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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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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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
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Georg
Held
,
Federica
Venturini
,
David C.
Grinter
,
Pilar
Ferrer
,
Rosa
Arrigo
,
Liam
Deacon
,
Wilson
Quevedo Garzon
,
Kanak
Roy
,
Alex
Large
,
Christopher
Stephens
,
Andrew
Watts
,
Paul
Larkin
,
Matthew
Hand
,
Hongchang
Wang
,
Linda
Pratt
,
James J.
Mudd
,
Thomas
Richardson
,
Suren
Patel
,
Michael
Hillman
,
Stewart
Scott
Open Access
Abstract: The ambient-pressure endstation and branchline of the Versatile Soft X-ray (VerSoX) beamline B07 at Diamond Light Source serves a very diverse user community studying heterogeneous catalysts, pharmaceuticals and biomaterials under realistic conditions, liquids and ices, and novel electronic, photonic and battery materials. The instrument facilitates studies of the near-surface chemical composition, electronic and geometric structure of a variety of samples using X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy in the photon energy range from 170 eV to 2800 eV. The beamline provides a resolving power hν/Δ(hν) > 5000 at a photon flux > 1010 photons s−1 over most of its energy range. By operating the optical elements in a low-pressure oxygen atmosphere, carbon contamination can be almost completely eliminated, which makes the beamline particularly suitable for carbon K-edge NEXAFS. The endstation can be operated at pressures up to 100 mbar, whereby XPS can be routinely performed up to 30 mbar. A selection of typical data demonstrates the capability of the instrument to analyse details of the surface composition of solid samples under ambient-pressure conditions using XPS and NEXAFS. In addition, it offers a convenient way of analysing the gas phase through X-ray absorption spectroscopy. Short XPS spectra can be measured at a time scale of tens of seconds. The shortest data acquisition times for NEXAFS are around 0.5 s per data point.
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Sep 2020
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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
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Andrea
Resta
,
Uta
Hejral
,
Sara
Blomberg
,
Stefano
Albertin
,
Alina
Vlad
,
Yves
Garreau
,
Corentin
Chatelier
,
Federica
Venturini
,
Pilar
Ferrer
,
Georg
Held
,
Dave
Grinter
,
Edvin
Lundgren
,
Alessandro
Coati
Diamond Proposal Number(s):
[21936]
Abstract: The reaction of ammonia oxidation over PtRh binary alloy has been studied with a surface science approach by operando techniques such as Near Ambient Pressure X-Ray Photoemission Spectroscopy (NAP-XPS) and Surface X-Ray Diffraction (SXRD) combined with mass spectrometry. The article will explore the surface evolution across five different oxygen to ammonia ratios in the millibar regime for two different temperatures. The presented data-set allows to link variations in the atomic structures measured by diffraction methods and surface species information from NAP-XPS to reaction products in the gas phase. We will show that NO production coincides with significant changes of the surface structure and the formation of a RhO2 surface oxide. It was also observed that the RhO2 surface oxide only fully forms when the nitrogen signal in the N1s has disappeared.
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Sep 2020
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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
E01-JEM ARM 200CF
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Gianfranco
Giorgianni
,
Chalachew
Mebrahtu
,
Manfred E.
Schuster
,
Alexander I.
Large
,
Georg
Held
,
Pilar
Ferrer
,
Federica
Venturini
,
David
Grinter
,
Regina
Palkovits
,
Siglinda
Perathoner
,
Gabriele
Centi
,
Salvatore
Abate
,
Rosa
Arrigo
Diamond Proposal Number(s):
[19472]
Abstract: Hydrotalcite-derived Ni and Fe-promoted hydrotalcite-derived Ni catalysts were found to outperform industrial catalysts in the CO2 methanation reaction, however the origin of the improved activity and selectivity of these catalysts is not clear. Here, we report a study of these systems by means of in situ X-ray photoelectron spectroscopy and near-edge X-ray absorption spectroscopy elucidating the chemical nature of the catalysts` surface under reaction conditions and revealing the mechanism by which Fe promotes activity and selectivity towards methane. We show that the increase of the conversion leads to hydroxylation of the Ni surface following the formation of water during the reaction. This excessive Ni surface hydroxylation has however a detrimental effect as shown by a controlled study. A dominant metallic Ni surface exists in conditions of higher selectivity towards methane whereas if an increase of the Ni surface hydroxylation occurs, a higher selectivity towards carbon monoxide is observed. The electronic structure analysis of the Fe species under reaction conditions reveals the existence of predominantly Fe(III) species at the surface, whereas a mixture of Fe(II)/Fe(III) species is present underneath the surface. Our results highlight that Fe(II) exerts a beneficial effect on maintaining Ni in a metallic state, whereas the extension of the Fe oxidation front from the surface towards the bulk is accompanied by a more extended Ni surface hydroxylation with a negative impact on the selectivity towards methane.
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Apr 2020
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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
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Simson
Wu
,
Yung-Kang
Peng
,
Tianyi
Chen
,
Jiaying
Mo
,
Alex
Large
,
Ian
Mcpherson
,
Hung-Lung
Chou
,
Ian
Wilkinson
,
Federica
Venturini
,
David
Grinter
,
Pilar
Ferrer Escorihuela
,
Georg
Held
,
Shik Chi Edman
Tsang
Abstract: The increasing availability of low-cost and low pressure, renewable H2 from wind and solar means has triggered tremendous interest in developing low pressure ammonia synthesis with N2 as energy carrier as well as green fertilizer. As such Cs-promoted Ru/MgO catalysts used in Kellogg process show superiority to Fe-based catalysts at milder conditions, however, as known, the surface poisoning of Ru sites by competitive strong H2 dissociative adsorption limits the overall rate. It is demonstrated for the first time that the use of simple polar MgO(111) to replace non-polar MgO as support can significantly alleviate the hydrogen poisoning and facilitate an unprecedented ammonia production rate by its high intrinsic proton capture ability.
