ABSTRACT
The structural, spectroscopic and electronic properties of Na and K birnessites were investigated from ambient conditions (birA) to complete dehydration, and the involved mechanisms were scrutinized. Density Functional Theory (DFT) simulations were employed to derive structural models for lamellar A0.33MnO2·xH2O (A = Na+ or K+, x = 0 or 0.66), subsequently compared with the experimental results obtained for Na0.30MnO2·0.75H2O and K0.22MnO2·0.77H2O materials. Thermal analysis (TGA-DSC), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, and Near Ambient Pressure X-ray Photoemission Spectroscopy (NAP-XPS) measurements were conducted for both birnessites. Dehydration under vacuum, annealing, or controlled relative humidity were considered. Results indicated that complete birnessite dehydration was a two-stage process. In the first stage, water removal from the interlayer of fully hydrated birnessite (birA) down to a molar H2O/A ratio of â¼2 (birB) led to the progressive shrinkage of the interlayer distance (3% for Na birnessite, 1% for K birnessite). In the second stage, water-free (birC) domains with a shorter interlayer distance (20% for Na birnessite, 10% for K birnessite) appeared and coexisted with birB domains. Then, birB was essentially transformed into birC when complete dehydration was achieved. The vibrational properties of birA were consistent with strong intermolecular interactions among water molecules, whereas partially dehydrated birnessite (birB) showed a distinct feature, with 3 (for Na-bir) and 2 (for K-bir) vibrations that were reproduced by DFT calculations for organized water into the interlayer (x = 0.66). The study also demonstrated that the electronic structure of Na birnessite depends on the interlayer water content. The external Na+ electronic level (Na 2p) was slightly destabilized (+0.3 eV binding energy) under near ambient conditions (birA) compared to drier conditions (birB and birC).
ABSTRACT
A stable and cost effective oxygen evolution reaction (OER) catalyst is crucial for the large-scale market penetration of proton exchange membrane (PEM) water electrolyzers. We show that the synthesis of iridium nanoparticles in either low purity ethanol or water, or in the absence of a surfactant, is detrimental to the electrocatalytic properties of the materials. Adding NaBH4 in excess improves the purity of the catalyst enhancing the OER activity up to 100 A gIr-1 at 1.51 V vs. RHE, the highest value reported so far for high purity Ir nanoparticles. The measured OER activity correlates with the capacitive current rather than with the charge corresponding to the IrIII/IrIV oxidation peak. Operando near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) on membrane electrode assemblies (MEAs) with the synthesized catalysts reveals a metallic core surrounded by a thin layer of IrIII/IV oxides/hydroxides. Oxidation of IrIII leaves behind a porous ultrathin layer of IrIV oxides/hydroxides, which dominate the surface during the OER, while IrV was not detected.
ABSTRACT
Despite thermal silicon oxide desorption is a basic operation in semiconductor nanotechnology, its detailed chemical analysis has not been yet realized via time-resolved photoemission. Using an advanced acquisition system and synchrotron radiation, heating schedules with velocities as high as 100 K.s-1 were implemented and highly resolved Si 2p spectra in the tens of millisecond range were obtained. Starting from a Si(111)-7 × 7 surface oxidized in O2 at room temperature (1.4 monolayer of oxygen), changes in the Si 2p spectral shape enabled a detailed chemical analysis of the oxygen redistribution at the surface and of the nucleation, growth and reconstruction of the clean silicon areas. As desorption is an inhomogeneous surface process, the Avrami formalism was adapted to oxide desorption via an original mathematical analysis. The extracted kinetic parameters (the Avrami exponent equal to ~2, the activation energy of ~4.1 eV and a characteristic frequency) were found remarkably stable within a wide (~110 K) desorption temperature window, showing that the Avrami analysis is robust. Both the chemical and kinetic information collected from this experiment can find useful applications when desorption of the oxide layer is a fundamental step in nanofabrication processes on silicon surfaces.
