In-Situ XAS Investigation of the Effect of Electrochemical Reaction on the Structure of Graphene in Aqueous Electrolytes

[[abstract]]In-situ X-ray Absorption Spectroscopy (XAS), Raman Spectroscopy, AFM and XPS have been used to investigate the effect of reactions occurring in aqueous electrolytes on the structure of a single-layer graphene produced by CVD. It was found that defects are readily and irreversibly produced by application of electrode voltages. The defects and the products were identified also by new features in the XAS spectra. Our findings show the poor stability of the CVD graphene, which could be a challenge in applications such as super-capacitors, fuel-cells, batteries and photo-catalysis.[[notice]]補正完畢[[incitationindex]]SCI[[booktype]]紙本[[booktype]]電子

Direct Observation of the Electroadsorptive Effect on Ultrathin Films for Microsensor and Catalytic-Surface Control

Microchemical sensors and catalytic reactors make use of gases during adsorption in specific ways on selected materials. Fine-tuning is normally achieved by morphological control and material doping. The latter relates surface properties to the electronic structure of the bulk, and this suggests the possibility of electronic control. Although unusual for catalytic surfaces, such phenomena are sometimes reported for microsensors, but with little understanding of the underlying mechanisms. Herein, direct observation of the electroadsorptive effect by a combination of X-ray photoelectron spectroscopy and conductivity analysis on nanometre-thick semiconductor films on buried control electrodes is reported. For the SnO2/NO2 model system, NO3 surface species, which normally decay at the latest within minutes, can be kept stable for 1.5 h with a high coverage of 15 % under appropriate electric fields. This includes uncharged states, too, and implies that nanoelectronic structures provide control over the predominant adsorbate conformation on exterior surfaces and thus opens the field for chemically reactive interfaces with in situ tunability

Introducing Ionic Current Detection for X Ray Absorption Spectroscopy in Liquid Cells

Photons and electrons are two common relaxation products upon X ray absorption, enabling fluorescence yield and electron yield detections for X ray absorption spectroscopy XAS . The ions that are created during the electron yield process are relaxation products too, which are exploited in this study to produce ion yield for XA detection. The ionic currents measured in a liquid cell filled with water or iron III nitrate aqueous solutions exhibit characteristic O K edge and Fe L edge absorption profiles as a function of excitation energy. Application of two electrodes installed in the cell is crucial for obtaining the XA spectra of the liquids behind membranes. Using a single electrode can only probe the species adsorbed on the membrane surface. The ionic current detection, termed as total ion yield TIY in this study, also produces an undistorted Fe L edge XA spectrum, indicating its promising role as a novel detection method for XAS studies in liquid cell

Probing Ionization Energies for Trace Gas Identification: The Micro Photo Electron Ionization Detector (PEID)

Micro gas sensors detect the presence of substances, but can hardly identify them. We developed a novel approach of probing referenceable ionization energies. It extends the photoionization principle towards tunable energies via replacement of photons by accelerated photo electrons. The device comprises UV-LED illumination, an atmospherically stable photoelectron emission layer with a nano-vacuum electronics accelerator realized in thin film technology and charged particle measurement. A voltage variation at the accelerator provides electrons of tunable energies. We were able to prove that variable electron energies can be used for substance detection. The resulting system reaches ambient conditions operability. The actual limitations and challenges are discussed

Multiscale Photon Based In Situ and Operando Spectroscopies in Time and Energy Landscapes

Following catalytic reactions, in situ and operando are now the focus of a number of dedicated experiments at light sources which have been developed to track the electronic and molecular structural dynamics of catalysts. The challenges for this goal are two fold first, the development of spectroscopic tools in the energy domain and time domain is required. The photocatalytic processes have early dynamics of tens of femtoseconds, while further reaction takes seconds, minutes, and even hours. Second, a combination of tools to probe processes not only in solids, but also in solutions and at interfaces, is now needed. In this special issue, we present recent developments at the synchrotron facility BESSY II using photon energy from the infrared and extreme ultraviolet up to the soft X ray regime for in situ and operando applications addressing these two major challenges. As this work is a result of contributions from several groups, each section will present the group s activities and related team members involve

