Electrochemical characterization of natural gold samples using the voltammetry of immobilized particles
The application of the voltammetry of immobilized particles for characterizing natural gold samples from different geological settings and dating vein deposits is described. This is based on recording characteristic electrochemical oxidation signatures of gold and silver following the attachment of metal sub-microsamples to graphite electrodes. Keywords: Electrochemistry, Gold, Mineralogy, Placer deposits, Vein deposits, Nuggets
Electrochemical monitoring of ROS influence on seedlings and germination response to salinity stress of three species of the tribe Inuleae.
Solid-state electrochemical methods have been applied to the establishment of patterns of plant growth and response to saline stress using seedlings of Inula helenium L., Dittrichia viscosa (L.) Greuter (Inula viscosa (L.) Aiton), Limbarda crithmoides (L.) Dumort (Inula crithmoides L.). Upon in situ electrochemical generation of reactive oxygen species (ROS) the reactivity with such species was monitored using voltammetric signals associated to the oxidation of polyphenolic components of the plants. A simple kinetic model based on second-order reaction between ROS and polyphenolic components is applied to electrochemical data yielding apparent rate constants which can be correlated with the…
Crystal structure and microstructure of synthetic hexagonal magnesium–cobalt cordierite solid solutions (Mg2−2xCo2xAl4Si5O18)
Co2+-containing cordierite glasses, of nominal compositions (Mg1−xCox)2Al4Si5O18(withx= 0, 0.2, 0.4, 0.6, 0.8 and 1), were prepared by melting colloidal gel precursors. After isothermal heating at 1273 K for around 28 h, a single-phase α-cordierite (high-temperature hexagonal polymorph) was synthesized. All materials were investigated using X-ray powder diffraction and field-emission scanning electron microscopy. The crystal structure and microstructure were determined from X-ray diffraction patterns. Rietveld refinement confirmed the formation of magnesium–cobalt cordierite solid solutions. The unit-cell volume increased with the increase of cobalt content in the starting glass. The crysta…
Preparation of Hg2+ selective fluorescent chemosensors based on surface modified core–shell aluminosilicate nanoparticles
A synthetic procedure for the preparation of functional structured inorganic–organic hybrid materials consisting of boehmite-silica core–shell nanoparticles and anthracene-containing amines covalently attached to the nanoparticles surface is reported. The system functionalised with the monoamine chain shows a very high sensing performance for Hg2+ detection in pure water reaching a detection limit of 0.2 ppb. Two additional advantages of these systems are their stability over a wide pH window and the feasibility to be recovered by a simple procedure.
Solid state electrochemical behavior of organosulfur compounds
Abstract The solid-sate electrochemistry of organosulfur compounds existing in petroleum and its derived matrices is described using the voltammetry of immobilized microparticles methodology. Cyclic and square wave voltammogrammetric responses of sulfur compounds responsible of aging of asphalt pavements, namely, thiophenes, disulfides, sulfides, sulfoxides and sulfones were determined at compound-modified graphite electrodes in contact with 0.10 M H2SO4. The electrochemical oxidation/reduction products were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy with energy dispersion x-ray detection (SEM-EDX) couple…
Cover Picture: Electrochemical Characterization of Coinage Techniques the 17th Century: The maravedís Case (Electroanalysis 9/2017)
Application of solid-state electrochemistry techniques to polyfunctional organic–inorganic hybrid materials: The Maya Blue problem
Abstract The time evolution of indigo plus palygorskite powdered mixtures during isothermal heating at different temperatures between 120 and 180 °C to form Maya Blue-type materials has been monitored by means of infrared spectrometry, diffuse reflectance spectrometry in the visible region and solid state electrochemical techniques. The kinetics of the formation process of such materials can be described in terms of two consecutive reactions, the first one consisting of the loss of zeolitic water of the palygorskite coupled with clay-indigo attachment and partial indigo to denydroindigo oxidation. The palygorskite dehydration acts as a rate-determining step fitting to a 3D Avrami-Erofe’ev k…
