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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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
E01-JEM ARM 200CF
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Jianwei
Li
,
Kit
Mccoll
,
Xuekun
Lu
,
Sanjay
Sathasivam
,
Haobo
Dong
,
Liqun
Kang
,
Zhuangnan
Li
,
Siyu
Zhao
,
Andreas G.
Kafizas
,
Ryan
Wang
,
Dan J. L.
Brett
,
Paul R.
Shearing
,
Furio
Corà
,
Guanjie
He
,
Claire J.
Carmalt
,
Ivan P.
Parkin
Diamond Proposal Number(s):
[24197, 22572]
Abstract: Cost‐effective and environment‐friendly aqueous zinc‐ion batteries (AZIBs) exhibit tremendous potential for application in grid‐scale energy storage systems but are limited by suitable cathode materials. Hydrated vanadium bronzes have gained significant attention for AZIBs and can be produced with a range of different pre‐intercalated ions, allowing their properties to be optimized. However, gaining a detailed understanding of the energy storage mechanisms within these cathode materials remains a great challenge due to their complex crystallographic frameworks, limiting rational design from the perspective of enhanced Zn2+ diffusion over multiple length scales. Herein, a new class of hydrated porous δ‐Ni0.25V2O5.nH2O nanoribbons for use as an AZIB cathode is reported. The cathode delivers reversibility showing 402 mAh g−1 at 0.2 A g−1 and a capacity retention of 98% over 1200 cycles at 5 A g−1. A detailed investigation using experimental and computational approaches reveal that the host “δ” vanadate lattice has favorable Zn2+ diffusion properties, arising from the atomic‐level structure of the well‐defined lattice channels. Furthermore, the microstructure of the as‐prepared cathodes is examined using multi‐length scale X‐ray computed tomography for the first time in AZIBs and the effective diffusion coefficient is obtained by image‐based modeling, illustrating favorable porosity and satisfactory tortuosity.
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Feb 2020
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B18-Core EXAFS
E01-JEM ARM 200CF
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Chiara
Genovese
,
Manfred E.
Schuster
,
Emma K.
Gibson
,
Diego
Gianolio
,
Victor
Posligua
,
Ricardo
Grau-crespo
,
Giannantonio
Cibin
,
Peter
Wells
,
Debi
Garai
,
Vladyslav
Solokha
,
Sandra
Krick Calderon
,
Juan J.
Velasco-velez
,
Claudio
Ampelli
,
Siglinda
Perathoner
,
Georg
Held
,
Gabriele
Centi
,
Rosa
Arrigo
Diamond Proposal Number(s):
[17031, 10306]
Open Access
Abstract: The carbon–carbon coupling via electrochemical reduction of carbon dioxide represents the biggest challenge for using this route as platform for chemicals synthesis. Here we show that nanostructured iron (III) oxyhydroxide on nitrogen-doped carbon enables high Faraday efficiency (97.4%) and selectivity to acetic acid (61%) at very-low potential (−0.5 V vs silver/silver chloride). Using a combination of electron microscopy, operando X-ray spectroscopy techniques and density functional theory simulations, we correlate the activity to acetic acid at this potential to the formation of nitrogen-coordinated iron (II) sites as single atoms or polyatomic species at the interface between iron oxyhydroxide and the nitrogen-doped carbon. The evolution of hydrogen is correlated to the formation of metallic iron and observed as dominant reaction path over iron oxyhydroxide on oxygen-doped carbon in the overall range of negative potential investigated, whereas over iron oxyhydroxide on nitrogen-doped carbon it becomes important only at more negative potentials.
