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Instruments / Technical Area	Publication Details	Published
B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS	Identifying the catalyst chemical state and adsorbed species during methanol conversion on copper using ambient pressure X-ray spectroscopies Baran Eren , Christopher G. Sole , Jesús Sánchez Lacasa , David Grinter , Federica Venturini , Georg Held , Santiago Esconjauregui , Robert S. Weatherup Physical Chemistry Chemical Physics DOI: 10.1039/D0CP00347F Diamond Proposal Number(s): [19299] Show Abstract ▼ Abstract: Methanol is a promising chemical for the safe and efficient storage of hydrogen, where methanol conversion reactions can generate a hydrogen-containing gas mixture. Understanding the chemical state of the catalyst over which these reactions occur and the interplay with the adsorbed species present is key to the design of improved catalysts and process conditions. Here we study polycrystalline Cu foils using ambient pressure X-ray spectroscopies to reveal the Cu oxidation state and identify the adsorbed species during partial oxidation (CH3OH + O2), steam reforming (CH3OH + H2O), and autothermal reforming (CH3OH + O2 + H2O) of methanol at 200 °C surface temperature and in the mbar pressure range. We find that the Cu surface remains highly metallic throughout partial oxidation and steam reforming reactions, even for oxygen-rich conditions. However, for autothermal reforming the Cu surface shows significant oxidation towards Cu2O. We rationalise this behaviour on the basis of the shift in equilibrium of the CH3OH* + O* ⇌ CH3O* + OH* caused by the addition of H2O.	Mar 2020
B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS B18-Core EXAFS E01-JEM ARM 200CF	Influence of synthesis conditions on the structure of nickel nanoparticles and their reactivity in selective asymmetric hydrogenation 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 Chemcatchem DOI: 10.1002/cctc.201901955 Open Access Show Abstract ▼ 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.	Dec 2019
I09-Surface and Interface Structural Analysis	Adsorption behavior of organic molecules: a study of benzotriazole on Cu(111) with spectroscopic and theoretical methods Chiara Gattinoni , Panayiotis Tsaousis , Chanan Euaruksakul , Rachel Price , David A. Duncan , Tod Pascal , David Prendergast , Georg Held , Angelos Michaelides Langmuir DOI: 10.1021/acs.langmuir.8b03528 Diamond Proposal Number(s): [12800] Show Abstract ▼ Abstract: The adsorption of organic molecules on solid substrates is important to applications in fields such as catalysis, photovoltaics, corrosion inhibition, adhesion, and sensors. The molecular level description of the surface-molecule interaction and of the adsorption structures in these complex systems is crucial to understand their properties and function. Here we present the investigation of one such system, benzotriazole (BTAH) on single crystal Cu(111) in vacuum conditions. BTAH is the most widely used corrosion inhibitor for copper and thus a molecule of great industrial relevance. We show that the co-application of a wide range of spectroscopic techniques with theoretical methods provides unique insight in the description of the atomistic details of the adsorbed structures. Specifically, spectroscopic photoemission, absorption and standing wave experiments combined with ab initio computational modeling allowed us to identify that benzotriazole forms overlayers of intact BTAH when deposited at low temperature and it dissociates into BTA and H at room temperature and above. The dissociated molecule then forms complex structures of mixed chains and dimers of BTA bound to copper adatoms. Our work also reveals that copper adatoms at low concentrations, such as the theoretically predicted superstructures cannot be be resolved by means of current X-ray photoelectron spectroscopy (XPS) as the modelled Cu 2p spectra are practically indistinguishable from those for a Cu surface without adatoms. Overall this study significantly deepens understanding of BTAH on Cu – a system studied for more than 50 years – and it highlights the benefits of combining spectroscopic and computational methods in order to obtain a complete picture of a complex adsorption system.	Jan 2019
