Revisiting the redox transitions of Polyaniline. Semiquantitative interpretation of electrochemically induced IR bands

[EN] The redox transitions of PANI in acidic medium have been monitored by a combination of cyclic voltammetry, in situ conductance and in situ FTIR spectroscopy. The results of the semiquantitative analysis strongly suggest that the classical tetrameric model of PANI does not satisfactorily describe the actual structures of the polymer at different redox states. An octameric model is revisited, with the inclusion of essential resonant structures, to provide an appropriate prediction of the relative IR intensity changes of the aromatic Csingle bondC stretching (at around 1520 cm¿1) and the quinoid Cdouble bondC stretching (at around 1590 cm¿1) vibrations observed by FTIR, which are difficult to interpret by considering only 4 aniline rings. Particularly, it is found that the emeraldine state is better described as a resonance hybrid of the classical bipolaronic and semiquinoid (polaron lattice) structures, while most of the charge transferred at the onset of the second voltammetric peak comes from the additional oxidation of this hybrid, which becomes unstable in the electrochemical environment producing mineralization to CO2 and release of soluble quinones.This work was financed by the Spanish Ministerio de Ciencia e Innovacion (project PID2019-105923RB-I00) and by Generalitat Valenciana (Conselleria de Educacion, Investigacion, Cultura y Deporte through project PROMETEO/2018/087). The authors of this work are deeply grateful to Prof. Jose Luis Vazquez Pico (Pepe, nowadays retired) for his mentorship, which was the seed to develop this work. We appreciate the wise advice he gave us during our careers which served us to deepen the science contained in this article, as well as for the friendship with which he honored us over the years.Huerta, F.; Quijada, C.; Montilla, F.; Morallón, E. (2021). Revisiting the redox transitions of Polyaniline. Semiquantitative interpretation of electrochemically induced IR bands. Journal of Electroanalytical Chemistry. 897:1-11. https://doi.org/10.1016/j.jelechem.2021.115593S11189

Synthesis of Graphitic Carbon Nanostructures from Sawdust and Their Application as Electrocatalyst Supports

We present a novel and facile synthetic method for fabricating graphitic carbon nanostructures (GCNs) from sawdust. This method is based on the use of catalysts (Fe or Ni) that allows the direct conversion of sawdust into highly graphitized carbon material. The following procedure was used to obtain these graphitic nanoparticles:  (a) impregnation of the sawdust particles with iron or nickel salts, (b) carbonization of the impregnated material at a temperature of 900 or 1000 °C, and (c) selective removal of the non-graphitized carbon (amorphous carbon) by an oxidant (KMnO4). The resulting carbon is made up of nanosized graphitic structures (i.e., nanocapsules, nanocoils, nanoribbons), which have a high crystallinity, as evidenced by TEM/SAED, XRD and Raman analysis. These GCNs were used as supports for platinum nanoparticles. Such prepared electrocatalysts show an electrocatalytical surface area close to 90 m2.g-1 Pt, and they present a similar or higher electrocatalytic activity toward methanol electrooxidation than the Pt/Vulcan electrocatalyst prepared in the same conditions.The financial support for this research work provided by the Spanish MCyT (MAT2005-00262, MAT2004-01479 and FEDER) is gratefully acknowledged.Peer reviewe

Characterization of activated carbon fiber/polyaniline materials by position-resolved microbeam small-angle X-ray scattering

Activated carbon fiber (ACF)/polyaniline (PANI) materials have been prepared using two different methods, viz. chemical and electrochemical polymerization. Electrochemical characterization of both materials shows that the electrodes with polyaniline have a higher capacitance than does a pristine porous carbon electrode. To analyze the distribution of PANI within the ACF, characterization by position-resolved microbeam small-angle X-ray scattering (μSAXS) has been carried out. μSAXS results obtained with a single ACF indicate that, for the experimental conditions used, a PANI coating is formed inside the micropores and that it is higher in the external regions of the ACF than in the core. Additionally, it seems that the penetration of PANI inside the fibers occurs in a larger extent for the chemical polymerization or, in other words, for the electrochemically polymerized sample there is a slightly larger accumulation of PANI in the external regions of the ACF.Fil: Salinas-Torres, D.. Universida de Alicante; EspañaFil: Sieben, Juan Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Lozano-Castelló, D.. Universida de Alicante; EspañaFil: Morallón, E.. Universida de Alicante; EspañaFil: Burghammer, M.. EuropeanSynchrotronRadiationFacility; FranciaFil: Riekel, C.. EuropeanSynchrotronRadiationFacility; FranciaFil: Cazorla Amorós, Diego. Universida de Alicante; Españ

Kinetic and thermodynamic study of the adsorption of As(III) from aqueous solutions by naturally occurring and modified montmorillonites

