Electrochemical behavior of glassy carbon electrodes modified by electrochemical oxidation

Glassy carbon electrodes were modified electrochemically by pretreatment in sulfate, phosphate or carbonate solutions by means of cycling the potential well into the positive limit of the solvent. Electrodes treated in this manner were then used to incorporate and concentrate a variety of redox species that were either cations or aromatic containing compounds, including Ru(bpy)²⁺₃, Ru(NH₃)³⁺₆, Cu(NH₃)²⁺₄, ferrocene, methylviologen, 1,4-benzoquinone, anthraquinone-2-sulfonate, riboflavin, flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD). Surface-equivalent concentrations ranged from 5 × 10^?9 to 1 × 10^?7 mol cm^?2 for electrodes pretreated for 10 min in sulfuric acid. An E_1/2 vs. pH study of 1,4-benzoquinone, riboflavin, FMN and FAD in modified electrodes shows that the pK_a values shift toward higher pH (nearly 2 pH units). Results concerning the incorporation of redox compounds detected only by mediation with other electroactive complexes and the study of the modified electrodes in electrocatalysis are also discussed.     

Na+ transport across the beta alumina-propylene carbonate interface

Interfacial Na⁺ ion transport between polycrystalline beta alumina and propylene carbonate has been studied using a galvanostatic transient technique which separates interfacial overpotential from bulk resistivity effects. No interfacial polarization is detected during ion entry into beta alumina and exit from beta alumina across a dry interface from 30–1000 μA cm^?2. Transport across an interface contaminated with adsorbed water follows Tafel-type i/E behavior with a transition coefficient (α) of 0.24 and exchange current (i₀) of 3.0×10^?6 A cm^?2 at 23°C. Interfacial transport appears to take place through an intermediate state in which the mobile ion is adsorbed on the interface. Large increases in interfacial polarization occur at both dry and hydrated interfaces for ionic currents exceeding the rate of adsorption or desorption.     

Electrostatic effect of specifically adsorbed electroinactive ions upon electrode processes: Part VII. Case of a charged adsorbed reactant. Dibromoacetate electroreduction in the presence of Br−, N3−, SCN− and Tl+ ions

The logarithmof the rate constant for CHBr₂COO^? electroreduction at constant applied potential, corrected for diffuse-layer effects according to Frumkin, varies linearly with the charge density q_i due to specifically adsorbed supporting ions. The rate of decrease ofwith increasing |q_i| as observed in the presence of the adsorbed anions Br^?, N₃^?, and SCN^? is about 5 times less than the rate of increase ofwith increasing the charge q_i due to adsorbed Tl⁺ cations. This behaviour, analogous to that observed in the reduction of the CCl₃COO^? ion [4], has been explained by considering that the time of adsorption of the electroactive anion CHBr₂COO^? is long enough to cause a perturbation in the distribution of the adsorbed supporting ions in the neighbourhood of the adsorbed anionic reactant.     

Kinetics of chloride substitution in [Pt(bpma)Cl]+ and [Pt(gly-met-S,N,N)Cl] complexes by thiourea, nitrites, and iodides

Substitution of chloride in [PtCl(bpma)]⁺ and [PtCl(gly-met-S,N,N)], where bpma is bis(2-pyridylmethyl)amine and gly-met-S,N,N is glycyl-l-methionine, was studied as a function of the entering nucleophile concentration and temperature. Reactions between the platinum(II) complexes and thiourea (TU), iodides (I^?), and nitrites(III) (NO ₂ ^? ) were carried out in aqueous solutions using conventional UV-VIS spectrophotometry. Suitable ionic conditions were reached by an addition of 0.1 M NaClO₄ and 0.01 M NaCl (to suppress hydrolysis). The second-order rate constants, k ₂, for the studied reactions with NO ₂ ^? varied between 0.036–0.038 M^?1 s^?1, and for the reactions with TU between 0.095–1.06 M^?1 s^?1, respectively. The reaction between TU and the [PtCl(bpma)]⁺ ion is ten times faster than that of the [PtCl(gly-met-S,N,N)] complex. An analysis of the activation parameters, ΔH ^≠ and ΔS ^≠, for the selected reactions clearly shows their associative nature.     