Revealing the active phase of copper during the electroreduction of CO2 in aqueous electrolyte by correlating in situ x-ray spectroscopy and in situ electron microscopy

The variation in the morphology and electronic structure of copper during the electroreduction of CO2 into valuable hydrocarbons and alcohols was revealed by combining in situ surface- and bulk-sensitive X-ray spectroscopies with electrochemical scanning electron microscopy. These experiments proved that the electrified interface surface and near-surface are dominated by reduced copper. The selectivity to the formation of the key C–C bond is enhanced at higher cathodic potentials as a consequence of increased copper metallicity. In addition, the reduction of the copper oxide electrode and oxygen loss in the lattice reconstructs the electrode to yield a rougher surface with more uncoordinated sites, which controls the dissociation barrier of water and CO2. Thus, according to these results, copper oxide species can only be stabilized kinetically under CO2 reduction reaction conditions

The 2HWC HAWC Observatory Gamma Ray Catalog

We present the first catalog of TeV gamma-ray sources realized with the recently completed High Altitude Water Cherenkov Observatory (HAWC). It is the most sensitive wide field-of-view TeV telescope currently in operation, with a 1-year survey sensitivity of ~5-10% of the flux of the Crab Nebula. With an instantaneous field of view >1.5 sr and >90% duty cycle, it continuously surveys and monitors the sky for gamma ray energies between hundreds GeV and tens of TeV. HAWC is located in Mexico at a latitude of 19 degree North and was completed in March 2015. Here, we present the 2HWC catalog, which is the result of the first source search realized with the complete HAWC detector. Realized with 507 days of data and represents the most sensitive TeV survey to date for such a large fraction of the sky. A total of 39 sources were detected, with an expected contamination of 0.5 due to background fluctuation. Out of these sources, 16 are more than one degree away from any previously reported TeV source. The source list, including the position measurement, spectrum measurement, and uncertainties, is reported. Seven of the detected sources may be associated with pulsar wind nebulae, two with supernova remnants, two with blazars, and the remaining 23 have no firm identification yet.Comment: Submitted 2017/02/09 to the Astrophysical Journa

The TeV Sun Rises: Discovery of Gamma rays from the Quiescent Sun with HAWC

We report the first detection of a TeV gamma-ray flux from the solar disk (6.3$\sigma$), based on 6.1 years of data from the High Altitude Water Cherenkov (HAWC) observatory. The 0.5--2.6 TeV spectrum is well fit by a power law, dN/dE = $A (E/1 \text{ TeV})^{-\gamma}$, with $A = (1.6 \pm 0.3) \times 10^{-12}$ TeV$^{-1}$ cm$^{-2}$ s$^{-1}$ and $\gamma = -3.62 \pm 0.14$. The flux shows a strong indication of anticorrelation with solar activity. These results extend the bright, hard GeV emission from the disk observed with Fermi-LAT, seemingly due to hadronic Galactic cosmic rays showering on nuclei in the solar atmosphere. However, current theoretical models are unable to explain the details of how solar magnetic fields shape these interactions. HAWC's TeV detection thus deepens the mysteries of the solar-disk emission.Comment: 15 pages, 8 figures including supplementary material. Accepted for publication in Physical Review Letter

Galactic Gamma-Ray Diffuse Emission at TeV energies with HAWC Data

The Galactic gamma-ray diffuse emission (GDE) is emitted by cosmic rays (CRs), ultra-relativistic protons and electrons, interacting with gas and electromagnetic radiation fields in the interstellar medium. Here we present the analysis of TeV diffuse emission from a region of the Galactic Plane over the range in longitude of $l\in[43^\circ,73^\circ]$, using data collected with the High Altitude Water Cherenkov (HAWC) detector. Spectral, longitudinal and latitudinal distributions of the TeV diffuse emission are shown. The radiation spectrum is compatible with the spectrum of the emission arising from a CR population with an "index" similar to that of the observed CRs. When comparing with the \texttt{DRAGON} \textit{base model}, the HAWC GDE flux is higher by about a factor of two. Unresolved sources such as pulsar wind nebulae and TeV halos could explain the excess emission. Finally, deviations of the Galactic CR flux from the locally measured CR flux may additionally explain the difference between the predicted and measured diffuse fluxes