Dewetting of PtCu Nanoalloys on TiO2 Nanocavities Provides a Synergistic Photocatalytic Enhancement for Efficient H2 Evolution

We investigate the co-catalytic activity of PtCu alloy nanoparticles for photocatalytic H2 evolution from methanol-water solutions. To produce the photocatalysts, a few nm-thick Pt-Cu bilayers are deposited on anodic TiO2 nanocavity arrays and converted by solid state dewetting, i.e. a suitable thermal treatment, into bimetallic PtCu nanoparticles. XRD and XPS results prove the formation of PtCu nanoalloys that carry a shell of surface oxides. XANES data support Pt and Cu alloying and indicate the presence of lattice disorder in the PtCu nanoparticles. The PtCu co-catalyst on TiO2 shows a synergistic activity enhancement and a significantly higher activity towards photocatalytic H2 evolution than Pt- or Cu-TiO2. We propose the enhanced activity to be due to Pt-Cu electronic interactions, where Cu increases the electron density on Pt favoring a more efficient electron transfer for H2 evolution. In addition, Cu can further promote the photo-activity by providing additional surface catalytic sites for hydrogen recombination. Remarkably, when increasing the methanol concentration up to 50 vol% in the reaction phase, we observe for PtCu-TiO2 a steeper activity increase compared to Pt-TiO2. A further increase in methanol concentration (up to 80 vol%) causes for Pt-TiO2 a clear activity decay, while PtCu-TiO2 still maintains a high level of activity. This suggests an improved robustness of PtCu nanoalloys against poisoning from methanol oxidation products such as CO

Critical Factors in the Anodic Formation of Extremely Ordered Titania Nanocavities

In the present work, we discuss the formation of a highly ordered form of TiO2 nanotubes (U-tubes) which are grown by anodizing Ti metal in a concentrated HF/H3PO4 electrolyte. The crucial parameters determining geometry and order of the tubes (such as, temperature, applied voltage, concentration of HF, and anodizing time) are investigated and discussed. Under optimized conditions, not only very high degree of order, but also a perfectly open tube top morphology is obtained. The amorphous titania tubes (cavities) consist of a phosphate rich inner layer and a fluoride rich outer layer. Thermal crystallization of these short amorphous cavities to anatase/rutile at temperatures (>400°C) in air leads to partial oxidation of the underneath metal - this and the short length of the tubes, usually around 200 nm, pose challenges for potential photoelectrochemical applications. However, the limited tube length can be overcome by a double anodizing technique. The extremely high order and unique nature of these types of self-ordered tubes allows for unprecedented control and enables various uses of the tubes

Cathodic Reduction of Passive Films on Iron in Borate and Phosphate Buffer Ph 8.4: Different Mechanisms Revealed by in Situ Techniques.

The electrochemical behavior of passive Fe and thin, sputter-deposited films of Fe{sub 2}O{sub 3} was studied in borate and phosphate buffer pH 8.4 solutions. Cyclic voltammograms and in situ light absorption measurements--which enable the monitoring of the oxide film thickness--indicate a similar behavior of the Fe electrode in both pH 8.4 solution, especially a presence of a oxide-free surface at low cathodic potentials. However, X-ray absorption near edge structure (XANES) studies--which allow a simultaneous monitoring of changes in the samples' average valency and thickness--reveal that the reactions taking place during reduction of the passive film on iron are completely different for the two electrolytes. In borate buffer (pH 8.4), reduction leads to a complete dissolution of the passive film and the end product of reduction is soluble Fe(2+). In phosphate buffer (pH 8.4), there is no dissolution in a direct step to low cathodic potentials, but the resulting reduction product is metallic iron. Hence, the formation of the bare oxide-free metal surface at cathodic potentials takes place by different mechanisms in the two pH 8.4 solutions, depending on the type of anion present in the solution

Enhanced Performance of Dye-Sensitized Solar Cells based on TiO2 Nanotube Membranes using Optimized Annealing Profile

We use free-standing TiO2 nanotube membranes that are transferred onto FTO slides in front-side illuminated dye-sensitized solar cells (DSSCs). We investigate the key parameters for solar cell arrangement of self-ordered anodic TiO2 nanotube layers on the FTO substrate and namely the influence of the annealing procedure on the DSSC light conversion efficiency. The results show that using an optimal temperature annealing profile can significantly enhance the DSSC efficiency (in our case 9.8 %), as it leads to a markedly lower density of trapping states in the tube oxide, and thus to strongly improved electron transport properties

Amorphous NiCu Thin Films Sputtered on TiO2 Nanotube Arrays: A Noble-Metal Free Photocatalyst for Hydrogen Evolution

In this work, NiCu co-catalysts on TiO2 are studied for photocatalytic hydrogen evolution. NiCu co-catalyst films are deposited at room temperature by argon plasma sputtering on high aspect-ratio anodic TiO2 nanotubes. To tune the Ni : Cu atomic ratio, alloys of various compositions were used as sputtering targets. Such co-catalyst films are found to be amorphous with small nanocrystalline domains. A series of parameters is investigated, i. e., i) Ni : Cu relative ratio in the sputtered films, ii) NiCu film thickness, and iii) thickness of the TiO2 nanotube layers. The highest photocatalytic activity is obtained with 8 μm long TiO2 nanotubes, sputter-coated with a 10 nm-thick NiCu films with a 1 : 1 Ni : Cu atomic ratio. This photocatalyst reaches a stable hydrogen evolution rate of 186 μL h−1 cm−2, 4.6 and 3 times higher than that of Ni- and Cu-TiO2, respectively, demonstrating a synergistic co-catalytic effect of Ni and Cu in the alloy co-catalyst film

