using 2D microfluidic experiments. Different pore topologies resulted in different oil recoveries, however the effect of pore topology was not constant across fluid pairs with different viscosity ratios. Pore size was shown to be a key factor in the recovery efficiency of polymer flooding. This demonstrates that microfluidic experiments offer a methodology to quickly assess a number of different pore topologies under different fluid flow conditions. A range of rock types were imaged in 3D using X-Ray micro-computed tomography to visualise and quantify the range of pore topologies which exist in carbonates. These pore systems were used to assess the reliability of using 2D digital image analysis for permeability prediction, and show that 3D digital image analysis is a far superior technique for reliable pore topological characterisation and permeability prediction. A highly correlated multi-linear regression between permeability and pore topological parameters shows the relevance of pore topologies in predicting permeability. In addition to the investigation of single phase flow in a range of different carbonate pore systems, an investigation into multiphase immiscible displacement in a single carbonate pore system has been conducted. Through the use of synchrotron X-Ray tomographic imaging of an experimental core-flood (oil-brine drainage followed by imbibition) insights into the dynamics of multiphase flow have been gained. The pathway followed by the non-wetting fluid during drainage is strongly linked to the pore topological parameters measured during the analysis of the experiment. Oil initially invades simple pores with low elongation, which are aligned with the flow direction, before invading increasingly complex pores, less aligned to the flow direction. A channelization of flow occurs associated with an area of large, elongate pores. This research demonstrates that pore topology, particularly elongation and orientation to flow direction, has a clear influence on flow and warrants further investigation.
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Mar 2021
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Open Access
Abstract: Batteries are the most abundant form of electrochemical energy storage. Lithium and sodium ion batteries account for a significant portion of the battery market, but high-performance electrochemically active materials still need to be discovered and optimized for these technologies. Recently, tin(II) oxide (SnO) has emerged as a highly promising battery electrode. In this work, we present a facile synthesis method to produce SnO microparticles whose size and shape can be tailored by changing the solvent nature. We study the complex relationship between wet-chemistry synthesis conditions and resulting layered nanoparticle morphology. Furthermore, high-level electronic structure theory, including dispersion corrections to account for van der Waals forces, is employed to enhance our understanding of the underlying chemical mechanisms. The electronic vacuum alignment and surface energies are determined, allowing the prediction of the thermodynamically favoured crystal shape (Wulff construction) and surface-weighted work function. Finally, the synthesized nanomaterials were tested as Li-ion battery anodes, demonstrating significantly enhanced electrochemical performance for morphologies obtained from specific synthesis conditions.
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Mar 2021
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Open Access
Abstract: Ternary lanthanide indium oxides LnInO3 (Ln = La, Pr, Nd, Sm) were synthesized by high-temperature solid-state reaction and characterized by X-ray powder diffraction. Rietveld refinement of the powder patterns showed the LnInO3 materials to be orthorhombic perovskites belonging to the space group Pnma, based on almost-regular InO6 octahedra and highly distorted LnO12 polyhedra. Experimental structural data were compared with results from density functional theory (DFT) calculations employing a hybrid Hamiltonian. Valence region X-ray photoelectron and K-shell X-ray emission and absorption spectra of the LnInO3 compounds were simulated with the aid of the DFT calculations. Photoionization of lanthanide 4f orbitals gives rise to a complex final-state multiplet structure in the valence region for the 4fn compounds PrInO3, NdInO3, and SmInO3, and the overall photoemission spectral profiles were shown to be a superposition of final-state 4fn–1 terms onto the cross-section weighted partial densities of states from the other orbitals. The occupied 4f states are stabilized in moving across the series Pr–Nd–Sm. Band gaps were measured using diffuse reflectance spectroscopy. These results demonstrated that the band gap of LaInO3 is 4.32 eV, in agreement with DFT calculations. This is significantly larger than a band gap of 2.2 eV first proposed in 1967 and based on the idea that In 4d states lie above the top of the O 2p valence band. However, both DFT and X-ray spectroscopy show that In 4d is a shallow core level located well below the bottom of the valence band. Band gaps greater than 4 eV were observed for NdInO3 and SmInO3, but a lower gap of 3.6 eV for PrInO3 was shown to arise from the occupied Pr 4f states lying above the main O 2p valence band.