Synthesis and characterization of praseodymium-containing ZrSiO4 solid solutions from gels
Abstract The preparation and characterization of a series of praseodymium–zircon solid solution (Prx–ZrSiO4) materials with increasing nominal amounts of Pr is reported. Pr-doped zircon gels were prepared by gelling mixtures of zirconium n-propoxide, praseodymium acetylacetonate and tetraethylorthosilicate, and annealed over the range of temperature up to the formation of Pr–zircon solid solutions. The reaction sequence was followed by X-ray powder diffraction (XRD), ultraviolet–visible diffuse reflectance (DR) and infrared spectroscopy (IR). The first crystalline phase detected on annealing gels was a tetragonal praseodymium-containing ZrO2 phase (t-Pr–ZrO2). On further annealing, the subs…
Estimation of individual Gibbs energies of cation transfer employing the insertion electrochemistry of solid Prussian blue
Abstract A novel method to determine the Gibbs energy of cation transfer between two miscible solvents is described. This method uses electrochemical data for the reversible cation-assisted solid-state reduction of Prussian blue using ferrocene as internal potential standard. Voltammetric data can be used for a direct measurement of the Gibbs energy of ion transfer from one solvent to another using midpeak potentials in solutions of suitable salts in each one of the solvents separately or mixtures of the solvents. Excess Gibbs energies of solvation in solvent mixtures can also be directly estimated. Gibbs energies of cation transfer of Li+, Na+ and K+ ions from water to MeOH, MeCN and DMSO …
Bisferrocenyl-functionalized pseudopeptides: access to separated ionic and electronic contributions for electrochemical anion sensing
Pseudopeptidic receptors containing ferrocene fragments have been prepared and their response to a series of anions was measured by a voltammetry of microparticles methodology. Such water-insoluble compounds yield anion-assisted reversible solid-state oxidations differing in their open-circuit potential and their midpeak potential recorded in cyclic voltammetric measurements. The difference between those potentials provides the individual thermodynamic contributions of electron and proton transfer, revealing that the mechanism of an ion-sensitive electrode can differ in potentiometry and voltammetry. The studied receptors are potentially interesting for potentiometric sensing, showing relat…
Electrochemical characterization of praseodymia doped zircon. Catalytic effect on the electrochemical reduction of molecular oxygen in polar organic solvents
The voltammetry of microparticles and scanning electrochemical microscopy methodologies are applied to characterize praseodymium centers in praseodymia-doped zircon (PrxZr(1−y)Si(1−z)O4; y + z = x; 0.02 < x < 0.10) specimens prepared via sol–gel synthetic routes. In contact with aqueous electrolytes, two overlapping Pr-centered cathodic processes, attributable to the Pr (IV) to Pr (III) reduction of Pr centers in different sites are obtained. In water-containing, air-saturated acetone and DMSO solutions as solvent, PrxZr(1−y)Si(1−z)O4 materials produce a significant catalytic effect on the electrochemical reduction of peroxide radical anion electrochemically generated. These electrochemical…
Electrochemically assisted anion insertion in Au(I)–Cu(I) heterotrimetallic clusters bearing ferrocenyl groups: Application to the fluoride/chloride discrimination in aqueous media
The heterotrimetallic Au(I)–Cu(I) aggregate [{Au3Cu2(C2C6H4Fc)6}Au3(PPh2C6H4PPh2)3](PF6)2 exhibits a well-defined solid state electrochemistry in contact with aqueous media, based on ferrocenyl-centred oxidation processes involving anion insertion. Upon attachment of microparticulate deposits of the cluster to graphite electrodes, distinctive electrochemical responses can be obtained for fluoride and chloride ions in aqueous media. Keywords: Heterometallic clusters, Gold, Copper, Fluoride/chloride discrimination, Electrochemical anion insertion