Oxygen electrodes in fused salts: Investigation and mechanistic remarks on the system (Ni)O2, H2O/OH− in the (Na,K)NO3 eutectic melt

A potentiometric investigation on the system (Ni)O₂, H₂O/OH^? was carried out within the temperature range 513?T?636 K in the (Na, K)NO₃ equimolar mixture containing OH^? ions in the concentration range 5×10^?6<[OH^?]<10^?1m and flushed with a mixture of O₂ and H₂O at variable partial pressures. The system has been found to behave reversibly in all hydroxide concentration and temperature intervals studied with respect to all the species involved in the over-all electrode reaction ½ O₂+H₂O+2e^?=2OH^? so that the following nernstian relationship could be written E=E_O2,H₂O/OH^?+RT/Fln{[O₂]^1/4[H₂O]^1/2/[OH^?]} This potentiometric behaviour was tentatively interpreted on the basis of mechanistic models involving, in some steps, solid nickel oxides formed on the electrode surface by contact with the melt. The actual formation and existence of these compounds on the electrode surface under the given experimental conditions was proved by a proper XPS investigation.     

Preparation and Characterization of GCE Coatings Combining DDDMAB and PDADMAC with FAD and HCM for Electrocatalytic Detection of Oxygen and Sulfur Oxoanions

Electrochemically active hybrid coatings based on cationic films, didodecyldimethylammonium bromide (DDDMAB), and poly(diallyldimethylammonium chloride) (PDADMAC) are prepared on glassy carbon electrode surface by cycling the film‐covered electrode repetitively in a pH 7 solution containing flavin adenine dinucleotide (FAD), and anionic hexacyanometalate (HCM) complexes, Fe(CN)₆^3? and Ru(CN)₆^4?. Cyclic voltammetric features of hybrid coatings resemble that of electron transfer process of surface‐confined redox species. Electrochemical quartz crystal microbalance (EQCM) was used to monitor the deposition of FAD on DDDMAB film. Cyclic voltammetric peak potentials of modified electrode were found to be shifted to more negative region with increasing pH of contacting solution with a slope value of 63.3mV per pH unit. The electrocatalytic behavior of FAD‐modified DDDMAB‐coated GCE and hybrid film electrodes was tested towards reduction of oxygen, S₂O₈^2?, SO₅^2? and oxidation of SO₃^2?. The application of FAD‐modified DDDMAB‐coated GCE for S₂O₈^2? estimation was demonstrated in amperometric mode. The sensitivity and detection limit (S/N=3) were 267.6 μA mM^?1 and 2×10^?6 M, respectively.     

Electrostatic effect of specifically adsorbed electroinactive ions upon electrode processes: Part V. Case of a charged adsorbed reactant. Trichloroacetate electroreduction in the presence of Br−, l−, SCN−, N3−, Ti+ and C(NH2)3+

The rate constant k_f for CCl₃COO^? electroreduction at constant applied potential, once corrected for diffuse-layer effects according to Frumkin, still depends on the charge density q_i due to specifically adsorbed supporting ions. Thus, in the presence of the adsorbed anions Br^?, I^?, SCN^? and N₃^?, the logarithm Φ of the rate constant corrected for diffuse-layer effects decreases linearly with |q_i|, albeit slightly. In the presence of the adsorbed cations Tl⁺ and C(NH₂)₃⁺, Φ increases with the positive charge density q_i due to the cation at a rate which is 3 to 8 times greater than the corresponding rate of decrease in the presence of the adsorbed anions. This behaviour has been interpreted on the basis of the theoretical treatment of ref. 22 by considering that the time of adsorption of the electroactive anion CCl₃COO^? is long enough to permit a perturbation in the distribution of the adsorbed supporting ions in the immediate vicinity of the adsorbed reactant.     

