The 2D Rancieite-type manganic acid and its alkali-exchanged derivatives: Part II — Electrochemical behavior

Various layered manganese oxides (phyllomanganates) with the Rancieite structural type were studied for their ability to intercalate lithium in an electrochemical cell. Series of such materials with various interlayer cations (H, Li, Na), various interlayer water contents and various manganese average oxidation states, were investigated, allowing to get precious information on the influence of such key parameters on the electrochemical behavior of phyllomanganates. The water content of electrode materials, different from that of open-air samples, was carefully measured thus allowing to interpret properly electrochemical data. Special attention was given to the first cycles, especially to the influence of an initial charge on the first discharge capacity and on the influence of such electrochemical pretreatment on further intercalation-deintercalation behavior. The electrochemical behavior at first cycles is complex, with the interlayer water playing a major role. Dehydrated materials at T> 200 °C showed a large initial capacity of about 220 mAh/g and a good capacity retention over the ten first discharge-charge cycles.     

Template-free synthesis of MnO2 nanowires with secondary flower like structure: Characterization and supercapacitor behavior studies

Manganese dioxide (MnO₂) nanowires with diameter about 30-70 nm is achieved via a two-step process: first, template-free cathodic electrodeposition from aqueous solution of Mn(NO₃)₂ on steel substrate and followed by heat treatment. The temperature-annealed sample was studied by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) methods and Fourier transform infrared (FT-IR) spectroscopy. The electrochemical performance of the MnO₂ sample was studied by cyclic voltammetry (CV) and chronopotentiometry in Na₂SO₄ solutions. The sample showed excellent supercapacitive behavior. The specific capacitance (SC) of 237 F g⁻¹ in a potential window of 0-0.9V was obtained at the scan rate of 2 mV s⁻¹. The SC calculated from the chronopotentiometry data is about 246 F g⁻¹. The SC was decreased by 16% after 1000 cycles.     

Underwater and water-assisted laser processing: Part 2—Etching, cutting and rarely used methods

In the second part of the article, the subtractive processes—laser etching and cutting—in the presence of liquid water will be reviewed; but the rarely used methods of water assisted/underwater laser processing, such as welding, silicon wafer breaking, surface modification of polymers, pulsed laser deposition, particle formation and water mask defined microstructures fabrication, will also be described. Etching and cutting under water provide better tolerances and smaller heat-affected zone widths and avoid the re-deposition of debris. Irradiation under water results in increased wetting of fluoropolymers, and laser ablation in water vapor provides deposition of highly crystalline hydroxyapatite coatings. Laser irradiation of solid targets in water has been used to fabricate Ag, Au, Ni, Cu and carbon nanoparticles. The results of an original study on the formation of free-standing high aspect ratio Pb(Zr_xTi_1−x)O₃ microplates fabricated by laser irradiation of Pb(Zr_xTi_1−x)O₃ ceramics in water are also reported. The platelets were up to 60 μm in diameter and 50–160 nm in thickness. The use of neutral liquids other than water and some medical applications of underwater/water-assisted laser light driven processes will also be briefly reviewed.     

Spectroscopic and thermal studies on the inclusion of trans‐cinnamic acid and a number of its hydroxyl‐derivatives with α, β and γ‐cyclodextrins molecules

The inclusion compounds of α‐, β‐ and γ‐cyclodextrins (α‐CD, β‐CD and γ‐CD) with trans‐cinnamic acid (t‐CIA), 3‐hydroxy‐trans‐cinnamic acid (t‐3OHCIA), 4‐hydroxy‐trans‐cinnamic acid (t‐4OHCIA) and 3,4‐dihydroxy‐trans‐cinnamic acid (t‐3,4OHCIA) were prepared and characterized, in the solid state, by means of thermogravimetry and Raman spectroscopy. The effects of the inclusion process on the guest molecules and on the hydrogen bond interactions of the guest were studied by monitoring sensitive vibrational modes, such as CO, CC and ring C H stretching modes. By combining Raman and TG data with ab initio calculations and information from CSD database on similar compounds, inclusion geometries for the different compounds are proposed. The size of the host cavity and the maximization of host/guest hydrogen‐bonding contacts appear to be the main factors determining the inclusion geometries. Copyright © 2009 John Wiley & Sons, Ltd.     