Dating archaeological strata in the Magna Mater temple using solid-state voltammetric analysis of leaded bronze coins
[EN] The application of solid state electrochemistry techniques for dating archaeological strata using lead-containing bronze coins is described. The proposed methodology was applied to samples coming from the Roman archaeological site of Magna Mater Temple (Rome, Italy) occurring in different strata dating back between the second half and the end of the 4(th) century A.D. and the 20(th) century. The voltammetric signatures of copper and lead corrosion products in contact with aqueous acetate buffer, as well as the catalytic effects produced on the hydrogen evolution reaction, were used for establishing the age of different strata and dating coins belonging to unknown age. Voltammetric data…
Determination of Individual Gibbs Energies of Anion Transfer and Excess Gibbs Energies Using an Electrochemical Method Based on Insertion Electrochemistry of Solid Compounds
A method is presented to determine, individually and with minimal extra-thermodynamic assumptions, the Gibbs energy for anion transfer between two solvents using solid state electrochemistry of alkynyldiphosphine dinuclear Au(I) complexes (AuC2R)2PPh2C6H4PPh2 (L1, R = Fc; L2, R = C6H4Fc) and the heterometallic Au(I)–Cu(I) [{Au3Cu2(C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (L3, R = Fc; L4, R = C6H4Fc) cluster complexes containing ferrocenyl units. These compounds exhibit a well-defined, essentially reversible solid-state oxidation in contact with different electrolytes, based on ferrocenyl-centered oxidation processes involving anion insertion. Voltammetric data can be used for a direct measurement of…
Synthesis, Characterization of FexZr1-xO2Solid Solution Nanoparticles and Bulk Powders Prepared Using a Sol-Gel Technique
Composition and Color of Maya Blue: Reexamination of Literature Data Based On the Dehydroindigo Model
[EN] An analysis of literature data studying the composition and color of Maya blue (MB) type materials prepared from indigo, dehydroindigo, and different aluminosilicates, accompanied by new spectral data, is presented. After thermal treatment at above 100 degrees C, indigo-based specimens displayed Raman and UV-vis spectroscopic features common to those of equivalent dehydroindigo-based replicants, thus supporting the socalled dehydroindigo model (J. Phys. Chem. B 2006, 110, 6027-6039) in which the dehydroindigo/indigo ratio, increasing with temperature, is crucial to determine the color of MB and its variability. The current analysis supports the view of MB as a polyfunctional hybrid mat…
Electrochemical discrimination of manufacturing types of pottery from Magna Mater Temple and Fora of Nerva and Caesar (Rome, Italy)
Abstract The voltammetry of immobilized microparticles (VIMP) methodology is applied to a series of pottery samples from the Roman sites of Nerva's Forum (second half of 9th-early 11th A.D), Caesar's Forum (second half of 9th-early 11th A.D) and Magna Mater Temple (III century). The VIMP sampling applied to voltammetric and electrochemical impedance spectroscopy (EIS) measurements was applied by the first time to acquire archaeometric information on archaeological pottery. VIMP measurements using pressed sample pellets on gold electrodes in contact with air-saturated 0.10 M H2SO4 have permitted to detect voltammetric signals for the reduction/oxidation of Fe and Mn minerals as well as catal…
Effect of TiO2 on the mullite formation and mechanical properties of alumina porcelain
Abstract The effect of adding TiO 2 to standard alumina porcelain on its microstructure and flexural strength was investigated. A series of alumina porcelain bodies containing increasing amounts of TiO 2 were prepared by extruding mixtures of raw materials and TiO 2 . Porcelain rods were fired under industrial scheduling in a manufacturing kiln. The overall degree of crystalline and amorphous phase content within the porcelain bodies was quantitatively determined using a Rietveld analysis. Results indicated a higher amount of mullite formation in porcelain bodies containing TiO 2 . Examination of the product materials using field emission scanning electron microscopy showed a high density o…
