Chemihiminescence by the interaction of XeO3 and the products of photolysis of uranyl solutions in sulfuric acid

Using the chemiluminescence oxidation of U(IV) and H₂O₂ with xenon trioxide as a model, it has been found that during the photolysis of solutions of UO₂SO₄ in sulfuric acid in the absence of any organic compounds, the accumulation of U(SO₄)₂ and H₂O₂ takes place as a result of the reaction of the primary products of the photoreduction of uranyl ion,i.e., UO₂ ⁺ and the OH radical.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 751–754, April, 1994.The work was financially supported by the Russian Foundation for Basic Research, Project 93-03-12291.     

Chemiluminescence in the reduction of XeO3 by europium(II)

Chemiluminescence has been observed in the reduction of perchloric aqueous solutions of XeO₃ with Eu²⁺ ions, Fast (several seconds) consumption of Eu^II occurs when the ratio of the initial concentrations of the reactants (Eu²⁺]₀ : [XeO₃]₀ < 6; however, the chemiluminescence remains sufficiently bright and prolonged (up to –10 min after nearly complete oxidation of Eu^II to Eu^III). The assumption was made that intermediates in the reduction of XeO₃ participate in the chemiluminescent stages of the process.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2909–2911, December, 1996.     

Concurrent oxygen reduction and methanol oxidation in sulfuric acid solutions on platinized platinum electrodes

Steady-state polarization curves are compared in solutions of 0.5 M H₂SO₄ + O₂ (saturated), 0.5 M H₂SO₄ + (0.005–0.1) M CH₃OH, and 0.5 M H₂SO₄ + (0.005–0.1) M CH₃OH + O₂ (saturated) on a Pt/Pt electrode. A considerable difference is found between the currents in mixed solutions and those expected based on the principle of additivity of currents in CH₃OH and O₂ individual solutions. The surface coverages with the CH₃OH and O₂ adsorption products are determined in the potential range of 0.2–0.9 V (RHE). Open-circuit potentials are measured in mixed solutions. The obtained results suggest that the direct heterogeneous interaction between methanol and oxygen occurs alongside with faradaic reactions. This is assumed to lead to a decrease in methanol electrooxidation currents at E ≥ 0.8 V and their increase at E ≤ 0.65 V.     

Electrochemical,spectroscopic, and thermal studies on interactions of linear poly(acrylic acid) with uranyl ions in aqueous solutions

The formation of complexes between linear poly(acrylic acid) (PAA) and uranyl ions in aqueous solutions was studied with conductometry, potentiometry, thermal analysis, Fourier transform infrared, and luminescence spectroscopy methods. The stoichiometry of the PAA/UO complex on repeating units of a PAA basis was determined to be 2:1. IR spectroscopy studies made on solid complexes showed that the carbonyl stretching absorption band of PAA was shifted to a higher wave number, and a new band at 1749 cm^?1 in the polycomplex spectrum was observed, confirming the existence of specific interactions between the carboxylate groups of PAA and metal ions. Luminescence spectroscopy studies showed an increase in the intensity of the uranyl‐ion emission spectra and new band formation at 483 nm, further confirming the interaction of UO ions with PAA in aqueous solutions. The thermal behavior of PAA/UO complexes further proved strong interactions in the complex structure. The thermal degradation of the polycomplexes included the main stages of destruction of both PAA and uranyl nitrate. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1610–1618, 2004     

Factors affecting the complexation of polyacrylic acid with uranyl ions in aqueous solutions: A luminescence study

A study was carried out in aqueous solutions using luminescence technique to investigate the effects of pH, salt concentration, and temperature on the polyacrylic acid/uranyl ion (PAA/UO) complex formation as well as competitive phenomena of enhancement and quenching effects on photoexcited state of uranyl ions. It was found that excess of H⁺ and OH^? is not favorable for complexation between uranyl ions and polymer. Added nitrate salts of Na⁺ and K⁺ had significant enhancement effect on emission spectra of PAA/UO complex. These results indicated that the metal ion/polymer chain complex collapsed by addition of salts and then complex became more compact with consequent phase separation. No significant effect of temperature on the PAA/UO complex stability has been observed between 25–50 °C. The quenching rate constants obtained from Stern–Volmer plots were found to be in the order of k_q(H⁺) >> k_q(K⁺) > k_q(Na⁺). © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2737–2744, 2005     

Mass transport and effective diffusion coefficient in the reduction of hydrogen ions from aqueous sulfuric acid solutions: Numerical modeling

This work presents results of the numerical solution to a system of equations of material balance and the movement of particles in solution under the influence of the forces of diffusion, migration, and convection, which describe the process of mass transport during the reduction of hydrogen ions at a rotating disk electrode from aqueous sulfuric acid solutions with and without excess supporting electrolyte. Results of the calculations show that the diffusion kinetics of hydrogen ion reduction can be observed only with measurements in dilute (≤10^?3 M) sulfuric acid solutions with an excess of indifferent supporting electrolyte. For more acidic solutions it is necessary to take into account the simultaneous diffusion of hydrogen and bisulfate ions. In the study of the regularities of hydrogen ion reduction in sulfuric acid solutions with a sulfate supporting electrolyte, it is necessary to take into account that with excess supporting electrolyte, the limiting current of hydrogen reduction is caused solely by the diffusion of bisulfate ions, but for small concentration ratios of the supporting electrolyte to acid, the influence of migration effects is significant.     