Optics	Compensation of x-ray mirror distortion by cooling temperature control Matthew Hand , Hongchang Wang , Maria Harkiolaki , Federica Venturini , Rosa Arrigo , Pilar Ferrer Escorihuela , Simon Alcock , Ioana Nistea , Andy Marshall , Stewart Scott , Liz Duke , Georg Held , Kawal Sawhney Proceedings of the 13th International Conference on Synchrotron Radiation Instrumentation – SRI2018 DOI: 10.1063/1.5084675 Open Access Show Abstract ▼ Abstract: Synchrotron radiation is emitted from a bending magnet source in a wide ray fan which is collected by the first optical element in a beamline. In order to maximize angular acceptance, and hence flux, it is beneficial to increase the length of this mirror and optical design requirements may necessitate that the optical surface be over 1 m in length. Such mirrors also require cooling as they may be subject to high heat loads from the incident radiation. Two beamlines, B07 and B24, at Diamond Light Source, UK, use 1.4 m long toroidal mirrors which utilize a similar side-clamped cooling manifold design. While this scheme has been successful in providing effective cooling of the mirror, it has also been discovered that it introduces deformation of the radius of curvature which is sufficient to alter the focusing characteristics of the mirror. At both beamlines, the horizontal focus of the beam was found to differ by up to several meter from the design position at the exit slit which resulted in poor flux throughput, reduced energy resolution and other side effects. A pencil beam scan method has been used to diagnose this issue and infer the position of the focus and mirror shape. Through the use of a standalone chiller to alter the temperature of the water within the cooling loop, it has been possible to correct the distortion of the radius and restore the focus to its nominal position.	Jan 2019
B18-Core EXAFS E01-JEM ARM 200CF	Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon 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 Nature Communications 9 DOI: 10.1038/s41467-018-03138-7 Diamond Proposal Number(s): [17031, 10306] Open Access Show Abstract ▼ 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.	Mar 2018
	Combined Experimental and Theoretical Study of Methyl Acetoacetate Adsorption on Ni{100} Panayiotis Tsaousis , Jorge Ontaneda , Luca Bignardi , Roger A. Bennett , Ricardo Grau-crespo , Georg Held The Journal Of Physical Chemistry C DOI: 10.1021/acs.jpcc.8b00204 Show Abstract ▼ Abstract: The enantioselective hydrogenation of methyl acetoacetate (MAA) over modified Ni-based catalysts is a key reaction in the understanding of enantioselective heterogeneous catalysis as it represents the only example of this class of reactions catalyzed by base metals. Yet, there is very little molecular-level information available about the adsorption complex formed by the reactants on Ni surfaces. Here, we report a combined experimental and theoretical study of the adsorption of MAA on the Ni{100} surface. X-ray photoelectron spectroscopy shows that MAA forms stable multilayers at low temperatures, which desorb between 200 and 220 K. At higher temperatures a single chemisorbed layer is formed, which decomposes between 300 and 350 K. Density functional theory modeling predicts an enolate species with bidentate coordination as the most stable chemisorbed species. Comparison of photoelectron spectroscopy and X-ray absorption data with simulations using this adsorption model show good qualitative and quantitative agreement. The molecular plane is tilted with respect to the surface plane by about 50°. This breaking of symmetry provides a mechanism for the enantioselective hydrogenation.	Mar 2018
	"Pop-On and Pop-Off" Surface Chemistry of Alanine on Ni{111} Under Elevated Hydrogen Pressures Richard E. J. Nicklin , Andrey Shavorskiy , Funda Aksoy Akgul , Zhi Liu , Roger A. Bennett , Marco Sacchi , Georg Held The Journal Of Physical Chemistry C DOI: 10.1021/acs.jpcc.8b00186 Show Abstract ▼ Abstract: The co-adsorption of hydrogen with a simple chiral modifier, alanine, on Ni{111} was studied using Density Functional Theory in combination with ambient-pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy at temperatures of 300~K and above, which are representative of chiral hydrogenation reactions. Depending on the hydrogen pressure, the surface enables protons to "pop on and off" the modifier molecules, thus significantly altering the adsorption geometry and chemical nature of alanine from anionic tridentate in ultra-high vacuum to predominantly zwitterionic bidentate at hydrogen pressures above 0.1 Torr. This hydrogen-stabilised modifier geometry allows alternative mechanisms for proton transfer and the creation of enatioselective reaction environments.	Mar 2018
