I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[16372]
Open Access
Abstract: The exact formation mechanism of tantalum oxides (and in general, metal/mixed metal oxides) from alkoxide precursors is still not fully understood, particularly when forming cluster-like or amorphous materials. The structural evolution of Ta-based oxides was studied in detail using X-ray total scattering experiments along with subsequent pair distribution function (PDF) analyses. Starting from a tantalum alkoxide precursor (Ta2(OEt)10), the formation of hydrolysed TaxOyHz clusters in highly diluted aqueous solution was analysed. From the PDF data, the connectivity and arrangement of TaxOy octahedra in the cluster could be deduced as well as the approximate size of the clusters (<1 nm). Construction of cluster models allowed for identification of common structural motifs in the TaxOyHz clusters, ruling out the formation of chain- or ring-like clusters. More likely, bulky clusters with a high number of corner-sharing octahedra are formed. After separation of the amorphous solid from the liquid, temperature-induced crystallisation processes were monitored via in situ total scattering experiments. Between room temperature and 600 °C, only small rearrangements of the amorphous structure are observed. At about 610 °C, amorphous TaxOyHz transforms directly into crystalline orthorhombic L-Ta2O5 without formation of any crystalline intermediate structures.
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Nov 2020
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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
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Ye
Fan
,
Kenichi
Nakanishi
,
Vlad P.
Veigang-radulescu
,
Ryo
Mizuta
,
J. Callum
Stewart
,
Jack E. N.
Swallow
,
Alice E.
Dearle
,
Oliver J.
Burton
,
Jack A.
Alexander-webber
,
Pilar
Ferrer
,
Georg
Held
,
Barry
Brennan
,
Andrew J.
Pollard
,
Robert S
Weatherup
,
Stephan
Hofmann
Diamond Proposal Number(s):
[22123]
Open Access
Abstract: We find that the use of Au substrate allows fast, self-limited WS2 monolayer growth using a simple sequential exposure pattern of low cost, low toxicity precursors, namely tungsten hexacarbonyl and dimethylsulfide (DMS). We use this model reaction system to fingerprint the technologically important metal organic chemical vapour deposition process by operando X-ray photoelectron spectroscopy (XPS) to address the current lack of understanding of the underlying fundamental growth mechanisms for WS2 and related transition metal dichalcogenides. Au effectively promotes the sulfidation of W with simple organosulfides, enabling WS2 growth with low DMS pressure (<1 mbar) and a suppression of carbon contamination of as-grown WS2, which to date has been a major challenge with this precursor chemistry. Full WS2 coverage can be achieved by one exposure cycle of 10 minutes at 700 °C. We discuss our findings in the wider context of previous literature on heterogeneous catalysis, 2D crystal growth, and overlapping process technologies such as atomic layer deposition (ALD) and direct metal conversion, linking to future integrated manufacturing processes for transition metal dichalcogenide layers.
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Oct 2020
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I11-High Resolution Powder Diffraction
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Qi
Xue
,
Yi
Xie
,
Simson
Wu
,
Tai-sing
Wu
,
Yun-liang
Soo
,
Sarah
Day
,
Chiu C.
Tang
,
Ho W.
Man
,
Sha T.
Yuen
,
Kwok-yin
Wong
,
Yin
Wang
,
Benedict T. W.
Lo
,
Shik C. E.
Tsang
Diamond Proposal Number(s):
[23230]
Abstract: We investigate the geometric and electronic properties of single-atom catalysts (SACs) within metal–organic frameworks (MOFs) with respect to electrocatalytic CO2 reduction as a model reaction. A series of mid-to-late 3d transition metals have been immobilised within the microporous cavity of UiO-66-NH2. By employing Rietveld refinement of new-generation synchrotron diffraction, we not only identified the crystallographic and atomic parameters of the SACs that are stabilised with a robust M⋯N(MOF) bonding of ca. 2.0 Å, but also elucidated the end-on coordination geometry with CO2. A volcano trend in the FEs of CO has been observed. In particular, the confinement effect within the rigid MOF can greatly facilitate redox hopping between the Cu SACs, rendering high FEs of CH4 and C2H4 at a current density of −100 mA cm−2. Although only demonstrated in selected SACs within UiO-66-NH2, this study sheds light on the rational engineering of molecular interactions(s) with SACs for the sustainable provision of fine chemicals.