Electrochemiluminescence of Carbon-based Quantum Dots: Synthesis,Mechanism and Application in Heavy Metal Ions Detection

In recent years, carbon-based quantum dots as luminophores and co-reactants have aroused broad interest for their ability to function in electrochemiluminescence (ECL) sensors due to their unique features, including excellent biocompatibility, low toxicity, and water solubility. In this mini review, the synthesis methods of carbon-based quantum dots are firstly introduced. Then, the mechanism of carbon-based quantum dots as luminophores and co-reactants and their latest progress application in the detection of heavy metal ions are explored. Finally, the current challenges and potential future development directions of carbon-based quantum dots in ECL sensing filed for heavy metal ions analysis are summarized.     

Electrochemical preparation of orthophenylenediamine on different cathodes in sulfuric acid

The electrochemical reduction of nitro group of orthonitroaniline (ONA) is carried out on Pb, Cu, and Sn electrodes. The effect of current density, temperature, and acid concentration on product yield is studied. The polarization curve for ONA in acidic condition is recorded. Under preparative electrolysis, ONA gives a mixture of hydroxylamine and phenylenediamine, the proportion of phenylenediamine increasing with the electrolysis time. The product formation is confirmed by thin-layer chromatography, melting-point test, UV-visible, IR, and NMR methods. The operating conditions are optimized for a good yield of orthophenylenediamine. The catalytic activity of different metals for the reduction of nitro group is discussed. The percent yield of orthophenylenediamine is found to be high on the lead electrode. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 2, pp. 215–221. The text was submitted by the authors in English.     

Formaldehyde interaction with adsorbed oxygen on open-circuit platinum electrodes in aqueous sulfuric acid solutions

The open circuit potential transients and cathodic potentiodynamic pulses were measured upon formaldehyde (methylene glycol) interaction with pre-adsorbed oxygen (O_ads) on Pt/Pt and pc Pt electrodes in aqueous sulfuric acid solutions. The slowest interaction of CH₂(OH)₂ with O_ads was observed in the high coverage range of the electrode surface (θ_O ～ 0.2 0.8 to 1). The process rate in this range is determined by the direct reaction of O_ads with CH₂(OH)₂ molecules from the bulk solution. In the middle surface oxygen coverage range (θ_O 0.2 to 0.8), CH₂(OH)₂ interaction with O_ads takes place by the mechanism of “conjugated reactions”. The kinetic parameters of reactions for CH₂(OH)₂, HCOOH, and CH₃ OH were compared. The rate of CH₂(OH)₂-O_ads interaction on Pt electrodes in the high oxygen coverage range was found higher by an order of magnitude than that of HCOOH and by two orders of magnitude than in the case of CH₃OH.     

Electrochemical reduction of zinc complexes from glycinate solutions

Kinetics of electrochemical reduction of zinc(II) complexes is studied in a wide range of solution pH using the polarization measurements and chronopotentiometry. Adsorption of glycinate ions on zinc electrode and complexing of zinc(II) with glycine are studied using the ¹³C NMR method. Based on the experimental data, the electrochemical behavior of zinc(II)–glycine–water system is considered.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 228–231.Original Russian Text Copyright © 2005 by Berezin, Sagdeev, Gudin, Roev, Mezhevich.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.     

Thin-layer chromatography of inorganic ions on polyethyleneimine cellulose in sulfuric acid and acid-ammonium sulfate media

Summary The thin-layer chromatographic behavior of 49 inorganic ions on polyethyleneimine (PEI) cellulose, a weakly basic anion-exchanger, has been systematically studied in sulfuric acid and ammonium sulfate media (both 0.01–1.0 moldm⁻³). The sorption on the cellulose decreases with increasing concentration of the acid or sulfate for most of the ions and to a lesser extent for Hg(II), Bi(III), Th(IV), Nb(V), and U(VI). The R_f values of Pd(II), Ru(III), Au(III), Pt(IV), and Ta(V) are extremely low in both systems. Ba(II), Pb(II), Sb(III), Mo(VI), and W(VI) are also strongly retained on the layer. Oxy-anions such as As(III) and Se(VI) are not adsorbed on the cellulose to any great extent, but Re(VII) distributes on the plate with a R_f value of about 0.5. The characteristic retention on PEI-cellulose layer of several polyvalent ions, which form anionic sulfato complexes, can be observed in ammonium sulfate media. Possibilities for separations of analytical interest are also demonstrated in both systems.     