Optical properties of silicon-implanted polycrystalline diamond membranes

We investigate the optical properties of polycrystalline diamond membranes containing silicon-vacancy (SiV) color centers in combination with other nano-analytical techniques. We analyze the correlation between the Raman signal, the SiV emission, and the background luminescence in the crystalline grains and in the grain boundaries, identifying conditions for the addressability of single SiV centers. Moreover, we perform a scanning transmission electron microscopy (STEM) analysis, which associates the microscopic structure of the membranes and the evolution of the diamond crystal along the growth direction with the photoluminescence properties, as well as a time-of-flight secondary ion mass spectrometry (ToF-SIMS) to address the distribution of silicon in implanted and un-implanted membranes. The results of the STEM and ToF-SIMS studies are consistent with the outcome of the optical measurements and provide useful insight into the preparation of polycrystalline samples for quantum nano-optics.Comment: 21 pages, 8 figure

Optical properties of structurally-relaxed Si/SiO2_2 superlattices: the role of bonding at interfaces

We have constructed microscopic, structurally-relaxed atomistic models of Si/SiO$_2$ superlattices. The structural distortion and oxidation-state characteristics of the interface Si atoms are examined in detail. The role played by the interface Si suboxides in raising the band gap and producing dispersionless energy bands is established. The suboxide atoms are shown to generate an abrupt interface layer about 1.60 \AA thick. Bandstructure and optical-absorption calculations at the Fermi Golden rule level are used to demonstrate that increasing confinement leads to (a) direct bandgaps (b) a blue shift in the spectrum, and (c) an enhancement of the absorption intensity in the threshold-energy region. Some aspects of this behaviour appear not only in the symmetry direction associated with the superlattice axis, but also in the orthogonal plane directions. We conclude that, in contrast to Si/Ge, Si/SiO$_2$ superlattices show clear optical enhancement and a shift of the optical spectrum into the region useful for many opto-electronic applications.Comment: 11 pages, 10 figures (submitted to Phys. Rev. B

Chemical composition of nanoporous layer formed by electrochemical etching of p-type GaAs

Abstract : We have performed a detailed characterization study of electrochemically etched p-type GaAs in a hydrofluoric acid-based electrolyte. The samples were investigated and characterized through cathodoluminescence (CL), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). It was found that after electrochemical etching, the porous layer showed a major decrease in the CL intensity and a change in chemical composition and in the crystalline phase. Contrary to previous reports on p-GaAs porosification, which stated that the formed layer is composed of porous GaAs, we report evidence that the porous layer is in fact mainly constituted of porous As2O3. Finally, a qualitative model is proposed to explain the porous As2O3 layer formation on p-GaAs substrate

Physicochemical Characterization of Passive Films and Corrosion Layers by Differential Admittance and Photocurrent Spectroscopy

Two different electrochemical techniques, differential admittance and photocurrent spectroscopy, for the characterization of electronic and solid state properties of passive films and corrosion layers are described and critically evaluated. In order to get information on the electronic properties of passive film and corrosion layers as well as the necessary information to locate the characteristic energy levels of the passive film/electrolyte junction like: flat band potential (Ufb), conduction band edge (EC) or valence band edge (EV), a wide use of Mott-Schottky plots is usually reported in corrosion science and passivity studies. It has been shown, in several papers, that the use of simple M-S theory to get information on the electronic properties and energy levels location at the film/electrolyte interface can be seriously misleading and/or conflicting with the physical basis underlying the M-S theory. A critical appraisal of this approach to the study of very thin and thick anodic passive film grown on base-metals (Cr, Ni, Fe, SS etc..) or on valve metals (Ta, Nb, W etc..) is reported in this work, together with possible alternative approach to overcome some of the mentioned inconsistencies. At this aim the theory of amorphous semiconductor Schottky barrier, introduced several years ago in the study of passive film/electrolyte junction, is reviewed by taking into account some of the more recent results obtained by the present authors. Future developments of the theory appears necessary to get more exact quantitative information on the electronic properties of passive films, specially in the case of very thin film like those formed on base metals and their alloys. The second technique described in this chapter, devoted to the physico-chemical characterization of passive film and corrosion layers, is a more recent technique based on the analysis of the photo-electrochemical answer of passive film/electrolyte junction under illumination with photons having suitable energy. Such a technique usually referred to as Photocurrent Spectroscopy (PCS) has been developed on the basis of the large research effort carried out by several groups in the 1970’s and aimed to investigate the possible conversion of solar energy by means of electrochemical cells. In this work the fundamentals of semiconductor/electrolyte junctions under illumination will be highlighted both for crystalline and amorphous materials. The role of amorphous nature and film thickness on the photo-electrochemical answer of passive film/solution interface is reviewed as well the use of PCS for quantitative analysis of the film composition based on a semi-empirical correlation between optical band gap and difference of electronegativity of film constituents previously suggested by the present authors. In this frame the results of PCS studies on valve metal oxides and valve metal mixed oxides will be discussed in order to show the validity of the proposed method. The results of PCS studies aimed to get information on passive film composition and carried out by different authors on base metals (Fe, Cr, Ni) and their alloys, including stainless steel, will be also compared with compositional analysis carried out by well-established surface analysis techniques