Structural,electrochemical, and adsorption studies of Ni and Zn benzylimidazole coordination polymers with terephthalate linkers

Two coordination polymers, [Ni(bim)₂(L1)(H₂O)₂] _n (CP-1) and [Zn(bim)(L1)(Cl)] _n (CP-2) (bim = 1-benzylimidazole, L1 = terephthalic acid), were synthesized and characterized by physicochemical and spectroscopic methods. The Ni(II) center in CP-1 is octahedral, while the Zn(II) center in CP-2 is tetrahedral. CP-1 and CP-2 were used to modify carbon paste electrodes to assess their effect on the electrochemical behavior of ferricyanide. The redox reactions of ferricyanide on both electrodes proved to be reversible and diffusion controlled, with ferricyanide diffusion coefficients for CP-1 and CP-2 of 1.88 × 10⁵ and 3.44 × 10⁵ cm² s^?1, respectively. These coordination polymers were also investigated for their adsorption behavior toward two dyes: Chicago sky blue and methylene blue. CP-1 and CP-2 both rapidly adsorbed the anionic Chicago sky blue dye by different intermolecular interactions; in contrast, the cationic methylene blue dye was adsorbed to a lesser extent. The adsorption of these CPs depends on the charge but not the size of the dye. Addition of methanolic potassium nitrate solution caused the release of the adsorbed dyes.     

Manganese Oxide Nanoparticles/Reduced Graphene Oxide as Novel Electrochemical Platform for Immobilization of FAD and its Application as Highly Sensitive Persulfate Sensor

In this study, manganese oxide nanoparticles/reduced graphene oxide(MnOxNPs/rGO) was used as support for strong immobilization of flavin adenine dinucleotide(FAD). A thin film of rGO cast on the electrode surface, followed by performing electrodeposition of MnOxNPs at applied constant potential of +1.4 V vs. Ag/AgCl for 200 s. Finally, FAD was electrodeposited onto the rGO/MnOxNPs film by potential cycling between 1.0 to ?1.0 V in solution containing 1 mg ml^?1 FAD. Electrochemical properties and catalytic activity of GCE/rGO‐MnOxNPs/FAD toward persulfate (S₂O₈^2?) reduction was investigated. Under optimized condition, the concentration calibration range, detection limit, and sensitivity were 0.1 μM–2 mM, 90 nM and 125.8 nA/μM, respectively, using hydrodynamic amperometry technique.     

Corrosion inhibition and adsorption behavior of imidazoline salt on N80 carbon steel in CO2-saturated solutions and its synergism with thiourea

The inhibition and adsorption behavior of 2-undecyl-1-sodium ethanoate-imidazoline salt (2M2) and thiourea (TU) on N80 mild steel in CO₂-saturated 3 wt.% NaCl solutions was studied at 25?°C, pH 4, and 1 bar CO₂ partial pressure using electrochemical methods. It was found that inhibition efficiency (η%) increased with increase in 2M2 concentration but decreased with increase in TU concentration with optimum η% value at 20 mg l^?1 TU. The data suggest that the compounds functioned via a mixed-inhibitor mechanism. The inhibition process is attributed to the formation of an adsorbed film of 2M2 and TU via the inhibitors polycentric adsorption sites on the metal surface which protects the metal against corrosion. A synergistic effect was observed between TU and 2M2. Potential of unpolarizability, E _u, was observed in the presence of 100 mg l^?1 TU which was shifted positively in the presence of 2M2–100 mg l^–1 TU blends, which suggests that the presence of 2M2 stabilized the adsorption of TU molecules on the surface of the metal. The adsorption characteristics of 2M2 were approximated by Langmuir adsorption isotherm.     

Sandwich-type amperometric immunosensor for human immunoglobulin G using antibody-adsorbed Au/SiO2 nanoparticles

A novel sandwich-type electrochemical immunosensor for human immunoglobulin G (hIgG) was developed using Au/SiO₂ nanoparticles (NPs) with adsorbed horseradish peroxidase-anti-hIgG as the secondary antibody layer. The signal readout is based on the amperometric response to the catalytic reduction of hydrogen peroxide at an AuNPs-polythionine modified glassy carbon electrode. Under optimized conditions, the linear range is from 0.1 to 200 ng·mL^?1, with a detection limit of 0.035 ng·mL^?1 (at an S/N of 3). The immunosensor exhibited a performance that is better than that based on Au/SiO₂NPs-excluded secondary antibody.     