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Apr 2020
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Álvaro
García
,
María
Retuerto
,
Carlota
Dominguez
,
Laura
Pascual
,
Pilar
Ferrer
,
Diego
Gianolio
,
Aida
Serrano
,
Pia
Assmann
,
Daniel G.
Sanchez
,
Miguel A.
Peña
,
Sergio
Rojas
Open Access
Abstract: In this work, we report the synthesis of Fe/N/C electrocatalysts using triazine based porous organic polymers as precursors. Iron-doped triazine porous organic polymers were obtained by in situ polymerization of iron precursor and 1,2- or 1,4- dicyanobenzene (DCB). In order to obtain the actual catalyst, the polymer obtained was subjected to thermal treatment under NH3. The catalysts obtained exhibit activity and durability for the oxygen reduction reaction in acid electrolyte. Thorough characterization of the catalysts reveal the formation of several types of iron species, including metallic iron, iron carbides and Fe-Nx moieties. The latter species is the main responsible for the high activity measured for the oxygen reduction reaction in acid electrolyte. 1,2-DCB results in more active catalysts than 1,4-DCB due to the higher fraction of FeNx ensembles in the former, probably because vicinal positions of N-bearing groups are more prone to coordinate Fe atoms.
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Dec 2019
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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
B18-Core EXAFS
E01-JEM ARM 200CF
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Rosa
Arrigo
,
Simone
Gallarati
,
Manfred E.
Schuster
,
Jake
Seymour
,
Diego
Gianolio
,
Ivan
Da Silva
,
June
Callison
,
Haosheng
Feng
,
John E.
Proctor
,
Pilar
Ferrer
,
Federica
Venturini
,
Dave
Grinter
,
Georg
Held
Open Access
Abstract: Unsupported and SiO 2 ‐supported Ni nanoparticles (NPs), were synthesised via hot‐injection colloidal route using oleylamine (OAm) and trioctylphosphine (TOP) as reducing and protective agents, respectively. By adopting a multi‐length scale structural characterization, it was found that by changing equivalents of OAM and TOP not only the size of the nanoparticles is affected but also the Ni electronic structure. The synthetized NPs were modified with ( R , R )‐tartaric acid (TA) and investigated in the asymmetric hydrogenation of methyl acetoacetate to chiral methyl‐3‐hydroxy butyrate. The comparative analysis of structure and catalytic performance for the synthetized catalysts has enabled us to identify a Ni metallic active surface, whereby the activity increases with the size of the metallic domains. Conversely, at the high conversion obtained for the unsupported NPs there was no impact of particle size on the selectivity. ( R )‐selectivity was very high only on catalysts containing positively charged Ni species such as over the SiO 2 ‐supported NiO NPs. This work shows that the chiral modification of metallic Ni NPs with TA is insufficient to maintain high selectivity towards the ( R )‐enantiomer at long reaction time and provide guidance for the engineering of long‐term stable enantioselective catalysts.
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Dec 2019
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B18-Core EXAFS
I10-Beamline for Advanced Dichroism
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María
Retuerto
,
Laura
Pascual
,
Federico
Calle-vallejo
,
Pilar
Ferrer
,
Diego
Gianolio
,
Amaru González
Pereira
,
Álvaro
García
,
Jorge
Torrero
,
María Teresa
Fernández-díaz
,
Peter
Bencok
,
Miguel A.
Peña
,
José Luis G.
Fierro
,
Sergio
Rojas
Open Access
Abstract: The design of active and durable catalysts for the H2O/O2 interconversion is one of the major challenges of electrocatalysis for renewable energy. The oxygen evolution reaction (OER) is catalyzed by SrRuO3 with low potentials (ca. 1.35 VRHE), but the catalyst’s durability is insufficient. Here we show that Na doping enhances both activity and durability in acid media. DFT reveals that whereas SrRuO3 binds reaction intermediates too strongly, Na doping of ~0.125 leads to nearly optimal OER activity. Na doping increases the oxidation state of Ru, thereby displacing positively O p-band and Ru d-band centers, weakening Ru-adsorbate bonds. The enhanced durability of Na-doped perovskites is concomitant with the stabilization of Ru centers with slightly higher oxidation states, higher dissolution potentials, lower surface energy and less distorted RuO6 octahedra. These results illustrate how high OER activity and durability can be simultaneously engineered by chemical doping of perovskites.
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May 2019
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Open Access
Abstract: Metal organic structures have gained recently an interest in many fields. Among them, metal–biomolecule framework materials with amino acids applied as organic linkers have attracted the growing attention. An application of tailored metal–biomolecule frameworks, easily decomposing in an acidic and/or reductive environment in a steerable way, is reported here. From these biocompatible, non-porous, and nanostructured drug carrier systems, the desirable portion of drug could be released depending on the portion of acid, i.e. immediately and/or in a multi-step process due to a structure decomposition. The application of naturally occurring elements as cystine ensures full biocompatibility of the obtained system as well as its degradation products. Presented materials offer potential application in drug delivery systems.
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Feb 2019
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