Síntesis y caracterización de polímeros electroactivos en sistemas multicapas.

RESUMEN Esta memoria desarrolla un estudio sobre macromoléculas electrogeneradas y depositadas sobre electrodos, cuya utilidad científica y tecnológica está en continuo desarrollo, y se encuentra enmarcada una de las líneas de investigación desarrollada desde hace tiempo en el Laboratorio de Electroquímica del Departamento de Química-Física de la Universitat de València, Este trabajo se ha focalizado en el estudio de las propiedades electroactivas del poli-(Azure A) mediante técnicas combinadas espectroelectroquímicas y electrogravimétricas en medio ácido, así como en el desarrollo de modelos de análisis de los resultados obtenidos con los que se ha conseguido conocer la naturaleza de las distintas reacciones que tienen lugar durante los procesos redox de este polímero. Con estas herramientas se abre el camino para profundizar en el conocimiento, ayudar en la mejora de las prestaciones e incrementar las utilidades de estas sustancias electroactivas, así como para otro tipo de polímeros conductores. Estas técnicas han permitido plantear un modelo de reacción para el poli-(Azure A) principalmente, pero las evidencias mostradas para otro polímero similar, el poli-(Azul de Metileno), podría hacer extensible este modelo propuestos a toda la familia de poli-(fenotiacinas) con ligeras variaciones debido al amplio abanico de estructuras moleculares que poseen este tipo de sustancias. En este modelo se tiene en cuenta la formación de un enlace intermonomérico durante la electrogeneración del poli-(Azure A) similar al formado durante la síntesis electroquímica de la poli-(Anilina) y por lo tanto, electroactivo, además del tradicional centro electroactivo situado en el heterociclo del monómero precursor (Azure A). Durante la transferencia electrónica entre estos centros electroactivos y el electrodo se produce un transporte de iones entre el polímero y la solución, en este caso un medio ácido. Como resultado, después de diferentes ensayos, se establece que cada uno de estos centros electroactivos intercambia con el medio un protón (considerada una especie iónica de transporte lento) y un anión (especie iónica de transporte rápido) durante la transferencia de dos electrones entre éstos y el electrodo. __________________________________________________________________________________________________This work is focused on the electrogenerated macromolecules (poly-(phenotiazines)) deposited on electrode surface. These macromolecules have been the object of much effort of the researchers owing to the chemical and biological importance. The good long-term stability and electroactivity achieved in these modified electrodes has allowed an attractive and wide development as biosensor and, recently, in pioneering biofuel cells-based devices. The poly-(Azure A) and poly-(Methylene Blue) has been studied by means of electrogravimetric, spectroscopic and electrochemical techniques in acid media. The obtained results together with the development of the new analysis of these results have allowed to find out the electrochemical mechanism of this interesting kind of molecules. The results showed that the doping/undoping processes during the overall redox of this kind of polymers takes places by the exchange of two charge carriers, one faster and another slower. The faster ionic exchange takes place with the participation of anion species acting as counter-ions whereas the slower one seems to be related with protons which could be implied as reactants. By means spectroscopic techniques, a new electroactive moiety has been localized in the new inter-phenotiazine amino link of these polymers formed during the electrogeneration. The spectromagnetic properties of this link are analogous to those of the emeraldine form of poly-(Aniline)

Electrochemical performance of activated screen printed carbon electrodes for hydrogen peroxide and phenol derivatives sensing

Screen-printed carbon electrodes (SPCEs) are widely used for the electroanalysis of a plethora of organic and inorganic compounds. These devices offer unique properties to address electroanalytical chemistry challenges and can successfully compete in numerous aspects with conventional carbon-based electrodes. However, heterogeneous kinetics on SPCEs surfaces is comparatively sluggish, which is why the electrochemical activation of inks is sometimes required to improve electron transfer rates and to enhance sensing performance. In this work, SPCEs were subjected to different electrochemical activation methods and the response to H2O2 electroanalysis was used as a testing probe. Changes in topology, surface chemistry and electrochemical behavior to H2O2 oxidation were performed by SEM, XPS, cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The combination of electrochemical activation methods using H2SO4 and H2O2 proved particularly effective. A reduction in charge transfer resistance, together with functionalization with some carbon‑oxygen groups on carbon ink surfaces, were likely responsible for such electrochemical improvement. The use of a two-step protocol with 0.5 M H2SO4 and 10 mM H2O2 under potential cycling conditions was the most effective activation procedure investigated herein, and gave rise to 518-fold higher sensitivity than that obtained for the untreated SPCEs upon H2O2 electrooxidation. The electrochemical behavior of acetaminophen, hydroquinone and dopamine is also shown, as a proof of concept upon the optimum activated SPCEs.This work was funded by the Spanish Ministry of Economy and Competitiveness (MINECO, http://www.mineco.gob.es/portal/site/mineco/idi), Projects No. BFU2016-75609-P (AEI/FEDER, UE) and CTQ2016-76231-C2-2-R, and by the Junta de Comunidades de Castilla-La Mancha (Spain), Project No. SBPLY/17/180501/000276/2 (cofunded with FEDER funds, EU). BGM is a post-doctoral research fellow of the Youth Employment Initiative (JCCM, Spain, cofunded with ESF funds, EU)