Linear-sweep polarographic determination of active chlorine in aqueous solutions containing phenylthiourea

The linear-sweep polarographic determination of active chlorine is based on its reaction with phenylthiourea in acidic phosphate buffer (pH 2.5) containing potassium chloride. The product, C,C-diphenyldithiodiformamidine, is strongly adsorbed and then reduced at a mercury electrode with two peaks at about ?0.35 V and ?0.87 V (vs. SCE). In the presence of 0.05 M potassium chloride, the potential of the first peak shifts positively to ?0.31 V. This peak provides high sensitivity and selectivity for the determination of traces of active chlorine. The linear range is 1×10^?7?2.5×10^?5 M and the detection limit is 5×10^?8 M (3.6 μg l^?1). The method is used for the direct determination of active chlorine in tap water. The mechanism of the reaction was studied by cyclic voltammetry, electrolysis and potentiometric titration. The first peak (?0.35 V) is ascribed to the reduction of a mercury (II) sulfide film produced by reaction of the adsorbed dithio product with mercury. In the presence of 0.05 M chloride, the formation of a mixed HgS·xHg₂Cl2 film shifts the peak to ?0.31 V.     

Removal of p-aminophenol and p-nitrophenol from aqueous solution through adsorption on bismuth,lead, and manganese ferrocyanides and their relevance to environmental issues

Removal of p-aminophenol (PAP) and p-nitrophenol (PNP) from aqueous solution have been studied through adsorption on bismuth, lead and manganese ferrocyanides (125 μm British Sieve Standard mesh size) at pH range 1.0–10.0 and room temperature (27 ± 1°C). The progress of adsorption was followed spectrophotometrically by measuring the absorbance of PAP and PNP solutions at their corresponding λ_max = 220 and 330 nm, respectively. At neutral pH, PNP was found to more adsorbed than PAP on all three metal ferrocyanides studied. Manganese ferrocyanide and bismuth ferrocyanide were found to have maximum and minimum adsorption, respectively for both adsorbents. The adsorption followed the Langmuir type of adsorption in the concentration range of 10^?4 to 10^?5 mol/L of PAP and PNP solutions.     

Determination of trace amounts of nickel by differential pulse adsorptive cathodic stripping voltammetry using calconcarboxylic acid as a chelating agent

A method for the determination of nickel(II) by stripping voltammetry is described. The method is based on the adsorptive accumulation of nickel(II) calconcarboxylic acid complex onto a hanging mercury drop electrode (HMDE), followed by the reduction of the adsorbed complex using differential pulse voltammetry. The optimum operating conditions and parameters were found to be 0.05 M NH₃/NH₄Cl buffer (pH = 9.5) as the supporting electrolyte, a ligand concentration of 1 × 10^?6 M, accumulation potential of ?0.5 V (vs. Ag/AgCl) and accumulation time of 60 s. At the optimized conditions, the peak current is proportional to the concentration of nickel in the range of 1.7 × 10^?9 to 4.7 × 10^?7 M (0.1–28 ng ml^?1) with a detection limit of 0.05 ng ml^?1. The relative standard deviation (n = 10) at nickel concentrations of 2, 10 and 15 ng ml^?1 varies in the range 0.76 to 2.1%. Possible interferences by metal ions, which are of great significance in real matrices, have been studied. The method was successfully applied to the determination of nickel content in a chocolate sample.     

Flash photolysis studies of the reaction of NH2 radicals with NO

The kinetics of the reaction NH₂ + NO → N₂ + H₂O were studied, using a conventional flash photolysis system. A value of k₁ = (1.1 ± 0.2) × 10¹⁰ & mole^?1 s^?1 was obtained at room temperature and in the pressure range 2–700 torr in the presence of nitrogen. A slight negative temperature coefficient was observed between 300 and 500 K, equivalent to a negative activation energy of 1.05 ± 0.2 kcal mole^?1.     

ESR of O− and O2− stabilized on95Mo ions in a molybdenum-silica gel support system

The O^? and O₂^? anion radicals adsorbed at surface molybdenum ions were investigated by the EPR method by using the⁹⁵Mo isotope. From the valuesg_∥ = 2.006,g= 2.021,a_∥ = 7.6G anda= 8.0G for the O^? anion-radical the unpaired electron density (≈2%) was calculated. It is concluded that the unpaired electron in O^? is also delocalized onto the lattice oxygen ions.     