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Mar 2018
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B18-Core EXAFS
E01-JEM ARM 200CF
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Diamond Proposal Number(s):
[15151]
Open Access
Abstract: Mechanochemistry offers a solventless, ‘waste free’ route to preparing metal oxide catalysts, however, there is limited information on the chemical steps involved. In this work, the perovskite LaMnO3 has been successfully synthesized via mechanochemistry from metal oxide powders, La2O3 and Mn2O3, at room temperature, using a planetary ball mill. Separate ex situ ‘time slices’ were taken during the milling procedure to provide insights into the underlying chemistry. The crystalline material was assessed using XRD, which identified 100% perovskite phase after 3 h of milling. Conversely, characterization by X-ray absorption spectroscopy (XAS) at both the Mn K-edge and La L3-edge provides a very different picture. The XAS data shows that there are significant structural alterations as early as 30 min of milling, with the La precursor dispersed over Mn2O3. Increasing milling time then allows for mechanical activation of both precursors and the formation of powdered LaMnO3, with no calcination step required. The XAS highlights that there is a significant amount of amorphous, oxygen deficient, content even when XRD has identified 100% perovskite phase. The samples were tested for the decomposition of the environmental pollutant N2O; at a milling time of 3 h, the LaMnO3 catalyst displays a much early onset production of N2 compared to a traditional sol–gel synthesized LaMnO3, resulting from increased oxygen deficiency at the surface, confirmed by XPS and STEM-EELS. This is an encouraging sign that mechanochemical routes can be harnessed to provide a sustainable route to preparing mixed metal oxide catalysts with enhanced catalytic performance.
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Dec 2019
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B18-Core EXAFS
E01-JEM ARM 200CF
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Ruoyu
Xu
,
Liqun
Kang
,
Johannes
Knossalla
,
Jerrik
Mielby
,
Qiming
Wang
,
Bolun
Wang
,
Junrun
Feng
,
Guanjie
He
,
Yudao
Qin
,
Jijia
Xie
,
Ann-christin
Swertz
,
Qian
He
,
Søren
Kegnæs
,
Dan J.l.
Brett
,
Ferdi
Schüth
,
Feng Ryan
Wang
Diamond Proposal Number(s):
[206191, 15151]
Abstract: Nanostructured carbons with different pore geometries are prepared with a liquid-free nanocasting method. The method uses gases instead of liquid to disperse carbon precursor, leach templates and remove impurities, minimizing synthetic procedures and the use of chemicals. The method is universal and demonstrated by the synthesis of 12 different porous carbons with various template sources. The effects of pore geometries in catalysis can be isolated and investigated. Two of the resulted materials with different pore geometries are studied as supports for Ru clusters in the hydrogenolysis of 5-hydroxymethylfurfural (HMF) and electrochemical hydrogen evolution (HER). The porous carbon supported Ru catalysts outperform commercial ones in both reactions. It was found that Ru on bottle-neck pore carbon shows highest yield in hydrogenolysis of HMF to 2,5-dimethylfuran (DMF) due to a better confinement effect. A wide temperature operation window from 110 °C to 140 °C, with over 75% yield and 98% selectivity of DMF has been achieved. Tubular pores enable fast charge transfer in electrochemical HER, requiring only 16 mV overpotential to reach current density of 10 mA cm.
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Jan 2019
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B18-Core EXAFS
E01-JEM ARM 200CF
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Diamond Proposal Number(s):
[15151, 21370, 19246, 22572]
Abstract: Selective transformation of biomass feedstocks to platform molecules is a key pursuit for sustainable chemical production. Compared to petrochemical processes, biomass transformation requires the defunctionalization of highly polar molecules at relatively low temperatures. As a result, catalysts based on functional organic polymers may play a prominent role. Targeting the hydrogenolysis of the platform chemical 5-hydroxymethylfurfural (5-HMF), here, we design a polyphenylene (PPhen) framework with purely sp2-hybridized carbons that can isolate 5-HMF via π–π stacking, preventing hemiacetal and humin formation. With good swellability, the PPhen framework here has successfully supported and dispersed seven types of metal particles via a newly developed swelling-impregnation method, including Ru, Pt, Au, Fe, Co, Ni, and Cu. Ru/PPhen is studied for 5-HMF hydrogenolysis, achieving a 92% yield of 2,5-dimethylfuran (DMF) under mild conditions, outperforming the state-of-the-art catalysts reported in the literature. In addition, PPhen helps perform a solventless reaction, achieving direct 5-HMF to DMF conversion in the absence of any liquid solvent or reagent. This approach in designing support–reactant/solvent/metal interactions will play an important role in surface catalysis.