Study of solid state kinetics using voltammetry of immobilized particles. Application to tetragonal to monoclinic transition in nanoparticulate zirconia and praseodymia-doped zirconia
Abstract The voltammetry of immobilized particles methodology is applied to study solid state reaction kinetics on the basis of the electrocatalytic ability of solids toward selected electrochemical processes. Measurement of the time variation of catalytic current for oxygen evolution reaction in aqueous alkaline media provides a direct estimate of fractional conversion of the reactant in the course of the reaction for testing different reaction kinetic models. This methodology is applied to analyze the formation of monoclinic zirconia and praseodymia-doped zirconia from tetragonal precursors. Discrimination between competing and successive reactions mechanisms is obtained for reactions inv…
Electrochemical dating of archaeological gold based on refined peak current determinations and Tafel analysis
Abstract This report proposes a refined method to date archaeological gold samples based on the Tafel analysis of the ascending part of voltammetric curves corresponding to the oxidation of surface flakes of gold in contact with hydrochloric acid aqueous electrolyte. This allows estimating the equilibrium potential of gold oxidation correcting for irreversibility effects. This equilibrium potential can be correlated with the coverage of adsorbed oxygen species and hence the estimated age of the gold samples. A satisfactory potential/time calibration graph was constructed from a set of archaeological samples including two sets of samples from the Mapungubwe Gold Collection, South Africa (120…
FIB-FESEM and EMPA results on Antoninianus silver coins for manufacturing and corrosion processes
[EN] A set of ancient Antoninianus silver coins, dating back between 249 and 274¿A.D. and minted in Rome, Galliae, Orient and Ticinum, have been characterized. We use, for the first time, a combination of nano-invasive (focused ion beam-field emission scanning electron microscopy-X-ray microanalysis (FIB-FESEM-EDX), voltammetry of microparticles (VIMP)) and destructive techniques (scanning electron microscopy (SEM-EDX) and electron microprobe analysis (EMPA)) along with non-invasive, i.e., micro-Raman spectroscopy. The results revealed that, contrary to the extended belief, a complex Ag-Cu-Pb-Sn alloy was used. The use of alloys was common in the flourishing years of the Roman Empire. In th…
Evaluation of aging processes of petroleum asphalt cements by solid state electrochemical monitoring
Abstract The changes in the chemistry of organosulfur compounds from asphalt cements during aging are studied using solid state voltammetry of immobilized microparticles. Five Brazilian asphalt cements were evaluated after three forced aging processes: Rolling Thin Film Oven Test (RTFOT), Pressure Aging Vessel (PAV) and SUNTEST. It was possible to identify the presence of thiophenes, sulfides and sulfoxides in the different samples and the reactional changes during the aging processes were proposed. Voltammetric data, supported by ATR-FTIR spectroscopy, indicate that aging asphalts involve the increase of the proportion of sulfoxide and thiophene components and that polythiophene compounds …
Solvent-Independent Electrode Potentials of Solids Undergoing Insertion Electrochemical Reactions: Part III. Experimental Data for Prussian Blue Undergoing Electron Exchange Coupled to Cation Exchange
Prussian blue-modified electrodes immersed in K+-containing solutions can be used to obtain a solvent-independent redox potential system. On the basis of theoretical modeling of diffusion processes occurring under the conditions of voltammetry of immobilized particles, voltammetric and chronoamperometric data can be combined to obtain solvent-independent electrode potentials for the K+-assisted one-electron reduction of Prussian blue to Berlin white. Data for water, MeOH, EtOH, MeCN, DMS, DMF, and NM are provided.
