Integration of electrochemical capacitance–voltage characteristics: a new procedure for obtaining free charge carrier depth distribution profiles with high resolution

Journal of Solid State Electrochemistry - A novel electrochemical profiling technique consisting in integration capacitance–voltage characteristics was proposed, developed and proven. The aim...     

Tip‐enhanced Raman spectroscopy – an interlaboratory reproducibility and comparison study

Since its first experimental realization, tip‐enhanced Raman spectroscopy (TERS) has emerged as a potentially powerful nanochemical analysis tool. However, questions about the comparability and reproducibility of TERS data have emerged. This interlaboratory comparison study addresses these issues by bringing together different TERS groups to perform TERS measurements on nominally identical samples. Based on the spectra obtained, the absolute and relative peak positions, number of bands, peak intensity ratios, and comparability to reference Raman and surface‐enhanced Raman spectroscopy (SERS) data are discussed. Our general findings are that all research groups obtained similar spectral patterns, irrespective of the setup or tip that was used. The TERS (and SERS) spectra consistently showed fewer bands than the conventional Raman spectrum. When comparing these three methods, the spectral pattern match and substance identification is readily possible. Absolute and relative peak positions of the three major signals of thiophenol scattered by 19 and 9 cm⁻¹, respectively, which can probably be attributed to different spectrometer calibrations. However, within the same group (but between different tips), the signals only scattered by 3 cm⁻¹ on average. This study demonstrated the suitability of TERS as an analytical tool and brings TERS a big step forward to becoming a routine technique. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and Study of Acid-Basic Properties of Ti(IV) and Zr(IV) Phosphates Immobylized in the Matrix of Clinoptilolite

Abstract

By combination of the ionexchange and ionic-molecular layering methods [1], the synthesis of natural zeolite derivatives (clinoptilolite) containing in its composition nano-size fragments of Ti(IV) and Zr(IV) phosphates was performed. It was determined by the X-Ray method, that the phosphates of Ti(IV) and Zr(IV) replicate crystal lattice of zeolite, manifesting in enhancing the line's intensity on X-Ray patterns. The Brensted's and Lewis's spectra of acidic centers distributions were obtained by Hammett's indicator spectrophotometric method [2] in the interval of pK, values from -4.4 to 14.2, which have shown that P(V) of the derivatives is represented mainly by HPO₄- and H₂PO₄-groups, with predomination of these latter. It is shown that the force of Brensted's acidic centers, influenced by H₂PO₄-groups. remains at the level of H₂PO_(aq)-anion, and the force of the centers due to HPO₄-groups shifts into alkaline region, about 0,5 unit of pK. The strong acidic Lewis's centers were detected at the levels of pK, from 0 to -4.0. The spectra of Ti(IV) and Zr(IV) phosphates is presented in (1) and (2) respectively. A set of the acquired results makes possible a suggestion about using P(V)-containing derivatives in processes which are catalyzed both with Brensted's and Lewis's centers participation.     

Synthesis of Thin-Film Acidic Ti(IV) and Zr(IV) Phosphates Deposited on Surface of Fiber and Investigation their Properties

Abstract

Cellulosic fibres present great interest as matrix for non-organic synthesis with the use of ion-molecular layering method [I]. This method consists in realization of the successive reactions with the surface functional groups. Synthesized materials can he of scientific and technical interest.     

An unusual way of formation of spirophosphoranes during the oxidative addition of hexafluoroacctone to σ5P-σ3P-diphosphorus compounds,and in the reaction of 2-chloro-l,2-dimethyl-3-phenyl-2-phenylseleno-l,3,5σ5-diazaphosphetidin-4-one with bis(2-chloroethyl)amine hydrochloride/ triethylamine

The reaction of (chloromethyl)dichlorophosphine 1 with N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea 2 furnished the σ⁵P-σ³P-diphosphorus compound 3 . The reaction of 3 with hexafluoroacetone proceeded in an unusual fashion, with the rupture of the P? P bond, resulting in 4,4-bis(trifluoromethyl)-3-chloro-2-hexfluoroisopropoxy-2-oxo-1,2-oxaphosphetane 7 and the spirophosphorane 4-chloromethyl-1,3,5,7-tetramethyl-1,3,5,7-tetraaza-4σ⁵-phosphaspiro-[3,3]heptan-2,6-dione 8 . The reaction of 2-chloro-1,2-dimethyl-3-phenyl-2-phenylseleno-1,3,2σ⁵-diazaphosphetidin-4-one 9 with bis(2-chloroethyl)amine hydrochloride/triethylamine 10 also proceeded in an unexpected fashion, leading to the spirophosphorane 11 as the only identified product. Single-crystal X-ray structure analyses of compounds 8 and 11 were conducted. The coordination geometry at phosphorus in both compounds shows a large deviation from idealized forms. This distortion arises mainly from the presence of the four-membered rings.     

Peierls instabilities in one-dimensional systems with Jahn-Teller-active monomers

A one-dimensional system is investigated which consists of monomers with Jahn-Teller-active vibrational coordinates. Peierls distortions in the ground states of the half- and quarter-filled systems are studied as a function of the electron-lattice and Jahn-Teller coupling constants. For both degrees of filling and for all the values of the coupling constants the band structure of the ground state is doubly degenerate. The interrelation is discussed between the present system and systems where the active internal degrees of freedom are not of the Jahn-Teller type.