Influence of structural defects on the insertion behavior of γ-MnO2: comparison of H and Li

In an attempt to correlate the crystallographic disorder of γ-MnO₂ compounds to their cationic uptake, the influence of their structural defects on their lithium and proton insertion behavior has been studied and compared. The rate of structural defects in the starting γ-MnO₂ compounds strongly modifies both the voltage vs. cation composition profiles (in terms of shape, average voltage of each electrochemical process, polarization and cycled capacity) and the cycling behavior during the first cycles. This work illustrates that the relationships between structure and cation insertion behavior are different for Li and for proton. The study allows to select for better performing samples in terms of maximum cycled capacity: Li insertion is favored by a very small amount of initial disorder (i.e. a low rate of structural defects in starting compound), while proton insertion requires maximum initial disorder (i.e. an intermediate rate of structural defects). Extrapolation of the results demonstrates the interest of Ramsdellite γ-MnO₂ compounds for cathode applications of rechargeable Li batteries.     

ThO+/0/-2不同电荷态对N2O氧化CO反应的影响

本文采用密度泛函理论,对ThO^+/0/-₂团簇参与CO与N₂O间氧化还原反应(CO+N₂O→CO₂+N₂)的机理展开研究,探讨钍氧团簇所带的电荷对该反应的影响.研究表明：ThO^+/0/-₂在反应中主要起传输氧原子的作用,其中ThO⁺₂与CO的反应以及ThO^+/0/-与N₂O的反应都为热力学上的放热反应,而ThO^0/-₂与CO的反应为热力学上的吸热反应.随着电荷态的改变,ThO^+/0/-₂与CO反应的总能垒(E_b)与总驱动力(-ΔG)有较大差异.因此,通过改变ThO₂的电荷态能调节其对CO/N₂O反应的催化活性,综合考虑,ThO⁺₂对...     

Graphene oxide based Pt-TiO2 photocatalyst: ultrasound assisted synthesis, characterization and catalytic efficiency

An ultrasound-assisted method was used for synthesizing nanosized Pt-graphene oxide (GO)-TiO₂ photocatalyst. The Pt-GO-TiO₂ nanoparticles were characterized by diffused reflectance spectroscopy, X-ray diffraction, N₂ BET adsorption-desorption measurements, atomic force microscopy and transmission electron microscopy. The photocatalytic and sonophotocatalytic degradation of a commonly used anionic surfactant, dodecylbenzenesulfonate (DBS), in aqueous solution was carried out using Pt-GO-TiO₂ nanoparticles in order to evaluate the photocatalytic efficiency. For comparison purpose, sonolytic degradation of DBS was carried out. The Pt-GO-TiO₂ catalyst degraded DBS at a higher rate than P-25 (TiO₂), prepared TiO₂ or GO-TiO₂ photocatalysts. The mineralization of DBS was enhanced by a factor of 3 using Pt-GO-TiO₂ compared to the P-25 (TiO₂). In the presence of GO, an enhanced rate of DBS oxidation was observed and, when doped with platinum, mineralization of DBS was further enhanced. The Pt-GO-TiO₂ catalyst also showed a considerable amount of degradation of DBS under visible light irradiation. The initial solution pH had an effect on the rate of photocatalytic oxidation of DBS, whereas no such effect of initial pH was observed in the sonochemical or sonophotocatalytic oxidation of DBS. The intermediate products formed during the degradation of DBS were monitored using electrospray mass spectrometry. The ability of GO to serve as a solid support to anchor platinum particles on GO-TiO₂ is useful in developing new photocatalysts.     

Interface-charged impurity scattering in semiconductor MOSFETs and MODFETs: temperature-dependent resistivity and 2D ‘metallic‘ behavior

We present the results on the anomalous 2D transport behavior by employing Drude–Boltzmann transport theory and taking into account the realistic charge impurity scattering effects. Our results show quantitative agreement with the existing experimental data in several different systems and address the origin of the strong and nonmonotonic temperature-dependent resistivity.     

The effect of benzo‐annelation on intermolecular hydrogen bond and proton transfer of 2‐methyl‐3‐hydroxy‐4(1H)‐quinolone in methanol: A TD‐DFT study

Excited‐state intermolecular or intramolecular proton transfer (ESIPT) reaction has important potential applications in biological probes. In this paper, the effect of benzo‐annelation on intermolecular hydrogen bond and proton transfer reaction of the 2‐methyl‐3‐hydroxy‐4(1H)‐quinolone (MQ) dye in methanol solvent is investigated by the density functional theory and time‐dependent density functional theory approaches. Both the primary structure parameters and infrared vibrational spectra analysis of MQ and its benzo‐analogue 2‐methyl‐3‐hydroxy‐4(1H)‐benzo‐quinolone (MBQ) show that the intermolecular hydrogen bond O₁―H₂?O₃ significantly strengthens in the excited state, whereas another intermolecular hydrogen bond O₃―H₄?O₅ weakens slightly. Simulated electron absorption and fluorescence spectra are agreement with the experimental data. The noncovalent interaction analysis displays that the intermolecular hydrogen bonds of MQ are obviously stronger than that of MBQ. Additionally, the energy profile analysis via the proton transfer reaction pathway illustrates that the ESIPT reaction of MBQ is relatively harder than that of MQ. Therefore, the effect of benzo‐annelation of the MQ dye weakens the intermolecular hydrogen bond and relatively inhibits the proton transfer reaction.     