	Adsorption of Methyl Acetoacetate at Ni{111}: Experiment and Theory Jorge Ontaneda , Richard E. J. Nicklin , Alix Cornish , Alberto Roldan , Ricardo Grau-crespo , Georg Held The Journal Of Physical Chemistry C DOI: 10.1021/acs.jpcc.6b10023 Show Abstract ▼ Abstract: The hydrogenation of methyl acetoacetate (MAA) over modified Ni catalysts is one of the most important and best studied reactions in heterogeneous enantioselective catalysis. Yet, very little molecular-level information is available on the adsorption complex of the reactant. Here, we report on a combined experimental and theoretical study of MAA adsorption on Ni{111}. XPS shows that the chemisorbed layer is stable up to 250 K; above 250 K, decomposition sets in. In ultra-high-vacuum conditions, multilayers grow below 150 K. DFT modeling predicts a deprotonated enol species with bidentate coordination on the flat Ni{111} surface. The presence of adatoms on the surface leads to stronger MAA adsorption in comparison with the flat surface, whereby the stabilization energy is high enough for MAA to drive the formation of adatom defects at Ni{111}, assuming the adatoms come from steps. Comparison of experimental XPS and NEXAFS data with theoretical modeling, however, identifies the bidentate deprotonated enol on the flat Ni{111} surface as the dominant species at 250 K, indicating that the formation of adatom adsorption complexes is kinetically hindered at low temperatures.	Nov 2016
	The Partial Oxidation of Methane Over Pd/Al2O3 Catalyst Nanoparticles Studied In-Situ by Near Ambient-Pressure X-ray Photoelectron Spectroscopy Rachel Price , Tugce Eralp-erden , Ethan Crumlin , Sana Rani , Sonia Garcia , Richard Smith , Liam Deacon , Chanan Euaruksakul , Georg Held Topics In Catalysis 59, 516 - 525 DOI: 10.1007/s11244-015-0520-8 Open Access Show Abstract ▼ Abstract: Near ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) is used to study the chemical state of methane oxidation catalysts in-situ. Al2O3–supported Pd catalysts are prepared with different particle sizes ranging from 4 to 10 nm. These catalysts were exposed to conditions similar to those used in the partial oxidation of methane (POM) to syn-gas and simultaneously monitored by NAP-XPS and mass spectrometry. NAP-XPS data show changes in the oxidation state of the palladium as the temperature increases, from metallic Pd0 to PdO, and back to Pd0. Mass spectrometry shows an increase in CO production whilst the Pd is in the oxide phase, and the metal is reduced back under presence of newly formed H2. A particle size effect is observed, such that CH4 conversion starts at lower temperatures with larger sized particles from 6 to 10 nm. We find that all nanoparticles begin CH4 conversion at lower temperatures than polycrystalline Pd foil.	Mar 2016
	Stereochemistry and thermal stability of tartaric acid on the intrinsically chiral Cu{531} surface Silvia Baldanza , Jacopo Ardini , Angelo Giglia , Georg Held Surface Science 643, 108 - 116 DOI: 10.1016/j.susc.2015.08.021 Show Abstract ▼ Abstract: Intrinsically chiral metal surfaces provide enantiospecific reaction environments without the need of co-adsorbed modifiers. Amongst the intrinsically chiral copper surfaces, Cu{531} has the smallest unit cell and the highest density of chiral sites. XPS, NEXAFS and TPD were employed to investigate the adsorption and decomposition behaviour of the two chiral enantiomers of tartaric acid on this surface. The results obtained from XPS and NEXAFS show that at saturation coverage both enantiomers of tartaric acid adsorb in a μ4 configuration through the two carboxylic groups, which are rotated with respect to each other by 90° ± ≈ 15° within the surface plane. At intermediate coverage the R,R enantiomer adopts a similar configuration, but the S,S enantiomer is different and shows a high degree of dissociation. Growth of multilayers is observed at high exposures when the sample is kept at below 370 K. TPD experiments show that multilayers desorb between 390 K and 470 K and decomposition of the chemisorbed layer occurs between 470 K and 600 K. The desorption spectra support a two-step decomposition mechanism with a Odouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashO or HO–HCdouble bond; length as m-dashCH–OH intermediate that leads to production of CO2 and CO. Enantiomeric differences are observed in the desorption features related to the decomposition of the chemisorbed layer.	Jan 2016

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