Hirohito Ogasawara

Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts

Electrocatalysis will play a key role in future energy conversion and storage technologies, such as water electrolysers, fuel cells and metal-air batteries. Molecular interactions between chemical reactants and the catalytic surface control the activity and efficiency, and hence need to be optimized; however, generalized experimental strategies to do so are scarce. Here we show how lattice strain can be used experimentally to tune the catalytic activity of dealloyed bimetallic nanoparticles for the oxygen-reduction reaction, a key barrier to the application of fuel cells and metal-air batteries. We demonstrate the core-shell structure of the catalyst and clarify the mechanistic origin of its activity. The platinum-rich shell exhibits compressive strain, which results in a shift of the electronic band structure of platinum and weakening chemisorption of oxygenated species. We combine synthesis, measurements and an understanding of strain from theory to generate a reactivity-strain relationship that provides guidelines for tuning electrocatalytic activity.

Connecting dopant bond type with electronic structure in n-doped graphene

Robust methods to tune the unique electronic properties of graphene by chemical modification are in great demand due to the potential of the two dimensional material to impact a range of device applications. Here we show that carbon and nitrogen core-level resonant X-ray spectroscopy is a sensitive probe of chemical bonding and electronic structure of chemical dopants introduced in single-sheet graphene films. In conjunction with density functional theory based calculations, we are able to obtain a detailed picture of bond types and electronic structure in graphene doped with nitrogen at the sub-percent level. We show that different N-bond types, including graphitic, pyridinic, and nitrilic, can exist in a single, dilutely N-doped graphene sheet. We show that these various bond types have profoundly different effects on the carrier concentration, indicating that control over the dopant bond type is a crucial requirement in advancing graphene electronics.

Spectroscopic probing of local hydrogen-bonding structures in liquid water

We have studied the electronic structure of liquid water using x-ray absorption spectroscopy at the oxygen K edge. Since the x-ray absorption process takes less than a femtosecond, it allows probing of the molecular orbital structure of frozen, local geometries of water molecules at a timescale that has not previously been accessible. Our results indicate that the electronic structure of liquid water is significantly different from that of the solid and gaseous forms, resulting in a pronounced pre-edge feature below the main absorption edge in the spectrum. Theoretical calculations of these spectra suggest that this feature originates from specific configurations of water, for which the H-bond is broken on the H-donating site of the water molecule. This study provides a fingerprint for identifying broken donating H-bonds in the liquid and shows that an unsaturated H-bonding environment exists for a dominating fraction of the water molecules.

Hydrogenation of Single-Walled Carbon Nanotubes

Towards the development of a useful mechanism for hydrogen storage, we have studied the hydrogenation of single-walled carbon nanotubes with atomic hydrogen using core-level photoelectron spectroscopy and x-ray absorption spectroscopy. We find that atomic hydrogen creates C-H bonds with the carbon atoms in the nanotube walls, and such C-H bonds can be completely broken by heating to 600 degrees C. We demonstrate approximately 65 +/- 15 at % hydrogenation of carbon atoms in the single-walled carbon nanotubes, which is equivalent to 5.1 +/- 1.2 wt % hydrogen capacity. We also show that the hydrogenation is a reversible process.

In Situ Observation of Surface Species on Iridium Oxide Nanoparticles during the Oxygen Evolution Reaction

An iridium oxide nanoparticle electrocatalyst under oxygen evolution reaction conditions was probed in situ by ambient-pressure X-ray photoelectron spectroscopy. Under OER conditions, iridium undergoes a change in oxidation state from Ir(IV) to Ir(V) that takes place predominantly at the surface of the catalyst. The chemical change in iridium is coupled to a decrease in surface hydroxide, providing experimental evidence which strongly suggests that the oxygen evolution reaction on iridium oxide occurs through an OOH-mediated deprotonation mechanism.

The interpretation of X-ray absorption spectra of water and ice

The changes in the X-ray Absorption Spectrum (XAS) of water upon formation of hydrogen bonds (H-bonds) are analyzed with the aid of Density Functional Theory (DFT) calculations. The tetrahedral symmetry of the ice structure removes the p-character from the 4a1 level, leading to very weak intensity in the pre-edge region. Breaking an accepting H-bond has very little effect on the absorption spectrum. Abroken donating H-bond, however, is identified through a strong pre-edge feature in XAS. The asymmetry on the hydrogen side causes a1 and b2 orbital mixing and the orbitals localize along the internal O–H bonds. 2002 Elsevier Science B.V. All rights reserved. Probing of the local hydrogen-bonding (Hbond) network is essential for the understanding of the structure of liquid water. In ice the molecules arrange themselves in a tetrahedral coordination with four nearest neighbors and an O–H–O hydrogen-bond angle of 180. The H-bond is strongly directional and it is desirable to determine how these bonds are locally broken in the liquid phase. There exist a number of diffraction-based techniques that can determine the radial distribution function of the O–O, O–H and H–H correlations [1–4]. Using these techniques the number of molecules in the first coordination shell can be estimated and the average bonding distances determined. Abroken H-bond can be defined through a too long H-bond distance or an H-bond