Identification of electroactive sites in Prussian Yellow films

Prussian Blue films were electrogenerated on the surface of the transparent ITO electrodes. The electrochemical oxidation to the Prussian Yellow form was investigated by means of in situ voltammetry and vis–NIR spectroscopic techniques. Changes of the whole spectra between 400 and 950 nm were analyzed and three characteristic wavelengths were selected to in situ follow the electrochemical changes of the films. Voltammetric peaks and absorbance derivative curves at these three wavelengths were deconvoluted and were interpreted such as the overlapping of different electrochemical processes. The correlation between these overlapped processes has allowed proposing three different electrochemical processes for the interpretation of the whole electrochemical response. One of these processes corresponds to the oxidation of View the MathML source units where the electrical charge is balanced by the exchange of neighbor potassium cations. The second one is associated to the oxidation of View the MathML source trapped sites and the third one also to the oxidation of View the MathML source units but in this last case, the absence of neighbor potassium cations causes that the electrical charge balance takes place by the exchange of some anions such as the chloride. These processes have been identified on the basis of previous results and on the interesting information provided by the coupling voltammetry and absorbance derivative curves at these characteristic wavelengths

Highly activated screen-printed carbon electrodes by electrochemical treatment with hydrogen peroxide

An easy effective method for the activation of commercial screen-printed carbon electrodes (SPCEs) using H2O2 is presented to enhance sensing performances of carbon ink. Electrochemical activation consists of 25 repetitive voltammetric cycles at 10 mV s−1 using 10 mM H2O2 in phosphate buffer (pH 7). This treatment allowed us to reach a sensitivity of 0.24 ± 0.01 μA μM−1 cm−2 for the electroanalysis of H2O2, which is 140-fold higher than that of untreated SPCEs and 6-fold more than screen-printed platinum electrodes (SPPtEs). Electrode surface properties were characterized by SEM, EIS and XPS. The results revealed atomic level changes at the electrode surface, with the introduction of new carbon‑oxygen groups being responsible for improved electro-transfer properties and sensitivity. Our method was compared with other previously described ones. The methodology is promising for the activation of commercial carbon inks-based electrodes for sensor applications.This work was funded by the Spanish Ministry of Economy and Competitiveness (MINECO, http://www.mineco.gob.es/portal/site/mineco/idi), Projects No. BFU2016-75609-P (cofunded with FEDER funds, EU) and CTQ2016-76231-C2-2-R. BGM is a post-doctoral research fellow of the Youth Employment Initiative (JCCM, Spain, cofounded with ESF funds, EU)

One-pot electrodeposition of multilayered 3D PtNi/polymer nanocomposite. H2O2 determination in aerosol phase

