Preferential synthesis of highly conducting Tl(TCNQ) phase II nanorod networks via electrochemically driven TCNQ/Tl(TCNQ) solid-solid phase transformation

Facile synthesis and characterization of the highly conducting, thermodynamically favored, Tl(TCNQ) phase II microrods/nanorods onto conducting (glassy carbon (GC)) and semiconducting (indium tin oxide (ITO)) surfaces have been accomplished via redox-based transformation of 7,7,8,8-tetracynoquinodimethane (TCNQ) microcrystals. This electrochemically irreversible process involves the one-electron reduction of surface-confined solid TCNQ into TCNQ·^? with concomitant incorporation of the Tl⁺ _(aq) cation, from the bulk solution, at the triple-phase boundary, GC or ITO│(TCNQ_(s)/TCNQ·^? _(s))│Tl⁺ _(aq), through a nucleation/growth mechanism. Consistent with the conceptually related M(TCNQ) systems (M⁺ = Li⁺, Na⁺, K⁺, Ag⁺, and Cu⁺), the TCNQ/Tl(TCNQ) interconversion is strongly dependent upon scan rate, Tl⁺ _(aq) electrolyte concentration, and the method of attaching solid TCNQ onto the electrode surface. Spectroscopic (infrared (IR) and Raman), microscopic (scanning electron microscopy (SEM)), and surface science (X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray (EDX), and X-ray diffraction (XRD)) characterization of the electrochemically synthesized material revealed formation of pure Tl(TCNQ) phase II. Importantly, the generic solid-state electrochemical approach used in this study not only offers facile protocol for controllable and preferential synthesis of Tl(TCNQ) phase II but also provides access to fabricate and tune the morphology to yield microrod/nanorod networks.

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Graphical abstract Controlled synthesis of the highly conducting Tl(TCNQ) phase II with either nanowire or rod-like morphologies is achieved via a redox-based solid-solid phase interconversion of TCNQ microcrystals in the presence of a Tl⁺ _(aq) electrolyte.

     

Multistate polarization addressing using a single beam in an azo polymer film

Peculiar light-matter interactions can break the rule that a single beam polarization can address only two states in an optical memory device. Multistate storage of a single beam polarization is achieved using self-induced surface diffraction gratings in a photoactive polymer material. The grating orientation follows the incident light beam's polarization direction. The permanent self-induced surface relief grating can be read out in real time using the same laser beam.     

Incoherent light-induced self-organization of molecules

Although coherent light is usually required for the self-organization of regular spatial patterns from optical beams, we show that peculiar light-matter interaction can break this evidence. In the traditional method of recording laser-induced periodic surface structures, a light intensity distribution is produced at the surface of a polymer film by an interference between two coherent optical beams. We report on the self-organization followed by propagation of a surface relief pattern. It is induced in a polymer film by using a low-power and small-size coherent beam assisted by a high-power and large-size incoherent and unpolarized beam. We demonstrate that we can obtain large size and well-organized patterns starting from a dissipative interaction. Our experiments open new directions to improving optical processing systems.     

Spontaneous nano pattern formation under pulsed exposure: relaxation kinetics study

Formation of spontaneous surface relief grating under pulsed exposure on the surface of an azo polymer film has been investigated. We did experiments in different repetition rates and pulse widths by use an electro mechanical chopper and a diode-pumped solid-state laser with wavelength of 532?nm as pump beam. Incidence of pump beam, has been set normal to the surface of azo-polymer film. Spontaneous surface relief grating with grating pitch of ~1,250?nm was formed. For low repetition rate, relaxation due to cis-trans isomerization becomes dominant and growth rate becomes slower. A threshold for spontaneous pattern formation was found. In addition to an increase in the diffraction intensity during illumination, anomalous variation of diffraction intensity by switching on and off the laser was observed. By switching off the recording beam sharp enhancement occurred. By switching on the recording beam, after a sharp decrease in the intensity of diffracted beam, it increased further under illumination. Anomalous variations, strongly depends on polarization of the probe beam and the irradiation time for the formation of spontaneous SRG. Sharp enhancement has been attributed to cis-trans thermal isomerization and sharp decrease has been attributed to isomeration in whole surface under illumination.     

Transition (Mn,Fe) and rare earth (La,Pr) metal doped ceria solid solutions for high performance photocatalysis: Effect of metal doping on catalytic activity

Research on Chemical Intermediates - In this work, various transition and rare earth metal ions (M3+; M = Mn3+, Fe3+, La3+, and Pr3+) doped CeO2 solid solutions were prepared by a...     

Characteristics of the breakup and fragmentation of an electrohydrodynamic melt jet

In this study, the breakup of a melt jet into a viscous medium is investigated in the presence of an intense electric field. Fragmentation of the melt jet occurs due to both hydrodynamic and electrohydrodynamic (EHD) forces within two kinds of silicone oil of different viscosities. The size and shape characteristics of the produced particles have been studied using SEM images, and the particle size distributions were found to exhibit considerable variations when a voltage was applied and when both the viscosity and temperature of the base fluid were changed. The morphologies of the particles were also affected by the same parameters. For instance, by applying EHD force, significant enhancements in size reduction and increased roundness of the particles occurred. The breakup process of the melt jet was found to be dominant by hydrodynamic or electrohydrodynamic instabilities, depending on the situation. Governing mechanisms (instability) in the cases of pure hydrodynamic and electrohydrodynamic fragmentations are discussed.     

A new paradigm for signal processing of Raman spectra using a smoothing free algorithm: Coupling continuous wavelet transform with signal removal method

Noise removal is considered a primary and inevitable step for background correction in experimentally obtained Raman spectra. Employing an appropriate algorithm for a smoothing‐free background correction technique not only increases the speed but also eliminates unwanted errors from the smoothing algorithms. Herein, we show a new smoothing‐free method for background correction, which we developed by merging continuous wavelet transform and signal removal method, which in combination, could be applied to noisy signals without smoothing. We used wavelet transformation for suppressing the side effects of noise and eliminating peaks from the spectrum, thereby providing spectral sections purely related to the background to be used in the background correction process. We applied a range of statistical analyses to test the performance of this algorithm, wherein a low deviation in background correction procedure was observed. Additionally, when we tested this algorithm for experimentally obtained real Raman spectra, it showed good capability to correct background of noisy signals without the requirement of a smoothing process. Copyright © 2013 John Wiley & Sons, Ltd.