[EN] Adsorption of As(III) from aqueous solutions using naturally occurring and modified Algerian montmorillonites was investigated as a function of contact time, pH and temperature. Kinetic studies reveal that uptake of As(III) ions is rapid within the first 3 hours and it slows down thereafter. Equilibrium studies show that As(III) shows the highest affinity towards Acidic-montmorillonite even at very low concentration of arsenic. A pseudo-second-order chemical reaction model was obtained for As(III). Adsorption isotherms of As(III) fitted the Langmuir and Freundlich isotherm models well. From the thermodynamic parameters, it is concluded that adsorption is exothermic, spontaneous and favorable. The results suggest that M1, M2 and Acidic-M2 could be used as effective filtering materials for removal of arsenic from water.This work has been financed by the AECID (projects AECID-PCI A/019533/08, A/023858/09 and C/031332/10) and Ministerio de Ciencia e Innovación (project MAT2010-15273). The National Agency for the Development of University Research (CRSTRA), the Directorate General of Scientific Research and Technological Development (DGRSDT) of Algeria.Zehhaf, A.; Benyouncef, A.; Quijada Tomás, C.; Taleb, S.; Morallón, E. (2012). Kinetic and thermodynamic study of the adsorption of As(III) from aqueous solutions by naturally occurring and modified montmorillonites. Biointerface Research in Applied Chemistry. 2(3):350-359. http://hdl.handle.net/10251/51537S3503592

The chemical and electrochemical oxidative polymerization of 2-amino-4-tert-butylphenol

[EN] Poly(2-amino-4-tert-butylphenol), poly(2A-4TBP), was synthesized from monomer aqueous solution using either electrochemical or chemical oxidation procedures. Several spectroscopic characterization techniques were employed to gain information on the chemical structure and redox behavior of the obtained materials. It was found that the chemical polymerization product could be described as an oligomer mixture containing up to 16 monomer units. In parallel to other polymers derived from o-aminophenol, phenoxazine rings constitute also the basic structure of poly(2A-4TBP). In addition, the occurrence of N-N couplings, which are favored by the presence of the voluminous tert-butyl substituent, seems also relevant. No significant structural differences were found between the chemically or electrochemically synthesized materials. © 2016 Published by Elsevier Ltd.Financial support from the Spanish Ministerio de Economía y Competitividad and FEDER funds (MAT2013-42007-P) and from the Generalitat Valenciana (PROMETEO2013/038) is gratefully acknowledged. M. Abidi thanks the Ministry of Higher Education and Scientific Research of Tunisia for funding her stay at the University of Alicante.Abidi, M.; López-Bernabeu, S.; Huerta, F.; Montilla-Jiménez, F.; Besbes-Hentati, S.; Morallón, E. (2016). The chemical and electrochemical oxidative polymerization of 2-amino-4-tert-butylphenol. Electrochimica Acta. 212:958-965. https://doi.org/10.1016/j.electacta.2016.07.060S95896521

Electro-oxidation of cyanide on active and non-active anodes: Designing the electrocatalytic response of cobalt spinels

[EN] The feasibility of the electrochemical technologies for wastewater treatment greatly relies on the design of efficient but inexpensive electrocatalysts. It is generally accepted that the so-called ¿non-active¿ anodes (like the boron-doped diamond (BDD) or SnO2-based anodes), producing highly oxidizing hydroxyl radicals, are the most promising candidates for pollutants abatement. In this work, the electrocatalytic performance of various cobalt oxides, pure and doped with Cu or Au, for CN¿ oxidation has been studied and compared with that of conventional graphite, BDD, SnO2-Sb and SnO2-Sb-Pt. The metal oxide electrodes were prepared by thermal decomposition of the salt precursors onto Ti. For the M-doped Co3O4 electrodes, the nominal M/Co ratios were Cu/ Co=0.07¿1.00; and Au/Co=0.05¿0.20. The electrodes were characterized by different techniques (XRD, SEM, EDX, XPS) and their electrocatalytic response was studied by cyclic voltammetry and galvanostatic electrolysis in a H-type cell in aqueous 0.1M NaOH. The obtained results show that the nature of the dopant plays a key role on the electrocatalytic behavior of cobalt spinels. Thus, while Cu catalyzes the CN¿ electro-oxidation, Au declines it. This is explained by the fact that, unlike Au (which segregates as Au-rich particles), Cu is effectively incorporated into the spinel structure by forming a solid solution (CuxCo3-xO4). In this solid solution, atomic scale Cu(spinel)-CN¿ specific interactions occur to catalyze the reaction, whereas in segregated Au particles the oxidation is hindered probably by a too-strong adsorption of cyanide and/or its inaccessibility to oxide active sites. Electrolysis runs have revealed that ¿active¿ over-saturated Cu-doped spinels (Cu/Co=1.00) exhibit higher current efficiencies than conventional graphite and ¿non-active¿ BDD and SnO2-based anodes. Hence, we hereby demonstrate that an inexpensive ¿active¿ electrocatalyst can show even higher efficiency than the most powerful BDD anode. These results highlight the significance of anode design in the application of the electrochemical technique for wastewater treatment.Financial support from the Spanish Ministerio de Economia y Competitividad and FEDER funds (MAT2016-76595-R, IJCI-2014-20012) is gratefully acknowledgedBerenguer, R.; Quijada, C.; La Rosa-Toro, A.; Morallón, E. (2019). Electro-oxidation of cyanide on active and non-active anodes: Designing the electrocatalytic response of cobalt spinels. Separation and Purification Technology. 208:42-50. https://doi.org/10.1016/j.seppur.2018.05.024S425020