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Nov 2020
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B18-Core EXAFS
E01-JEM ARM 200CF
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Diamond Proposal Number(s):
[23723, 17198]
Abstract: The general and cost-effective synthesis of single atom electrocatalysts (SAECs) still remains a great challenge. Herein, we report a general synthetic protocol for the synthesis of SAECs via a simple condensation–carbonization process, in which furfural and cyanamide were condensation polymerized in the presence of polystyrene nanospheres and metal ions, followed by a pyrolysis to N-doped carbon nanosheet (NCNS) supported SAECs. Six types of SAECs containing platinum, palladium, gold, nickel, cobalt and iron were synthesized to demonstrate the generality of the synthesis protocol. This methodology affords a facile solution to the trade-off between support conductivity and metal loading of SAECs by optimizing the ratio of carbon/nitrogen precursors, i.e., furfural and cyanamide. The presence of single metal atoms was confirmed by high-angle annular dark field scanning transmission electron microscopy and X-ray absorption fine structure measurements. The three-dimensional distribution of single platinum atoms was vividly revealed by depth profile analysis using a scanning transmission electron microscope. The resulting SAECs showed excellent performance for glycerol electro-oxidation and water splitting in alkaline solutions. Notably, Pt/NCNSs possessed an unprecedent mass-normalized current density of 5.3 A per milligram of platinum, which is 32 times that of the commercial Pt/C catalyst. Density functional theory calculations were conducted to reveal the adsorption behavior of glycerol over the SAECs. Using Ni/NCNSs and Co/NCNSs as anodic and cathodic electrocatalysts, we constructed a solar panel powered electrolytic cell for overall water splitting, leading to an overall energy efficiency of 8.8%, which is among the largest solar-to-hydrogen conversion efficiencies reported in the literature.
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Nov 2020
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B18-Core EXAFS
E01-JEM ARM 200CF
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Diamond Proposal Number(s):
[23723, 17198]
Abstract: Herein, we report a facile route to synthesize isolated single iron atoms on nitrogen-sulfur-codoped carbon matrix via a direct pyrolysis process in which hemoglobin, a by-product of the meat industry, was utilized as a precursor for iron, nitrogen and sulfur while bamboo-shaped carbon nanotubes served as a support owing to their excellent conductivity and numerous defects. The resulting metal-nitrogen complexed carbon showed outstanding catalytic performance for the oxygen evolution reaction (OER) in alkaline solutions. At an overpotential of 380 mV, the optimal sample yielded a current density of 83.6 mA cm−2, which is 2.5 times that of benchmark IrO2 (32.8 mA cm−2), rendering it as one of the best OER catalysts reported so far. It also showed negligible activity decay in alkaline solutions during long-term durability tests. Control experiments and X-ray absorption fine structure analyses revealed that Fe-Nx species in the samples are the active sites for OER. Further density functional theory calculations indicated that the presence of sulfur in the carbon matrix modified the electronic structures of active species, thereby leading to the superior activity of the sample.
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Jun 2020
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B18-Core EXAFS
E01-JEM ARM 200CF
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Xi
Sun
,
Simon R.
Dawson
,
Tanja E.
Parmentier
,
Grazia
Malta
,
Thomas E.
Davies
,
Qian
He
,
Li
Lu
,
David J.
Morgan
,
Nicholas
Carthey
,
Peter
Johnston
,
Simon A.
Kondrat
,
Simon J.
Freakley
,
Christopher J.
Kiely
,
Graham J.
Hutchings
Diamond Proposal Number(s):
[22766, 20643, 19580]
Abstract: Single-site catalysts can demonstrate high activity and selectivity in many catalytic reactions. The synthesis of these materials by impregnation from strongly oxidizing aqueous solutions or pH-controlled deposition often leads to low metal loadings or a range of metal species. Here, we demonstrate that simple impregnation of the metal precursors onto activated carbon from a low-boiling-point, low-polarity solvent, such as acetone, results in catalysts with an atomic dispersion of cationic metal species. We show the generality of this method by producing single-site Au, Pd, Ru and Pt catalysts supported on carbon in a facile manner. Single-site Au/C catalysts have previously been validated commercially to produce vinyl chloride, and here we show that this facile synthesis method can produce effective catalysts for acetylene hydrochlorination in the absence of the highly oxidizing acidic solvents previously used.
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Apr 2020
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