B18-Core EXAFS
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Diamond Proposal Number(s):
[39912]
Open Access
Abstract: Copper (Cu) is a recyclable, abundant, and promising catalyst for energy transition reactions like electrochemical conversion of nitrate (NO₃RR) and CO2 electroreduction. However, conventional Cu-based electrocatalysts struggle with activity, selectivity, and durability, especially under harsh electrochemical conditions. Exsolution—the in-situ generation of metallic nanoparticles on oxide supports in a single step—enables tightly anchored, size-controlled particles, enhancing stability and performance. Incorporating Cu into Sr1-α(Ti, Fe)O₃-γ perovskites, an earth-abundant system with promising ionic-electronic conductivity and adequate oxygen vacancies, overcomes the limitations of traditional Sr(Ti, Fe)O₃ in facilitating nanoparticle exsolution. This work demonstrates controlled Cu nanoparticle exsolution from Sr₀.₉₅Ti₀.₃Fe₀.₇₋ₓCuₓO₃₋ᵧ perovskites at temperatures as low as 400°C, notably milder than conventional exsolution conditions. By systematically varying reduction parameters, we achieve control over nanoparticle size (13-38 nm) and population density (118-650 particles/μm²). Electrochemical characterisation using nitrate reduction as a probe reaction demonstrates how exsolution conditions directly influence surface reactivity, establishing these materials as tuneable platforms for (electro)catalytic applications.
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Dec 2025
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I09-Surface and Interface Structural Analysis
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Ali
Sufyan
,
Tyler
James
,
Connor
Fields
,
Shabnam
Naseri
,
Filipe L. Q.
Junqueira
,
Sofia
Alonso Perez
,
Sally
Bloodworth
,
Gabriella
Hoffman
,
Mark C.
Walkey
,
Elizabeth S.
Marsden
,
Richard J.
Whitby
,
Yitao
Wang
,
David A.
Duncan
,
Tien-Lin
Lee
,
James N.
O'Shea
,
Andreas
Larsson
,
Brian
Kiraly
,
Philip
Moriarty
Diamond Proposal Number(s):
[31574]
Open Access
Abstract: Core-level and tunnelling spectroscopies applied to noble gas endofullerenes offer complementary insights into electron transfer rates, addressing both intramolecular and extramolecular processes. Elastic and inelastic tunnelling spectroscopy of empty C60 and Kr@C60 on Pb/Cu(111) each show that the encapsulated atom is essentially invisible to scanning probes. We interpret the lineshape of the lowest unoccupied molecular orbital (LUMO) of Pb-adsorbed (endo)fullerenes in tunnelling spectra as a signature of the dynamic Jahn-Teller (DJ-T) effect. This effect persists in electronically decoupled second-layer molecules, which also display distinct vibronic progressions in on-resonance tunnelling. DFT calculations reproduce the LUMO alignment and low density of states at the Fermi level seen in experimental tunnelling spectra for (endo)fullerenes on Pb, and, in line with submolecular resolution STM images, also predict that an atom-down orientation of the fullerene cage is energetically most favourable (although other adsorption geometries differ only by tens of meV at most). In contrast to the tunnelling data, core-level-focussed techniques -namely, photoemission, X-ray absorption, and resonant Auger-Meitner electron spectroscopy -of Ar@C60/Pb(111) indicate that the encapsulated atom is heavily coupled to the molecular environment, with both a clear influence of substrate screening on the core-level lineshape and the absence of spectator signal in decay spectra.
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Oct 2025
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[21791]
Open Access
Abstract: We investigate how synthesis method affect the crystallite size and atomic structure of cobalt iron oxide nanoparticles. By using a simple solvothermal method, we first synthesize cobalt ferrite nanoparticles of ca. 2 and 7 nm, characterized by Transmission Electron Microscopy (TEM), Small Angle X-ray scattering (SAXS), X-ray and neutron total scattering. The smallest particle size corresponds to only a few spinel unit cells, nevertheless, Pair Distribution Function (PDF) analysis of X-ray and neutron total scattering data show that the atomic structure in even the smallest nanoparticles is well described by the spinel structure, however with significant disorder and a contraction of the unit cell parameter. These effects can be explained by surface oxidation of the small nanoparticles, which is confirmed by X-ray near edge absorption spectroscopy (XANES). Neutron total scattering data and PDF analysis reveal a larger degree of inversion of the spinel of the smallest nanoparticles. Neutron total scattering data furthermore allows magnetic PDF (mPDF) analysis, which show that the ferrimagnetic domains correspond to ca. 80% of the crystallite size in the larger particles. A similar but less well-defined magnetic ordering was observed for the smallest nanoparticles. Finally, we use a co-precipitation synthesis method at room temperature to synthesize ferrite nanoparticles of similar size as the smallest crystallites synthesized by the solvothermal method. Structural analysis with PDF demonstrates that the ferrite nanoparticles synthesized via this method exhibit a significantly more defective structure compared to those synthesized via a solvothermal method.