Synthesis and Characterization of Iron-Doped ZrSiO4 Solid Solutions from Gels
The mechanism of formation and the structural features of tetragonal Fe–ZrO2-amorphous silica composites and particulated Fe-doped ZrSiO4 solid solutions were studied. A series of specimens with compositions Fex–ZrSiO4, 0 ≤ x ≤ 0.10 were prepared by sol–gel techniques and thermally annealed over the range of temperature between 400°C and 1600°C. Results confirmed the formation of tetragonal Fe–ZrO2 solid solution as first crystalline phase on the whole process leading to Fe-doped ZrSiO4 solid solution. The annealing temperature for the preparation of Fe-containing ZrSiO4 solid solutions was dependent on the nominal amount of iron. The Fex–ZrSiO4 solid solutions, with 0.02 < x < 0.08, were a…
Identification of vegetal species in wooden objects using in situ microextraction-assisted voltammetry of microparticles
[EN] A method for identifying vegetal species in wooden objects using microextraction-assisted voltammetry of microparticles is described. The proposed methodology, aimed at facilitating tasks of patrimony conservation, is based on the recording of the voltammetric response of microparticulate films of compounds resulting from microextraction with organic solvents (ethanol, acetone, and chloroform) of micro- or sub-microsamples of wood in contact with aqueous buffers. Upon application of bivariate and multivariate chemometric techniques, the obtained voltammetric responses led us to identify different taxonomic groups from the characteristic voltammetric profiles. Application to a series of…
Electrochemical Characterization of Coinage Techniques the 17(th) Century: The maravedis Case
[EN] The voltammetry of immobilized particles (VIMP) methodology was applied to the discrimination of Spanish maravedis produced in 10 different mints between 1661 and 1664 using characteristic signatures for the reduction of cuprite and tenorite in the patina of the coins and catalytic effects on the hydrogen evolution reaction (HER). The variation of the apparent tenorite/cuprite ratio with depth was fitted to potential laws differing from one mint to another for A Coruna, Burgos, Cordoba, Cuenca, Granada, Madrid, Trujillo, Segovia, Sevilla and Valladolid coins. Electrochemical data permitted to detect the changes in the composition (with lowering of the silver content) and manufacturing …
Tuning the size and shape of nano-boehmites by a free-additive hydrothermal method
A synthetic procedure allowing the control of boehmite micro and nanoparticles is presented. The proposed hydrothermal synthetic procedure is based on the control of three reaction parameters, the pH and temperature of precipitation of xerogels and the water/xerogel ratio for the hydrothermal process, carried out at 200 °C for 48 h. Results obtained by measurements on transmission electron microscopy (TEM) images indicate that at pH 5 micro or nanorods of controlled length between ca. 300 and 50 nm were obtained depending on the temperature of precipitation of the xerogel (25 or 100 °C) and the water/xerogel ratio used (1/1, 6/1, 15/1). On the contrary, at pH 10, nanoplatelets with major ba…
ATR-FTIR and XRD quantification of solid mixtures using the asymptotic constant ratio (ACR) methods. Application to geological samples of sodium and potassium feldspars
Two asymptotic constant ratio methods applied to the quantification of individual components of solid samples using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray diffraction (XRD) are described. The methods involve the measurement of the peak current/peak areas of selected signals (diffraction peaks in XRD and absorption bands in ATR-FTIR) relative to the signal of standard added in constant proportion to the sample and the sample enriched with the analyte following the usual standard additions methodology. The proposed method compensates the absorption effects appearing in XRD and the presence of overlapping absorption bands of interferents by me…
Dating of Archaeological Gold by Means of Solid State Electrochemistry
[EN] In archaeology and history of art, age determination is a fundamental analytical problem. While several techniques for age determination of various materials, like radiocarbon dating, are established, these methods cannot be applied for metals, for which new techniques have to be developed. For the first time a dating method for archaeological gold objects is described which is based on a corrosion clock and electrochemical measurements, using the voltammetry of immobilized particles. Samples are prepared by one touch' with a graphite pencil, only transferring a few nanograms of the archaeological gold. The method has been calibrated with the help of a series of well-documented gold sp…
An electrochemical analysis suggests role of gynodioecy in adaptation to stress in Cortaderia selloana