ABSTRACT
Organic layers chemically grafted on silicon offer excellent interfaces that may open up the way for new organic-inorganic hybrid nanoelectronic devices. However, technological achievements rely on the precise electronic characterization of such organic layers. We have prepared ordered grafted organic monolayers (GOMs) on Si(111), sometimes termed self-assembled monolayers (SAMs), by a hydrosilylation reaction with either a 7-carbon or an 11-carbon alkyl chain, with further modification to obtain amine-terminated surfaces. X-ray photoelectron spectroscopy (XPS) is used to determine the band bending (â¼ 0.3 eV), and ultraviolet photoelectron spectroscopy (UPS) to measure the work function (â¼ 3.4 eV) and the HOMO edge. Scanning tunneling microscopy (STM) confirms that the GOM surface is clean and smooth. Finally, conductive AFM is used to measure electron transport through the monolayer and to identify transition between the tunneling and the field emission regimes. These organic monolayers offer a promising alternative to silicon dioxide thin films for fabricating metal-insulator-semiconductor (MIS) junctions. We show that gold nanoparticles can be covalently attached to mimic metallic nano-electrodes and that the electrical quality of the GOMs is completely preserved in the process.
ABSTRACT
Soft X-ray induced chemistry of H(2)O, CO and CH(3)OH and the effects of the water and nitric acid hydrate (HNO(3).1.65H(2)O) matrix on the photochemistry of CO and CH(3)OH have been investigated using NEXAFS spectroscopy. For pure H(2)O, CO and CH(3)OH ices, we show that the destruction rates are strongly limited by back reactions, leading to strikingly high survival rates of these molecules upon the harsh irradiation conditions to which they are submitted. We also evidence the interplay between the photochemical reactions of CO and CH(3)OH and those of the matrix. The OH and O radicals released by the photolysis of H(2)O and HNO(3) react with the CO and CH(3)OH and their fragments, considerably reducing the survival rates compared to pure CO and pure CH(3)OH ices, especially in presence of nitric acid, and dramatically enhancing the formation of CO(2) at the expense of CO. Because NEXAFS spectroscopy allows identifying which reactions are important among those possible, it emerges a simple picture of the photochemical routes of CO and CH(3)OH in the H(2)O and HNO(3)/H(2)O environments.
Subject(s)
Carbon Monoxide/chemistry , Ice , Methanol/chemistry , Nitric Acid/chemistry , Photochemical Processes , X-Ray Absorption SpectroscopyABSTRACT
A vapor-deposited NH(3) ice film irradiated at 20 K with 150 eV photons has been studied with near-edge x-ray absorption fine structure (NEXAFS) spectroscopy at the nitrogen K-edge. Irradiation leads to the formation of high amounts (12%) of molecular nitrogen N(2), whose concentration as a function of the absorbed energy has been quantified to 0.13 molecule/eV. The stability of N(2) in solid NH(3) has been also studied, showing that N(2) continuously desorbs between 20 and 95 K from the irradiated ammonia ice film. Weak concentrations (<1%) of other photoproducts are also detected. Our NEXAFS simulations show that these features own to NH(2), N(2)H(2), and N(3)(-).
ABSTRACT
The changes in the structure and composition of vapor-deposited ice films irradiated at 20 K with soft x-ray photons (3-900 eV) and their subsequent evolution with temperatures between 20 and 150 K have been investigated by near-edge x-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K edge. We observe the hydroxyl OH, the atomic oxygen O, and the hydroperoxyl HO(2) radicals, as well as the oxygen O(2) and hydrogen peroxide H(2)O(2) molecules in irradiated porous amorphous solid water (p-ASW) and crystalline (I(cryst)) ice films. The evolution of their concentrations with the temperature indicates that HO(2), O(2), and H(2)O(2) result from a simple step reaction fuelled by OH, where O(2) is a product of HO(2) and HO(2) a product of H(2)O(2). The local order of ice is also modified, whatever the initial structure is. The crystalline ice I(cryst) becomes amorphous. The high-density amorphous phase (I(a)h) of ice is observed after irradiation of the p-ASW film, whose initial structure is the normal low-density form of the amorphous ice (I(a)l). The phase I(a)h is thus peculiar to irradiated ice and does not exist in the as-deposited ice films. A new "very high density" amorphous phase-we call I(a)vh-is obtained after warming at 50 K the irradiated p-ASW ice. This phase is stable up to 90 K and partially transforms into crystalline ice at 150 K.