Cation exchange, interlayer spacing, and thermal analysis of Na/Ca-montmorillonite modified with alkaline and alkaline earth metal ions

Na-montmorillonites were exchanged with Li⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺, while Ca-montmorillonites were treated with alkaline and alkaline earth ions except for Ra²⁺ and Ca²⁺. Montmorillonites with interlayer cations Li⁺ or Na⁺ have remarkable swelling capacity and keep excellent stability. It is shown that metal ions represent different exchange ability as follows: Cs⁺?>?Rb⁺?>?K⁺?>?Na⁺?>?Li⁺ and Ba²⁺?>?Sr²⁺?>?Ca²⁺?>?Mg²⁺. The cation exchange capacity with single ion exchange capacity illustrates that Mg²⁺ and Ca²⁺ do not only take part in cation exchange but also produce physical adsorption on the montmorillonite. Although interlayer spacing d ₀₀₁ depends on both radius and hydration radius of interlayer cations, the latter one plays a decisive role in changing d ₀₀₁ value. Three stages of temperature intervals of dehydration are observed from the TG/DSC curves: the release of surface water adsorbed (36?C84?°C), the dehydration of interlayer water and the chemical-adsorption water (47?C189?°C) and dehydration of bound water of interlayer metal cation (108?C268?°C). Data show that the quantity and hydration energy of ions adsorbed on montmorillonite influence the water content in montmorillonite. Mg²⁺-modified Na-montmorillonite which absorbs the most quantity of ions with the highest hydration energy has the maximum water content up to 8.84%.     

Prediction of semiconducting SiP_2 monolayer with negative Possion's ratio,ultrahigh carrier mobility and CO_2 capture ability

Using particle swarm optimization(PSO) methodology for crystal structure prediction,we predicted a novel two-dimensional(2 D) monolayer of silicide diphosphorus compound:SiP_2,which exhibits good stability as examined via cohesive energy,mechanical criteria,molecular dynamics simulation and all positive phonon spectrum,respectively.The SiP_2 monolayer is an indirect semiconductor with the band gap as 1.8484 eV(PBE) or 2.681 eV(HSE06),which makes it more advantageous for high-frequencyresponse optoelectronic materials.Moreover,the monolayer is a relatively hard auxetic material with negative Possion's ratios,and also possesses a ultrahigh carrier mobility(1.069 × 10~5 cm~2 V~1 s~1) which is approximately four times the maximum value in phosphorene and comparable to the value of graphene and CP monolayers.Furthermore,the effects of strains on band structures and optical properties of SiP2 monolayer have been studied,as well as CO_2 molecules can be strongly chemically adsorbed on the SiP_2 monolayer.A semiconductor-to-metal transition for-9.5% strain ratio case and a huge optical absorption capacity on the order of 106 cm ~1 in visible region present.These theoretical findings endow SiP2 Monolayer to be a novel 2 D material holding great promises for applications in highperformance electronics,optoelectronics,mechanics and CO_2 capturing material.     

Cetyltrimethylammonium-coated magnetic nanoparticles for the extraction of bromate,followed by its spectrophotometric determination

We report on a combination of magnetic solid-phase extraction and spectrophotometric determination of bromate. Cetyltrimethylammonium ion was adsorbed on the surface of phenyl-functionalized silica-coated Fe₃O₄ nanoparticles (Ph-SiO₂@Fe₃O₄), and these materials served as the sorbent. The effects of surfactant and amount of sorbent, the composition of the desorption solution, the extraction time and temperature were optimized. Under optimized conditions, an enrichment factor of 12 was achieved, and the relative standard deviation is 2.9 % (for n?=?5). The calibration plot covers the 1–50 ng mL^?1 range with reasonable linearity (r ²?>?0.998); and the limit of detection is 0.5 ng mL^?1. The method is not interfered by ionic compounds commonly found in environmental water samples. It was successfully applied to the determination of bromate in spiked water samples.

The production of H(2S) atoms in the energy-transfer reaction of O2(1Δg) with HO2(X̃2A″)

The reaction of O₂(¹Δg) with HO₂(X?) was studied in an isothermal flow reactor in the pressure range 7?p? 10.7 mbar at temperatures between 299?T? 423 K. H-atom production was observed in the reaction O₂(¹Δg) + HO₂(òA′) - H(²S)+ 2O₂ (³Σ_g^?). The rate of this reaction (k₁) is estimated to be k₁ = (1 ± 0.5) × 10¹⁴ CM³ Mol^?1 s^?1. The implications of this reaction to recent determinations of the rate of the reaction H + O₂(¹Δg) are discussed.