M-Au/TiO2 (M = Ag, Pd, Pt) composites were prepared through a facile one-pot photodeposition synthesis and evaluated for solar water splitting (SWS) with and without a sacrificial agent. The M-Au combination exhibits a dominant role in augmenting the H2 generation activity by forming a bi-metallic system. Degussa P25 was used as a TiO2 substrate to photodeposit Au followed by Au + M (M = Ag/Pd/Pt). The SWS activity of the M-Au/TiO2 was determined through photocatalytic H2 production in the presence of methanol as a sacrificial agent under one sun conditions with an AM1.5 filter. The highest H2 yield was observed for Pt0.5-Au1/TiO2 and was around 1.3 ± 0.07 mmol h(-1) g(-1), with an apparent quantum yield (AQY) of 6.4%. Pt0.5-Au1/TiO2 also demonstrated the same activity for 25 cycles of five hours each for 125 h. Critically, the same Pt0.5-Au1/TiO2 catalyst was active in overall SWS (OSWS) without any sacrificial agent, with an AQY = 0.8%. The amount of Au and/or Pt was varied to obtain the optimum composition and it was found that the Pt0.5-Au1/TiO2 composition exhibits the best activity. Detailed characterization by physico-chemical, spectral and microscopy measurements was carried out to obtain an in-depth understanding of the origin of the photocatalytic activity of Pt0.5-Au1/TiO2. These in-depth studies show that gold interacts predominantly with oxygen vacancies present on titania surfaces, and Pt preferentially interacts with gold for an effective electron-hole pair separation at Pt-Au interfaces and electron storage in metal particles. The Pt in Pt0.5-Au1/TiO2 is electronically and catalytically different from the Pt in Pt/TiO2 and it is predicted that the former suppresses the oxygen reduction reaction.
The notion of spontaneous formation of an inhomogeneous superconducting state is at the heart of most theories attempting to understand the superconducting state in the presence of strong disorder. Using scanning tunneling spectroscopy and high resolution scanning transmission electron microscopy, we experimentally demonstrate that under the competing effects of strong homogeneous disorder and superconducting correlations, the superconducting state of a conventional superconductor, NbN, spontaneously segregates into domains. Tracking these domains as a function of temperature we observe that the superconducting domains persist across the bulk superconducting transition, Tc, and disappear close to the pseudogap temperature, T*, where signatures of superconducting correlations disappear from the tunneling spectrum and the superfluid response of the system.
Phenylalanine (Phe) is an essential amino acid classified as neutral and nonpolar due to the hydrophobic nature of the benzyl side chain. In the field of materials science, the chemical modification of phenylalanine at C or N terminus has enabled to synthesize a large number of low-molecular-weight gelators over the past decade. Thus, many physical (or supramolecular) softgel materials have been fabricated by self-assembly of Phe-derived building blocks, which can be programmed with atomic level information and modification. The process of self-assembly and gelation must balance the parameters that influence the solubility as well as the contrasting forces that dictate epitaxial growth into entangled fibrillar aggregates. Gelator-gelator and solvent-gelator interactions are known to be highly important for the gelation process, and the non-covalent nature of these interactions provides physical gels with important properties such as reversible phase transitions and responsiveness towards external stimuli. Among other applications, these gels have been used for drug delivery, as extracellular matrix for tissue engineering, for oil spills recovery, removal of dyes, extraction of heavy metals or pollutants, and for the detection of explosives. In this tutorial review, we highlight the advances in the design, synthesis and applications of supramolecular gels made of Phe and derivatives.
Lanthanum belongs to the group of elements known as "lanthanons," which also includes cerium, europium, promethium, and thulium. It is the most electropositive element of the rare earth group, is uniformly trivalent, and is similar in its chemical properties to the alkaline earth elements. The effects of this element and its compounds on cellular systems are of considerable interest because of their increasing use in industry and as a substitute or antagonist for calcium in a variety of cellular reactions. Lanthanum is also being employed extensively in studying anatomical barriers, membrane structure, and subcellular transport systems, particularly the calcium pathway.
We introduce topological definitions of expansivity, shadowing, and chain recurrence for homeomorphisms. They generalize the usual definitions for metric spaces. We prove various theorems about topologically Anosov homeomorphisms (maps that are expansive and have the shadowing property) on noncompact and non-metrizable spaces that generalize theorems for such homeomorphisms on compact metric spaces. The main result is a generalization of Smale's spectral decomposition theorem to topologically Anosov homeomorphisms on first countable locally compact paracompact Hausdorff spaces.
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