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Sep 2024
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I22-Small angle scattering & Diffraction
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Open Access
Abstract: Organic phosphates (OP) are important nutrient components for living cells in natural environments, where they readily interact with ubiquitous iron phases such as hydrous ferric oxide, ferrihydrite (FHY). FHY partakes in many key bio(geo)chemical reactions including iron-mediated carbon storage in soils, or iron-storage in living organisms. However, it is still unknown how OP affects the formation, structure and properties of FHY. Here, we document how β-glycerophosphate (GP), a model OP ligand, affects the structure and properties of GP–FHY nanoparticles synthesized by coprecipitation at variable nominal molar P/Fe ratios (0.01 to 0.5). All GP–FHY precipitates were characterized by a maximum solid P/Fe ratio of 0.22, irrespective of the nominal P/Fe ratio. With increasing nominal P/Fe ratio, the specific surface area of the GP–FHY precipitates decreased sharply from 290 to 3 m2 g−1, accompanied by the collapse of their pore structure. The Fe–P local bonding environment gradually transitioned from a bidentate binuclear geometry at low P/Fe ratios to monodentate mononuclear geometry at high P/Fe ratios. This transition was accompanied by a decrease in coordination number of edge-sharing Fe polyhedra, and the loss of the corner-sharing Fe polyhedra. We show that Fe(III) polymerization is impeded by GP, and that the GP–FHY structure is highly dependent on the P/Fe ratio. We discuss the role that natural OP-bearing Fe(III) nanophases have in biogeochemical reactions between Fe–P and C species in aquatic systems.
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Apr 2024
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E01-JEM ARM 200CF
E02-JEM ARM 300CF
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Diamond Proposal Number(s):
[16991, 18188]
Open Access
Abstract: The 16e square-planar bis-thiolato-Au(III) complexes [AuIII(1,2-dicarba-closo-dodecarborane-1,2-dithiolato)2][NBu4] (Au-1) and [AuIII(4-methyl-1,2-benzenedithiolato)2][NBu4] (Au-2) have been synthesized and fully characterized. Au-1 and Au-2 were encapsulated in the symmetrical triblock copolymer poloxamer (Pluronic®) P123 containing blocks of poly(ethylene oxide) and poly(propylene oxide), giving micelles AuMs-1 and AuMs-2. High electron flux in scanning transmission electron microscopy (STEM) was used to generate single gold atoms and gold nanocrystals on B/S-doped graphitic surfaces, or S-doped amorphous carbon surfaces from AuMs-1 and AuMs-2, respectively. Electron energy loss spectroscopy (EELS) data suggested strong interactions of gold atoms/nanocrystals with boron in the B/S-doped graphitic matrix. Density-functional theory (DFT) calculations, also supported the experimental findings, pointing towards strong Au–B bonds, depending on the charge on the Au–(B-graphene) fragment and the presence of further defects in the graphene lattice.
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Dec 2023
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B21-High Throughput SAXS
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Diamond Proposal Number(s):
[28659]
Open Access
Abstract: The large-scale use of glyphosate pesticides in food production has attracted attention due to environmental damage and toxicity risks. Several regulatory authorities have established safe limits or concentrations of these pesticides in water and various food products consumed daily. The irreversible inhibition of acetylcholinesterase (AChE) activity is one of the strategies used for pesticide detection. Herein, we found that lipopeptide sequences can act as biomimetic microenvironments of AChE, showing higher catalytic activities than natural enzymes in an aqueous solution, based on IC50 values. These biomolecules contain in the hydrophilic part the amino acids L-proline (P), L-arginine (R), L-tryptophan (W), and L-glycine (G), covalently linked to a hydrophobic part formed by one or two long aliphatic chains. The obtained materials are referred to as compounds 1 and 2, respectively. According to fluorescence assays, 2 is more hydrophobic than 1. The circular dichroism (CD) data present a significant difference in the molar ellipticity values, likely related to distinct conformations assumed by the proline residue in the lipopeptide supramolecular structure in solution. The morphological aspect was further characterized using small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM), which showed that compounds 1 and 2 self-assembly into cylindrical and planar core–shell structures, respectively. The mimetic AchE behaviour of lipopeptides was confirmed by Ellman's hydrolysis reaction, where the proline residue in the peptides act as a nucleophilic scavenger of organophosphate pesticides. Moreover, the isothermal titration calorimetry (ITC) experiments revealed that host–guest interactions in both systems were dominated by enthalpically-driven thermodynamics. UV-vis kinetic experiments were performed to assess the inhibition of the lipopeptide catalytic activity and the IC50 values were obtained, and we found that the detection limit correlated with the increase in hydrophobicity of the lipopeptides, implying the micellization process is more favorable.