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Mar 2021
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B21-High Throughput SAXS
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Diamond Proposal Number(s):
[18022]
Abstract: The human immunoglobulin G (IgG) class is the most prevalent antibody in serum, with the IgG1 subclass being the most abundant. IgG1 is comprised of two Fab regions connected to a Fc region through a 15-residue hinge peptide. Two glycan chains are conserved in the Fc region in IgG, however their importance for the structure of intact IgG1 has remained unclear. Here, we subjected glycosylated and deglycosylated monoclonal human IgG1 (designated as A33) to a comparative multidisciplinary structural study of both forms. Following deglycosylation using PNGase F, analytical ultracentrifugation showed that IgG1 remained monomeric and the sedimentation coefficients s020,w of IgG1 decreased from 6.45 S by 0.16-0.27 S. This change was attributed to the reduction in mass following glycan removal. X-ray and neutron scattering revealed changes in the Guinier structural parameters after deglycosylation. While the radius of gyration RG was unchanged, the cross-sectional radius of gyration, RXS-1, increased by 0.1 nm and the commonly occurring distance peak M2 of the distance distribution curve P(r) increased by 0.4 nm. These changes revealed that the Fab-Fc separation in IgG1 was perturbed following deglycosylation. To explain these changes, atomistic scattering modelling based on Monte Carlo simulations resulted in 123,284 and 119,191 trial structures for glycosylated and deglycosylated IgG1 respectively. From these, 100 X-ray and neutron best-fit models were determined. For these, principal component analyses identified five groups of structural conformations that were different for glycosylated and deglycosylated IgG1. The Fc region in glycosylated IgG1 showed a restricted range of conformations relative to the Fab regions, while the Fc region in deglycosylated IgG1 showed a broader conformational spectrum. These more variable Fc conformations account for the loss of binding to the FcγR receptor in deglycosylated IgG1.
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Mar 2021
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I09-Surface and Interface Structural Analysis
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Peter
Knecht
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Bodong
Zhang
,
Joachim
Reichert
,
David A.
Duncan
,
Martin
Schwarz
,
Felix
Haag
,
Paul
Ryan
,
Tien-lin
Lee
,
Peter S.
Deimel
,
Peter
Feulner
,
Francesco
Allegretti
,
Willi
Auwärter
,
Guillaume
Médard
,
Ari Paavo
Seitsonen
,
Johannes V.
Barth
,
Anthoula C.
Papageorgiou
Diamond Proposal Number(s):
[24320]
Abstract: The controlled arrangement of N-heterocyclic carbenes (NHCs) on solid surfaces is a current challenge of surface functionalization. We introduce a strategy of using Ru porphyrins in order to control both the orientation and lateral arrangement of NHCs on a planar surface. The coupling of the NHC to the Ru porphyrin is a facile process which takes place on the interface: we apply NHCs as functional, robust pillars on well-defined, preassembled Ru porphyrin monolayers on silver and characterize these interfaces with atomic precision via a battery of experimental techniques and theoretical considerations. The NHCs assemble at room temperature modularly and reversibly on the Ru porphyrin arrays. We demonstrate a selective and complete functionalization of the Ru centers. With its binding, the NHC modifies the interaction of the Ru porphyrin with the Ag surface, displacing the Ru atom by 1 Å away from the surface. This arrangement of NHCs allows us to address individual ligands by controlled manipulation with the tip of a scanning tunneling microscope, creating patterned structures on the nanometer scale.
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Mar 2021
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I05-ARPES
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Christopher W.
Nicholson
,
Maxime
Rumo
,
Aki
Pulkkinen
,
Geoffroy
Kremer
,
Björn
Salzmann
,
Marie-laure
Mottas
,
Baptiste
Hildebrand
,
Thomas
Jaouen
,
Timur K.
Kim
,
Saumya
Mukherjee
,
Keyuan
Ma
,
Matthias
Muntwiler
,
Fabian O.
Von Rohr
,
Cephise
Cacho
,
Claude
Monney
Diamond Proposal Number(s):
[24880]
Open Access
Abstract: Strain is ubiquitous in solid-state materials, but despite its fundamental importance and technological relevance, leveraging externally applied strain to gain control over material properties is still in its infancy. In particular, strain control over the diverse phase transitions and topological states in two-dimensional transition metal dichalcogenides remains an open challenge. Here, we exploit uniaxial strain to stabilize the long-debated structural ground state of the 2D topological semimetal IrTe2, which is hidden in unstrained samples. Combined angle-resolved photoemission spectroscopy and scanning tunneling microscopy data reveal the strain-stabilized phase has a 6 × 1 periodicity and undergoes a Lifshitz transition, granting unprecedented spectroscopic access to previously inaccessible type-II topological Dirac states that dominate the modified inter-layer hopping. Supported by density functional theory calculations, we show that strain induces an Ir to Te charge transfer resulting in strongly weakened inter-layer Te bonds and a reshaped energetic landscape favoring the 6×1 phase. Our results highlight the potential to exploit strain-engineered properties in layered materials, particularly in the context of tuning inter-layer behavior.
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Mar 2021
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