Interaction of activated carbon electrodes with sulfuric acid solutions

Impedance and potentiodynamic studies have been carried out to investigate reversible processes on the surface of electrodes based on activated carbon (AC). Relationships have been found between the reversible capacity and true resistance, on the one hand, and the potential, on the other. Stoichiometric characteristics of AC charging in sulfuric acid have been obtained. A mechanism of the reversible surface process is suggested. It is concluded that Faraday pseudocapacity makes a considerable contribution to charging of AC electrolytes. The amount of gas liberated in the course of AC wetting in electrolyte has been measured. It is assumed that the amount of liberated gas depends on the amount of active oxygen involved in the current-forming reaction. Based on the data obtained, a redox surface reaction is substantiated in general form.     

共反应试剂增强电致化学发光信号生物传感器

在电致化学发光（ECL）生物传感器的构建中,利用共反应试剂促进发光基团的发光效率是一种常见、方便且非常有效的方法. 然而,如何更好地利用共反应试剂使其更加有效地与发光基团作用是提高该类生物传感器灵敏度的重要因素. 本文结合作者课题组部分工作综述了三种共反应试剂放大ECL信号的构建：共反应试剂内置于检测底液;共反应试剂共存于电极表面;酶促生成共反应试剂,并提出了今后ECL信号放大构建的展望.     

罗丹明B的电致化学发光行为研究

研究发现罗丹明B在碱性溶液中铂电极上有较强的电致化学发光行为.通过对不同NaOH浓度,以及对不同支持电解质的考察,确定最佳电致化学发光条件.在最优条件下,在1.2×10-7~1.1×10-6mol/L浓度范围内,罗丹明B的电致化学发光强度与其浓度成线性关系,最低检测限为9.0×10-8mol/L(S/N=3).将罗丹明B同一些生物活性物质相配合,然后通过罗丹明B的ECL技术对生物活性物质进行检测.     

Effect of antimony on the reduction of anodic Pbo_2 film on Pb-Sb alloys in sulfuric acid solution

The reduction processes of anodic PbO2 films formed on Pb-Sb alloys in 4.5mol·dm-3 H2SO4 solution at 1.4 V(vs.Hg/Hg2SO4) for 1 h have been investigated by pho-tocurrent method,chronoamperometry,linear sweep voltammetry as well as X-ray diifractornetry.It was found that the reduction of most of the β-PbO2 and part of the α-PbO2 to PbSO4 can be completed within I s between 0.9 V and 1.0 V(vs.Hg/Hg2SO4) and proceeds much faster than that of the remaining a-PbO2 into photoactive α·PbOx (1相似文献   

二茂铁催化鲁米诺电致化学发光反应的研究

在碱性Tris缓冲体系中 ,鲁米诺与过氧化氢的电致化学发光反应要在 4 5 0mV以上的电位下才可以发生 ,加入羧基二茂铁 (FCA)可以使这一发光反应的起始电位负移 ,而且发光信号随电极电位的增大而急剧增强。详细考察了这一催化发光体系 ,研究了影响发光强度的各种因素 ,建立了Luminol H2 O2 FCA发光体系测定FCA的电致化学发光新方法。方法测定二茂铁的检出限可达 1.5nmol/L ,二茂铁浓度在 5 .0× 10 -9～ 2 .0×10 -4mol/L范围内与电致化学发光强度呈良好的线性响应关系     

The effect of iodide on the electrochemical reduction of thick oxide films formed on platinum electrodes in sulfuric acid solution

The reduction of thick oxide films formed on Pt under severe anodic conditions was studied in the presence of adsorbed I^?. The Pt electrode covered with a thick oxide film does not adsorb I^?. However, when a superficial monolayer oxide on the thick oxide has been reduced, I^? is irreversibly adsorbed. Iodide adsorbed on its surface blocks the adsorption of hydrogen and retards markedly the cathodic reduction of the inner thick oxide remaining. It was found that the reduction rate of the inner oxide depends only on the coverage by hydrogen, which coexists with adsorbed I^?. These results support the proton-electron theory which has previously been proposed for the explanation of the characteristic reduction of the thick oxide films.     

Structure-relationships in electrocatalysis: oxygen reduction and hydrogen oxidation reactions on Pt(111) and Pt(100) in solutions containing chloride ions

Kinetics of the oxygen reduction reaction (orr) and the hydrogen evolution–oxidation reactions (her/hor) were studied on the Pt(111) and Pt(100) surfaces in 0.05 M H₂SO₄ containing Cl⁻. The orr is strongly inhibited on the (100) surface modified by adsorbed Cl⁻ (Cl_ad), and it occurs as a 3.5e⁻ reduction via solution phase peroxide formation. In the hydrogen adsorption (H_upd) potential region, the orr is even more inhibited, and corresponds only to a 2 e⁻ reduction at the negative potential limit where the electrode is covered by one monolayer of H_upd and some (unknown) amount of Cl_ad. On the Pt(111)---Cl_ad surface, the orr is inhibited relatively little (in addition to that caused by strong bisulfate anion adsorption on this surface), and the reaction pathway is the same as in Cl⁻ free solution. The kinetics of the hor on Pt(111) are the same in pure solution and in a solution containing Cl⁻, since Cl_ad does not affect platinum sites required for the breaking of the H---H bond. A relatively large inhibition of the hor is observed on the (100) surface, implying that strongly adsorbed Cl_ad is present on the surface even near 0 V.