Cortaderia selloana is an invasive, gynodioecious species prevalent in Mediterranean area which contains both female and hermaphrodite specimens in the wild population. Using voltammetric data we show that the female and hermaphrodite specimens exhibit differential electrochemical response. Cortaderia selloana leaves from two different provenances in the Valencia Mediterranean area, Sueca and Cullera (Comunitat Valenciana, Spain), in the surroundings of the Albufera Natural Park, a peculiar ecosystem containing unspoilt dune beaches and forests, were studied to determine correlation of flower morphology with the plant's ability to adapt to stress conditions. Our data suggests that gynodioec…
Microstructure of Fe–ZrSiO4 solid solutions prepared from gels
Abstract Microstructural changes associated with chemical and structural evolution from gels to Fe x –ZrSiO 4 solid solutions are reported. Mineralizer-free Fe x –ZrSiO 4 gels in the compositional range 0 ≤ x ≤ 0.15 were prepared by sol–gel liquid-phase route from mixtures of alkoxides of silicon and zirconium, and iron (III) acetylacetonate, and annealed at different temperatures and/or times. The first step on the whole process to the final Fe x –ZrSiO 4 solid solutions was the formation of aggregated of tetragonal Fe-doped ZrO 2 nanocrystals with diameters smaller than 50 nm. At this stage the tetragonal Fe–ZrO 2 were embedded in amorphous silica resulting nanocomposite materials. The …
Electrochemistry of Iron-Doped Zircon and Zirconia Materials and Electrocatalytic Effects on Nitrite Oxidation and Reduction
Microstructural Evolution from Praseodymium-Containing Zircon Gels to Prx-ZrSiO4 Solid Solutions
Structural evolution and coupled microstructural transformations occurred on annealing mineralizer-free Pr-containing ZrSiO4 gels up to final praseodymium-doped zircon yellow pigments are reported. Gels with nominal compositions Prx-ZrSiO4, 0 ≤ x ≤ 0.125, were prepared from mixtures of zirconium and silicon alkoxides and praseodymium acetylacetonate. Crystallization pathway and microstructural changes of thermally treated dried gels were followed by infrared spectroscopy, X-ray diffraction, field emission scanning and transmission electron microscopies, respectively. Results indicated that the crystallization pathway through the whole process of final Prx-ZrSiO4 solid solutions formation di…
Corrigendum to “ATR-FTIR and XRD quantification of solid mixtures using the asymptotic constant ratio (ACR) methods. Application to geological samples of sodium and potassium feldspars” [Spectrochim. Acta A 236 (2020) 118328]
Polythiophenes as markers of asphalt and archaeological tar pitch aging. Characterization using solid-state electrochemistry
The voltammetry of immobilized microparticles (VIMP) was used to characterize organosulfur components from ovens found at the Spanish archaeological sites of Cueva de Nerja (ca. 35,000cal BC), la Illeta dels Banyets (4th century BCE) and Gestalgar (12th–13th CE), and asphalt probes subjected to PAV and SUNTEST aging protocols. The voltammetric responses of the archaeological samples and the asphalt probes after photodegradation were quite similar, indicating the presence of polythiophene components which could act as age/degradation markers. Keywords: Voltammetry, Archaeology, Asphalt, Tar pitch, Organosulfur compounds
Raman spectroscopy characterization of 10-cash productions from the late Chinese emperors to the Republic
[EN] The use of Raman spectroscopy for discriminating monetary emissions, a recurrent problem in much archaeological studies, is described. The method involves the record of Raman signatures of tenorite and crystalline and defective cuprite in the patina based on the idea that subtle, mint-characteristic variations in the composition and metallography of the base metal during the manufacturing process are reflected in the variation in depth of the composition and crystallinity of the corrosion patina. The technique was applied to a series of 10-cash copper coins produced around the transition between the Kuang Hsu and Hsuan Tung last Chinese emperors and the first Republic whose averaged co…
Archaeometric analysis of Roman bronze coins from the Magna Mater temple using solid-state voltammetry and electrochemical impedance spectroscopy
Voltammetry of microparticles (VMP) and electrochemical impedance spectroscopy (EIS) techniques, complemented by SEM-EDX and Raman spectroscopy, were applied to a set of 15 Roman bronze coins and one Tessera from the temple of Magna Mater (Rome, Italy). The archaeological site, dated back between the second half and the end of the 4th century A.D., presented a complicated stratigraphic context. Characteristic voltammetric patterns for cuprite and tenorite for sub-microsamples of the corrosion layers of the coins deposited onto graphite electrodes in contact with 0.10 M HClO4 aqueous solution yielded a grouping of the coins into three main groups. This grouping was confirmed and refined usin…
Selective electrochemical discrimination between dopamine and phenethylamine-derived psychotropic drugs using electrodes modified with an acyclic receptor containing two terminal 3-alkoxy-5-nitroindazole rings.