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Aug 2022
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I07-Surface & interface diffraction
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Diamond Proposal Number(s):
[21922]
Open Access
Abstract: A high-throughput method for the fabrication of ordered arrays of Au nanoparticles is presented. It is based on pulsed electrodeposition into porous anodic alumina templates. In contrast to many synthesis routes, it is cyanide-free, prior separation of the alumina template from the aluminium substrate is not required, and the use of contaminating surfactants/capping agents often found in colloidal synthesis is avoided. The aspect ratio of the nanoparticles can also be tuned by selecting an appropriate electrodeposition time. We show how to fabricate arrays of nanoparticles, both with branched bases and with hemispherical bases. Furthermore, we compare the different morphologies produced with electron microscopies and grazing-incidence synchrotron X-ray diffraction. We find the nanoparticles are polycrystalline in nature and are compressively strained perpendicular to the direction of growth, and expansively strained along the direction of growth. We discuss how this can produce dislocations and twinning defects that could be beneficial for catalysis.
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May 2022
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I09-Surface and Interface Structural Analysis
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Qi
Wang
,
Jiacheng
Yang
,
Antoni
Franco-Canellas
,
Christoph
Buerker
,
Jens
Niederhausen
,
Pierre
Dombrowski
,
Felix
Widdascheck
,
Tobias
Breuer
,
Gregor
Witte
,
Alexander
Gerlach
,
Steffen
Duhm
,
Frank
Schreiber
Diamond Proposal Number(s):
[18860]
Open Access
Abstract: As crucial element in organic opto-electronic devices, heterostructures are of pivotal importance. In this context, a comprehensive study of the properties on a simplified model system of a donor–acceptor (D–A) bilayer structure is presented, using ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED) and normal-incidence X-ray standing wave (NIXSW) measurements. Pentacene (PEN) as donor and perfluoropentacene (PFP) as acceptor material are chosen to produce bilayer structures on Au(111) and Cu(111) by sequential monolayer deposition of the two materials. By comparing the adsorption behavior of PEN/PFP bilayers on such weakly and strongly interacting substrates, it is found that: (i) the adsorption distance of the first layer (PEN or PFP) indicates physisorption on Au(111), (ii) the characteristics of the bilayer structure on Au(111) are (almost) independent of the deposition sequence, and hence, (iii) in both cases a mixed bilayer is formed on the Au substrate. This is in striking contrast to PFP/PEN bilayers on Cu(111), where strong chemisorption pins PEN molecules to the metal surface and no intermixing is induced by subsequent PFP deposition. The results illustrate the strong tendency of PEN and PFP molecules to mix, which has important implications for the fabrication of PEN/PFP heterojunctions.
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Mar 2021
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I06-Nanoscience (XPEEM)
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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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I20-Scanning-X-ray spectroscopy (XAS/XES)
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George F.
Tierney
,
Donato
Decarolis
,
Norli
Abdullah
,
Scott M.
Rogers
,
Shusaku
Hayama
,
Martha
Briceno De Gutierrez
,
Alberto
Villa
,
C. Richard A.
Catlow
,
Paul
Collier
,
Nikolaos
Dimitratos
,
Peter
Wells
Diamond Proposal Number(s):
[17283]
Open Access
Abstract: Sol-immobilization is increasingly used to achieve supported metal nanoparticles (NPs) with controllable size and shape; it affords a high degree of control of the metal particle size and yields a narrow particle size distribution. Using state-of-the-art beamlines, we demonstrate how X-ray absorption fine structure (XAFS) techniques are now able to provide accurate structural information on nano-sized colloidal Au solutions at μM concentrations. This study demonstrates: (i) the size of Au colloids can be accurately tuned by adjusting the temperature of reduction, (ii) Au concentration, from 50 μM to 1000 μM, has little influence on the average size of colloidal Au NPs in solution and (iii) the immobilization step is responsible for significant growth in Au particle size, which is further exacerbated at increased Au concentrations. The work presented demonstrates that an increased understanding of the primary steps in sol-immobilization allows improved optimization of materials for catalytic applications.
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May 2019
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