In this work, 3D-structured nanocomposites were synthesized in one pot by electrochemical deposition of alternating layers of an azo type polymer (polyazure-A) with platinum and nickel nanoparticles. The hybrid PtNi/poly(AzA) film was electrochemically deposited on screen-printed carbon electrodes by layer-by-layer assembly as a function of the number of cyclic voltammograms for electrodeposition of the conducting polymer and the electrode potential applied for electro-reduction of the metal salts. The physicochemical characteristics of the resulting films were studied using electrochemical and microscopic techniques. The 3D molecular nanoarchitecture presents a hollow porous structure dependent on the electrode potential set for the electro-reduction of Pt and Ni nanoparticles. The electrochemical sensor was validated in terms of sensitivity, limit of detection, stability and repeatability, exhibiting a highly sensitive H2O2 detection, with LoD 68.5 nM (S/N = 3) at 0.05 V vs. Ag-SPCE for the electrode modified with 20 cycles for the conducting polymer electrodeposition and −2.0 V for metal ions reduction. The aim of this work also included the outcome of the electrochemical sensor after incorporating the room temperature ionic liquid 1‑butyl‑2,3-dimethylimidazolium tetrafluoroborate within the PtNi/poly(AzA) film, which notably improved the analytical parameters of the system, with LoD 14.5 nM at the same potential. Therefore, as proof of concept, the PtNi/poly(AzA) film-based electrode was explored towards the suitability of an electrochemical sensor for the determination of hydrogen peroxide in aerosol phase. The outstanding features of the PtNi/poly(AzA) film-based electrode modified with the aforementioned ionic liquid allowed for the continuous monitoring of H2O2 in an aerosol stream generated with an ultrasonic diffuser at the low applied potential of 0.05 V. In addition, monitoring H2O2 samples through a series of ON/OFF switches for over 3 h, the sensor provided a fast and reproducible response.Grants PID2019–106468RB-I00 and PID2019–108136RB-C32 funded by MCIN/AEI/10.13039/501100011033 and grant 2022‐GRIN‐34199 funded by the own research plan of the UCLM and co-financed by the European Fund for Regional Development (FEDER). RJP is the beneficiary of a postdoctoral contract associated with the first indicated project from the MCIN/AEI. This research was also partially funded by the Next-Generation EU funding (Zambrano21–10, AGB)

Design and Characterization of Effective Ag, Pt and AgPt Nanoparticles to H2O2 Electrosensing from Scrapped Printed Electrodes

The use of disposable screen-printed electrodes (SPEs) has extraordinarily grown in the last years. In this paper, conductive inks from scrapped SPEs were removed by acid leaching, providing high value feedstocks suitable for the electrochemical deposition of Ag, Pt and Ag core-Pt shell-like bimetallic (AgPt) nanoparticles, onto screen-printed carbon electrodes (ML@SPCEs, M = Ag, Pt or AgPt, L = metal nanoparticles from leaching solutions). ML@SPCEs were characterized by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The results were compared to those obtained when metal nanoparticles were synthesised using standard solutions of metal salts (MS@SPCEs). Both ML@SPCEs and MS@SPCEs exhibited similar cyclic voltammetric patterns referred to the electrochemical stripping of silver or the adsorption/desorption of hydrogen/anions in the case of platinum, proving leaching solutions extremely effective for the electrodeposition of metallic nanoparticles. The use of both ML@SPCEs and MS@SPCEs proved effective in enhancing the sensitivity for the detection of H2O2 in phosphate buffer solutions (pH = 7). The AgPtL@SPCE was used as proof of concept for the validation of an amperometric sensor for the determination of H2O2 within laundry boosters and antiseptic samples. The electrochemical sensor gave good agreement with the results obtained by a spectrophotometric method with H2O2 recoveries between 100.6% and 106.4%.This work was funded by the Spanish Ministry of Economy and Competitiveness (MINECO, http://www.mineco.gob.es/portal/site/mineco/idi), Projects No. BFU2016-75609-P (AEI/FEDER, EU) and CTQ2016-76231-C2-2-R, and by the Junta de Comunidades de Castilla-La Mancha (Spain), Project No. SBPLY/17/180501/000276/2 (cofunded with FEDER funds, EU). B.G–M is a post-doctoral research fellow of the Youth Employment Initiative (JCCM, Spain, cofunded with ESF funds, EU)

A Comparative Study of Poly(Azure A) Film-Modified Disposable Electrodes for Electrocatalytic Oxidation of H2O2: Effect of Doping Anion

In the present paper, poly(azure A) (PAA) films were electrosynthetized in the presence of different doping anions on disposable screen-printed carbon electrodes (SPCEs). The anions used included inorganic monoatomic (chloride and fluoride), inorganic polyatomic (nitrate and sulfate) and organic polyatomic (dodecyl sulfate, DS) species. The coated electrodes thus obtained were characterized by electrochemical techniques and SEM. They showed improved electrocatalytic activities towards hydrogen peroxide oxidation compared to that of a bare SPCE. In particular, the insertion of DS anions inside PAA films provided a special sensitivity to the electrocatalysis of H2O2, which endowed these electrodes with promising analytical features for H2O2 quantification. We obtained a wide linear response for H2O2 within a range of 5 µM to 3 mM and a limit of detection of 1.43 ± 0.10 µM (signal-to-noise ratio of 3). Furthermore, sensitivity was 72.4 ± 0.49 nA·µM−1∙cm−2 at a relatively low electrocatalytic oxidation overpotential of 0.5 V vs. Ag. The applicability of this boosted system was tested by the analysis of H2O2 in commercial samples of a hair lightener and an antiseptic and was corroborated by spectrophotometric methods