Electrochemical discrimination between dopamine and psychotropic drugs which have in common a skeletal structure of phenethylamine, can be obtained using acyclic receptors L(1) and L(2), containing two terminal 3-alkoxy-5-nitroindazole rings. Upon attachment to graphite electrodes, L(1) and L(2) exhibit a well-defined, essentially reversible solid state electrochemistry in contact with aqueous media, based on electrolyte-assisted reduction processes involving successive cation and anion insertion/binding. As a result, a distinctive, essentially Nernstian electrochemical response is obtained for phenethylammonium ions of methamphetamine (METH), p-methoxyamphetamine (PMA), amphetamine (AMPH),…
Electrochemical identification of toxigenic fungal species using solid-state voltammetry strategies.
An electrochemical methodology for the characterization of mycotoxin-producing fungal species from the genera Aspergillus and Fusarium using solid-state voltammetry is described. Upon attachment of fungal colony microsamples to glassy carbon electrodes in contact with aqueous acetate buffer, characteristic voltammetric signals mainly associated to the oxidation of polyphenolic metabolites are recorded. The possibility of fungi-localized electrochemical processes was assessed by means of electron microscopy and field emission scanning electrochemical microscopy coupled to the application of oxidative potential inputs. Using pattern recognition methods, the determined voltammetric profiles we…
Estimation of free energies of anion transfer from solid-state electrochemistry of alkynyl-based Au(I) dinuclear and Au(I)–Cu(I) cluster complexes containing ferrocenyl groups
A method is presented to determine the free energy for anion transfer between two solvents. This is based on solid-state electrochemistry of alkynyl-based dinuclear Au(I) complexes (AuC2R)2PPh2C6H4PPh2 (L1: R=Fc; L2: R=C6H4Fc) and heterometallic Au(I)–Cu(I) [{Au3Cu2 (C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (L3: R=Fc; L4: R=C6H4Fc) complexes. These compounds exhibit a reversible ferrocenyl-centred solid-state oxidation processes involving anion insertion in contact with aqueous, MeOH and MeCN electrolytes. Voltammetric data can be used for a direct measurement of the free energy of ion transfer using midpeak potentials in solutions of suitable salts in the solvents separately or in mixtures of the s…
Electrochemical characterization of mangrove sediments: A proposal of new proxies for organic matter oxidation
Abstract The voltammetric response of microparticulate deposits resulting from solvent evaporation of ethanolic extracts of mangrove sediments in contact with aqueous acetate buffer is hereby described. Dated sediment cores sampled from the Peruvian mangrove system (“Manglares de Tumbes” National Sanctuary) presented voltammetric responses dominated by oxidative signals of organic components that exhibit significant variations depending on the depth. Voltammetric data allowed for the definition of electrochemical indexes representative of the electrochemically oxidable organic matter fraction. These electrochemical indexes were fEAOM (for the total amount of organic matter being electrochem…