In situ x-ray photoelectron spectroscopy studies of water on metals and oxides at ambient conditions

In-situ X-ray photoelectron spectroscopy studies of water metals and oxides at ambient conditions Ev Vi si ua t w tio ww n Ed .a ct itio iv n eP of DF ac .c tiv om eP DF fo rm So or ftw e d e ar ta e. ils on S Yamamoto 1 , H Bluhm 2 , K Andersson 1,3,6 , G Ketteler 4,7 , H Ogasawara 1 , M Salmeron 4,5 and A Nilsson 1,3 Stanford Synchrotron Radiation Laboratory, P.O.B. 20450, Stanford, CA 94309, USA. Lawrence Berkeley National Laboratory, Chemical Sciences Division, Berkeley, CA 94720, USA. FYSIKUM, Stockholm University, AlbaNova University Center, SE-106 91 Stockholm, Sweden. Lawrence Berkeley National Laboratory, Materials Sciences Division, Berkeley, CA 94720, USA. Department of Materials Science and Engineering, University of California, Berkeley, CA 94720, USA. E-mail: nilsson@slac.stanford.edu Running head: In-Situ XPS studies of water on metals and oxides at ambient conditions Present address: Center for Individual Nanoparticle Functionality (CINF), Department of Physics, Technical University of Denmark, Fysikvej 312, DK-2800 Kgs. Lyngby, Denmark. Present address: Department of Applied Physics, Chalmers University of Technology, SE-412 96 Goteborg, Sweden. Abstract . X-ray photoelectron spectroscopy (XPS) is a powerful tool for surface and interface analysis, providing the elemental composition of surfaces and the local chemical environment of adsorbed species. Conventional XPS experiments have been limited to ultrahigh vacuum (UHV) conditions due to a short mean free path of electrons in a gas phase. The recent advances in instrumentation coupled with third-generation synchrotron radiation sources enables in-situ XPS measurements at pressures above 5 Torr. In this review, we describe the basic design of the ambient pressure XPS setup that combines differential pumping with an electrostatic focusing. We present examples of the application of in-situ XPS to studies of water adsorption on the surface of metals and oxides including Cu(110), Cu(111), TiO 2 (110) under environmental conditions of water vapor pressure. On all these surfaces we observe a al general trend where hydroxyl groups form first, followed by molecular water adsorption. The importance of surface OH groups and their hydrogen bonding to water molecules in water adsorption on surfaces is discussed in detail.

Probing the transition state region in catalytic CO oxidation on Ru

Catching CO oxidation Details of the transition state that forms as carbon monoxide (CO) adsorbed on a ruthenium surface is oxidized to CO2 have been revealed by ultrafast excitation and probe methods. Öström et al. initiated the reaction between CO and adsorbed oxygen atoms with laser pulses that rapidly heated the surface and then probed the changes in electronic structure with oxygen x-ray absorption spectroscopy. They observed transition-state configurations that are consistent with density functional theory and a quantum oscillator model. Science, this issue p. 978 Ultrafast x-ray spectroscopy reveals electronic changes that occur during the oxidation of carbon monoxide on a ruthenium surface. Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC–O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

Autocatalytic water dissociation on Cu(110) at near ambient conditions

Autocatalytic dissociation of water on the Cu(110) metal surface is demonstrated on the basis of X-ray photoelectron spectroscopy studies carried out in situ under near ambient conditions of water vapor pressure (1 Torr) and temperature (275-520 K). The autocatalytic reaction is explained as the result of the strong hydrogen-bond in the H2O-OH complex of the dissociated final state, which lowers the water dissociation barrier according to the Brønsted-Evans-Polanyi relations. A simple chemical bonding picture is presented which predicts autocatalytic water dissociation to be a general phenomenon on metal surfaces.

Hydrogen adsorption on Pt(100), Pt(110), Pt(111) and Pt(1111) electrode surfaces studied by in situ infrared reflection absorption spectroscopy

Abstract Hydrogen adsorption on Pt(100), Pt(1111) (6(100) × (111)), Pt(110) and Pt(111) electrode surfaces was studied by both voltammetry and in situ infrared reflection absorption spectroscopy. The terminal hydrogens absorbed on Pt(100), Pt(1111) and Pt(110) electrodes were observed at 1990–2080 cm −1 as bands appearing at potentials more negative than 0.25, 0.1 and 0 V versus SHE, respectively. However, a well-oriented pt(111) electrode did not give a significant absorption of the terminal hydrogens under similar conditions. The terminal hydrogen adsorption was sensitive to the surface crystallographic orientation.