Excited‐state structural dynamics and vibronic coupling of 1,3‐dithiole‐2‐thione—resonance Raman spectroscopy and density functional theory calculation study

1,3‐Dithiole‐2‐thione (DTT) was synthesized and characterized using NMR, FT‐Raman, FT‐IR, UV spectroscopies. Resonance Raman spectra (RRs) were obtained with 341.5, 354.7 and 368.9 nm excitation wavelengths and density functional calculations were done to elucidate the electronic transitions and the RRs of DTT in cyclohexane solution. The RRs indicate that the Franck‐Condon region photodynamics is predominantly along the CS stretch+ H‐CC‐H scissor υ₄, accompanied by the H‐CC‐H scissor υ₃, S‐C‐S symmetric stretch υ₆, CC stretch υ₂, and overtone of the non‐totally symmetric SC‐S2 out‐of‐plane deformation 2υ₁₁. The excited‐state dynamics and the force constant of CS stretch calculated by the RRs were discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Part I. The 2D classical Coulomb gas near the zero-density Kosterlitz-Thouless critical point: Correlations and critical line

The 2D classical Coulomb gas undergoes the famous Kosterlitz-Thouless (KT) transition between a high-temperature conducting phase and a low-temperature insulating phase. We present various studies of the correlations in the insulating phase near the zero-density critical point. First, we briefly recall the phenomenological approach of Kosterlitz and Thouless. This theory predicts that the decay of the charge correlation is entirely controlled by the bare Coulomb potential between opposite charges only renormalized by the dielectric constante. Then, we present an analysis of the low-fugacity expansions of the correlations. The particle correlations are found to decay as 1/r⁴. The large-distance decay of the charge correlation is shown to be tightly related to the behavior of l/s in the regime of interest. Systematic resummations allow one to recover the algebraic decay predicted by the heuristic KT model. This settles on a rigorous basis various assumptions of this model. In particular, the nested pair mechanism naturally arises in the resummation scheme. Finally, we describe the phase diagram of the system according to the most recent calculations which include finite-density effects.     

Quantum Hall effect: The resistivity of a 2D electron gas—a thermodynamic approach

Based on a thermodynamic approach, we have calculated the resistivity of a 2D electron gas, assumed dissipationless in a strong quantum limit. Standard measurements, with extra current leads, define the resistivity caused by a combination of Peltier and Seebeck effects. The current causes heating (cooling) at the first (second) sample contacts, due to the Peltier effect. The contact temperatures are different. The measured voltage is equal to the Peltier effect-induced thermoemf which is linear in current. As a result, the resistivity is non-zero as I→0. The resistivity is a universal function of magnetic field and temperature, expressed in fundamental units h/e². The universal features of magnetotransport data observed in the experiment confirm our predictions.     

Vibrational spectra of rhombohedral TeO3 compared to those of ReO3‐like proto‐phase and α‐TeO2 (paratellurite): lattice dynamic and crystal chemistry aspects

Vibrational spectra of rhombohedral TeO₃ (r‐TeO₃) are analyzed along with those of ReO₃‐like proto‐phase (c‐TeO₃) and α‐TeO₂ (paratellurite), emphasizing their lattice dynamic and crystal chemistry aspects. It is shown that (1) r‐TeO₃ can be regarded as resulting from the condensation of a particular R‐point soft phonon of c‐TeO₃; (2) the Raman spectra of r‐TeO₃ and α‐TeO₂ are indicative of the two fundamentally different (from the crystal chemistry point of view) types of crystalline oxides, namely, framework‐type and island‐type, respectively. Copyright © 2010 John Wiley & Sons, Ltd.     

Crystal and molecular structure of 2‐amino‐5‐chloropyridinium hydrogen selenate—its IR and Raman spectra,DFT calculations and physicochemical properties

The new organic‐inorganic salt, 2‐amino‐5‐chloropyridinium hydrogen selenate, has been synthesised and characterised by means of FT‐IR, FT‐Raman and single crystal X‐ray crystallography. Its vibrational spectra have been discussed on the basis of quantum chemical DFT calculations using the B3LYP/6‐31G(d,p) approach. The crystal and molecular structures have been compared and the role of the intermolecular interactions in this crystal has been analysed. The N HO interactions between the hydrogen atoms of the organic cation and oxygen atoms of hydrogen selenate anion determine the supramolecular arrangement in three‐dimensional space. The possible application of the studied composite material as a Raman laser has been discussed. Copyright © 2008 John Wiley & Sons, Ltd.