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Oct 2020
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E01-JEM ARM 200CF
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Qian
Guo
,
Hui
Luo
,
Jifang
Zhang
,
Qiushi
Ruan
,
Arun
Prakash Periasamy
,
Yuanxing
Fang
,
Zailai
Xie
,
Xuanhua
Li
,
Xinchen
Wang
,
Junwang
Tang
,
Joe
Briscoe
,
Magdalena
Titirici
,
Ana Belen
Jorge
Diamond Proposal Number(s):
[22447]
Open Access
Abstract: Hematite is a promising candidate as photoanode for solar-driven water splitting, with a theoretically predicted maximum solar-to-hydrogen conversion efficiency of ∼16%. However, the interfacial charge transfer and recombination greatly limits its activity for photoelectrochemical water splitting. Carbon dots exhibit great potential in photoelectrochemical water splitting for solar to hydrogen conversion as photosensitisers and co-catalysts. Here we developed a novel carbon underlayer from low-cost and environmental-friendly carbon dots through a facile hydrothermal process, introduced between the fluorine-doped tin oxide conducting substrate and hematite photoanodes. This led to a remarkable enhancement in the photocurrent density. Owing to the triple functional role of carbon dots underlayer in improving the interfacial properties of FTO/hematite and providing carbon source for the overlayer as well as the change in the iron oxidation state, the bulk and interfacial charge transfer dynamics of hematite are significantly enhanced, and consequently led to a remarkable enhancement in the photocurrent density. The results revealed a substantial improvement in the charge transfer rate, yielding a charge transfer efficiency of up to 80% at 1.25 V vs. RHE. In addition, a significant enhancement in the lifetime of photogenerated electrons and an increased carrier density were observed for the hematite photoanodes modified with a carbon underlayer, confirming that the use of sustainable carbon nanomaterials is an effective strategy to boost the photoelectrochemical performance of semiconductors for energy conversion.
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Sep 2020
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B18-Core EXAFS
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Open Access
Abstract: Magic-size clusters are ultra-small colloidal semiconductor systems that are intensively studied due to their monodisperse nature and sharp UV-vis absorption peak compared with regular quantum dots. However, the small size of such clusters (<2 nm), and the large surface-to-bulk ratio significantly limit characterisation techniques that can be utilised. Here we demonstrate how a combination of EXAFS and XANES analyses can be used to obtain information about sample stoichiometry and cluster symmetry. Investigating two types of clusters that show sharp UV-vis absorption peaks at 311 nm and 322 nm, we found that both samples possess approximately 2[thin space (1/6-em)]:[thin space (1/6-em)]1 Cd[thin space (1/6-em)]:[thin space (1/6-em)]S ratio and have similar nearest-neighbour structural arrangements. However, both samples demonstrate a significant departure from the tetrahedral structural arrangement, with an average bond angle determined to be around 106.1° showing a bi-fold bond angle distribution. Our results suggest that both samples are quasi-isomers – their core structures have identical chemical compositions, but different atomic arrangements with distinct bond angle distributions.
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Sep 2020
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[16243]
Open Access
Abstract: Interesting electronic properties arise in vertically stacked graphene sheets, some of which can be controlled by mutual orientation of the adjacent layers. In this study, we investigate the MBE grown multilayer graphene on Ir(111) by means of STM, LEED and XPS and we examine the influence of the substrate on the geometric and electronic properties of bilayer graphene by employing XSW and ARPES measurements. We find that the MBE method does not limit the growth to two graphene layers and that the wrinkles, which arise through extended carbon deposition, play a crucial role in the multilayer growth. We also find that the bilayer and trilayer graphene sheets have graphitic-like properties in terms of the separation between the two layers and their stacking. The presence of the iridium substrate imposes a periodic potential induced by the moiré pattern that was found to lead to the formation of replica bands and minigaps in bilayer graphene. From tight-binding fits to our ARPES data we find that band renormalization takes place in multilayer graphene due to a weaker coupling of the upper-most graphene layer to the iridium substrate.
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Sep 2020
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B18-Core EXAFS
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Diamond Proposal Number(s):
[15151]
Open Access
Abstract: The control of the growth of hematite nanoparticles from iron chloride solutions under hydrothermal conditions in the presence of two different structure promoters has been studied using a range of both structural and spectroscopic techniques including the first report of photo induced force microscopy (PiFM) to map the topographic distribution of the structure-directing agents on the developing nanoparticles. We show that the shape of the nanoparticles can be controlled using the concentration of phosphate ions up to a limit determined to be ~6 × 10−3 mol. Akaganéite (β-FeOOH) is a major component of the nanoparticles formed in the absence of structure directors but only present in the very early stages (< 8 h) of particle growth when phosphate is present. The PiFM data suggest a correlation between the areas in which phosphate ions are adsorbed and areas where akaganéite persists on the surface. In contrast, goethite (α-FeOOH) is a directly observed precursor of the hematite nanorods when 1,2-diamino propane is present. The PiFM data shows goethite in the center of the developing particles consistent with a mechanism in which the iron hydroxide re-dissolves and precipitates at the nanorod ends as hematite.