Structural and morphological alterations induced by cobalt substitution in LaMnO3 perovskites

[EN] The chemical composition of a LaMnO3 perovskite was modified sequentially by an improved sol-gel method to include cobalt centers in some B sites formerly occupied by Mn. In this way, a representative set of materials of general formula LaMn1-xCoxO3 was obtained whose composition extends from LaMnO3 to LaCoO3. These perovskites, as promising materials for oxygen reduction or oxygen evolution reactions, were characterized by several imaging (SEM), spectroscopic (XPS, EDX) and diffraction (XRD) techniques to elucidate their structure and to demonstrate the existence of composition differences between the catalytic surface and the bulk material. Specifically, it was found that lanthanum ions prevail at the surface of the catalyst but high cobalt-substitution levels stimulate the surface enrichment in B cations in their respective higher oxidation states (Mn4+ and Co3+ against Mn3+ and Co2+). This phenomenon opens the possibility of tuning their electrocatalytic properties and to synthesize suitable materials for electrochemical reactions involving molecular oxygen. (C) 2019 Elsevier Inc. All rights reserved.The authors thank MINECO and FEDER (MAT2016-76595-R) for the financial support. J.X.F.-L. gratefully acknowledges MINECO for the financial support through FPI contract (BES-2017-081598).Flores-Lasluisa, JX.; Huerta, F.; Cazorla-Amoros, D.; Morallón, E. (2019). Structural and morphological alterations induced by cobalt substitution in LaMnO3 perovskites. Journal of Colloid and Interface Science. 556:658-666. https://doi.org/10.1016/j.jcis.2019.08.112S65866655

Modulation of the silica sol-gel composition for the promotion of direct electron transfer to encapsulated cytochrome

The direct electron transfer between indium-tin oxide electrodes (ITO) and cytochrome c encapsulated in different sol-gel silica networks was studied. Cyt c@silica modified electrodes were synthesized by a two-step encapsulation method mixing a phosphate buffer solution with dissolved cytochrome c and a silica sol prepared by the alcohol-free sol-gel route. These modified electrodes were characterized by cyclic voltammetry, UV-vis spectroscopy, and in situ UV-vis spectroelectrochemistry. The electrochemical response of encapsulated protein is influenced by the terminal groups of the silica pores. Cyt c does not present electrochemical response in conventional silica (hydroxyl terminated) or phenyl terminated silica. Direct electron transfer to encapsulated cytochrome c and ITO electrodes only takes place when the protein is encapsulated in methyl modified silica networks.We gratefully acknowledge Jesus Yanez and Prof. Jose Miguel Martin-Martinez from the Laboratory of Adhesion and Adhesives (University of Alicante) for their assistance in the measurements of contact angle. We also acknowledge the Financial support from the Spanish Ministerio de Economia y Competitividad and FEDER y Ciencia (MAT2010-15273), Generalitat Valenciana (PROMETEO2013/038), and the Fundacion Ramon Areces (CIVP16A1821). Alonso Gamero-Quijano is grateful to Generalitat Valenciana (Santiago Grisolia Program) for the funding of his research fellowship.Gamero-Quijano, A.; Huerta, F.; Morallón, E.; Montilla, F. (2014). Modulation of the silica sol-gel composition for the promotion of direct electron transfer to encapsulated cytochrome. Langmuir. 30(34):10531-10538. https://doi.org/10.1021/la5023517S1053110538303

The oxidation of ascorbate at copolymeric sulfonated poly(aniline) coated on glassy carbon electrodes

Self-doped poly(aniline)s as electrode coatings to catalyze ascorbate oxidation are revisited in this article. Sulfonated poly(aniline) (SPAN) was deposited on glassy carbon electrodes as a copolymer of aniline and its sulfonated derivative, 2-aminobenzenesulfonic acid (2-ABSA). The resulting deposits are reproducible and show good stability and electroactivity at pH &gt; 7, enabling studies at typical physiological pH values. Calibration curves were obtained using a rotating disc electrode at a sampling potential of 0.2 V, displaying linear dependence in the region 0–20 mM ascorbate. A kinetic model based on the Michaelis–Menten reaction mechanism, previously validated for poly(aniline) composites, was used to analyse the form of the calibration curve leading to values of the effective reaction constants KME and k?ME. New calibration curves constructed for different sampling potentials were used to elucidate the rate limiting step at saturated kinetics. Rotating disc voltammetry performed at increasing pH (from pH 2 to 9) showed a dramatic decrease in the limiting current, without any evidence for a change in the reaction mechanism.<br/