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Aug 2020
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E01-JEM ARM 200CF
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Diamond Proposal Number(s):
[21253]
Open Access
Abstract: The rejection of particles with different charges and sizes, ranging from a few Ångstroms to tens of nanometers, is key to a wide range of industrial applications, from wastewater treatment to product purification in biotech processes. Carbon nanotubes (CNTs) have long held the promise to revolutionize filtration, with orders of magnitude higher fluxes compared to commercial membranes. CNTs, however, can only reject particles and ions wider than their internal diameter. In this work, the fabrication of aligned boron nitride nanotube (BNNT) membranes capable of rejecting nanoparticles smaller than their internal diameter is reported for the first time. This is due to a mechanism of charge-based rejection in addition to the size-based one, enabled by the BNNTs surface structure and chemistry and elucidated here using high fidelity molecular dynamics and Brownian dynamics simulations. This results in ∼40% higher rejection of the same particles by BNNT membranes than CNT ones with comparable nanotube diameter. Furthermore, since permeance is proportional to the square of the nanotubes’ diameter, using BNNT membranes with ∼30% larger nanotube diameter than a CNT membrane with comparable rejection would result in up to 70% higher permeance. These results open the way to the design of more effective nanotube membranes, capable of high particle rejection and, at the same time, high water permeance.
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Jul 2020
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I05-ARPES
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Liheng
An
,
Xiangbin
Cai
,
Ding
Pei
,
Meizhen
Huang
,
Zefei
Wu
,
Zishu
Zhou
,
Jiangxiazi
Lin
,
Zhehan
Ying
,
Ziqing
Ye
,
Xuemeng
Feng
,
Ruiyan
Gao
,
Cephise
Cacho
,
Matthew
Watson
,
Yulin
Chen
,
Ning
Wang
Diamond Proposal Number(s):
[24366]
Abstract: Twisted bilayer graphene provides a new two-dimensional platform for studying electron interaction phenomena and flat band properties such as correlated insulator transition, superconductivity and ferromagnetism at certain magic angles. Here, we present experimental characterization of interaction effects and superconductivity signatures in p-type twisted double-bilayer WSe2. Enhanced interlayer interactions are observed when the twist angle decreases to a few degrees as reflected by the high-order satellites in the electron diffraction patterns taken from the reconstructed domains from a conventional moiré superlattice. In contrast to twisted bilayer graphene, there is no specific magic angle for twisted WSe2. Flat band properties are observable at twist angles ranging from 1 to 4 degrees. Our work has facilitated future study in the area of flat band related properties in twisted transition metal dichalcogenide layered structures.
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Jul 2020
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I06-Nanoscience
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Diamond Proposal Number(s):
[17563]
Open Access
Abstract: Exchange-bias has been reported in bulk nanocrystalline Fe2MnAl, but individual thin films of this Heusler alloy have never been studied so far. Here we study the structural and magnetic properties of nanocrystalline thin films of Fe2–xMn1+xAl (x = –0.25, 0, 0.25) obtained by sputtering and ex-situ post-deposition annealing. We find that Fe2MnAl films display exchange-bias, and that varying Mn concentration determines the magnitude of the effect, which can be either enhanced (in Fe1.75Mn1.25Al) or suppressed (in Fe2.25Mn0.75Al). X-ray diffraction (XRD) shows that our films present a mixed L21-B2 Heusler structure where increasing Mn concentration favors the partial transformation of the L21 phase into the B2 phase. Scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDX) reveal that this composition-driven L21→B2 transformation is accompanied by phase segregation at the nanoscale. As a result, the Fe2–xMn1+xAl films that show exchange-bias (x = 0, 0.25) are heterogeneous, with nanograins of an Fe-rich phase embedded in a Mn-rich matrix (a non-negative matrix factorisation algorithm was used to give an indication of the phase composition from EDX data). Our comparative analysis of XRD, magnetometry and X-ray magnetic circular dichroism (XMCD), shows that Fe-rich nanograins and Mn-rich matrix are composed of a ferromagnetic L21 phase and an antiferromagnetic B2 phase, respectively, thus revealing that exchange-coupling between these two phases is the cause of the exchange-bias effect. Our work should inspire the development of single-layer, environmentally-friendly spin valve devices based on nanocomposite Heusler films.
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May 2020
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