Electrodos de Diamante Dopado con Boro para el tratamiento electroquímico de aguas

Boron-doped diamond electrodes have emerged as anodic material due to their high physical, chemical and electrochemical stability. These characteristics make it particularly interesting for electrochemical wastewater treatments and especially due to its high overpotential for the Oxygen Evolution Reaction. Diamond electrodes present the maximum efficiency in pollutant removal in water, just limited by diffusion-controlled electrochemical kinetics. Results are presented for the elimination of benzoic acid and for the electrochemical treatment of synthetic tannery wastewater. The results indicate that diamond electrodes exhibit the best performance for the removal of total phenols, COD, TOC, and colour.Los electrodos de diamante dopados con boro han surgido como un nuevo material anódico debido a su propiedades como estabilidad física, química y electroquímica. Estas características hacen a estos electrodos especialmente interesantes para el tratamiento electroquímico de aguas residuales, debido sobre todo a su elevado sobrepotencial para la reacción de formación de oxígeno. Los electrodos de diamante presentan una eficiencia máxima para la eliminación de contaminantes en el agua, sólo limitada por la cinética del proceso electroquímico controlado por difusión. Se muestran algunos ejemplos como en la eliminación de ácido benzoico y en el tratamiento electroquímico de aguas sintéticas del curtido de pieles. Los resultados indican que los electrodos de diamante muestran el mejor rendimiento para la eliminación de fenoles, DQO, COT, y del color

Electroassisted Incorporation of Ferrocene within Sol–Gel Silica Films to Enhance Electron Transfer

The sol–gel method is a straightforward technique that allows electrode modification with silica thin films. Furthermore, the silica pores could be functionalized to enhance the electrical conductivity and reactivity of the silica films. In this context, silica thin films were functionalized with ferrocene species. This functionalization was performed by electroassisted accumulation, generating a micro-structured composite electrode (Fc@SiO2 electrode). These modified electrodes were characterized by electrochemical and spectroelectrochemical methods, pointing out that ferrocene species were confined with high stability within the microporous silica thin film, demonstrating the good adsorption capacity of the silica. While the spectroelectrochemical characterization indicates that only a fraction of the confined species within the silica films were electroactive, the electrochemical results demonstrate that the Fc@SiO2 film enhances the electrochemical response of cytochrome c in a solution, which gives rise to further applications of these films for redox-controlled release and electrochemical detection of other redox-active proteins.This research was funded by the Spanish Ministerio de Ciencia e Innovación (grants PDC2021-120884-I00 and TED2021-129894B-I00), Generalitat Valenciana (grants Prometeo CIPROM/2021/062 and Advanced Materials MFA/2022/058 programs), and European Union (Grants NextGenerationEU PRTR-C17.I1) for financial support

Membraneless energy conversion and storage using immiscible electrolyte solutions

peer-reviewedBreakthrough alternative technologies are urgently required to alleviate the critical need to decarbonise our energy supply. We showcase non-conventional approaches to battery and solar energy conversion and storage (ECS) system designs that harness key attributes of immiscible electrolyte solutions, especially the membraneless separation of redox active species and ability to electrify certain liquid–liquid interfaces. We critically evaluate the recent development of membraneless redox flow batteries based on biphasic systems, where one redox couple is confined to an immiscible ionic liquid or organic solvent phase, and the other couple to an aqueous phase. Common to all solar ECS devices are the abilities to harvest light, leading to photo-induced charge carrier separation, and separate the products of the photo-reaction, minimising recombination. We summarise recent progress towards achieving this accepted solar ECS design using immiscible electrolyte solutions in photo-ionic cells, to generate redox fuels, and biphasic “batch” water splitting, to generate solar fuels.ACCEPTEDpeer-reviewe

Potential-Modulated Ion Distributions in the Back-to-Back Electrical Double Layers at a Polarised Liquid|Liquid Interface Regulate the Kinetics of Interfacial Electron Transfer

Biphasic interfacial electron transfer (IET) reactions at polarisable liquid|liquid (L|L) interfaces underpin new approaches to electrosynthesis, redox electrocatalysis, bioelectrochemistry and artificial photosynthesis. Herein, using cyclic and alternating current voltammetry, we demonstrate that under certain experimental conditions, the biphasic 2-electron O2 reduction reaction can proceed by single-step IET between a reductant in the organic phase, decamethylferrocene, and interfacial protons in the presence of O2. Using this biphasic system, we demonstrate that the applied interfacial Galvani potential difference ΔwoØ provides no direct driving force to realise a thermodynamically uphill biphasic IET reaction in the mixed solvent region. We show that the onset potential for a biphasic single-step IET reaction does not correlate with the thermodynamically predicted standard Galvani IET potential and is instead closely correlated with the potential of zero charge at a polarised L|L interface. We outline that the applied ΔwoØ required to modulate the interfacial ion distributions, and thus kinetics of IET, must be optimised to ensure that the aqueous and organic redox species are present in substantial concentrations at the L|L interface simultaneously in order to react.M.D.S. acknowledges funding from Science Foundation Ireland (SFI) under grant no. 13/SIRG/2137 and the European Research Council through a Starting Grant (agreement no. 716792). A.G.-Q. acknowledges funding received from an Irish Research Council (IRC) Government of Ireland Postdoctoral Fellowship Award (grant number GOIPD/2018/252) and a Marie Skłodowska-Curie Postdoctoral Fellowship (Grant Number MSCA-IF-EF-ST 2020/101018277)

Promotion of Direct Electron Transfer to Cytochrome c by Functionalized Thiophene-based Conducting Polymers

Controlling direct electron transfer (DET) to redox proteins is of great interest for fundamental studies on biochemical processes and the development of biotechnological devices, such as biosensors or enzymatic fuel cells. Cytochrome c is a classical model protein for studying DET reactions that plays a key role in the onset of cellular apoptosis and the mitochondrial respiratory chain. In this contribution, we explored DET between cyt c and conducting polymers bearing the chemical structure of thiophene, specifically PEDOT, and its OH-containing derivative, PHMeEDOT. The combination of electrochemistry and in situ FTIR spectroscopy allowed us to gain more insight into the inner mechanism of DET at physiological pH. Hydrophilic interactions favour the correct orientation of the heme crevice of cytochrome c towards the polymer surface. When a positive charge is injected into the conducting polymer, the increasing electrostatic repulsion between protein and surface induces the desorption of lysine residues near the heme group and stimulates protein flipping. This effect was more pronounced at PEDOT- than PHMeEDOT-modified electrodes since the latter shows stronger interactions with lysine residues, partially hindering protein rotation at moderate potential. The potential-induced reorientation process was similar on both polymer surfaces, only at high positive potentials.Financial support by Spanish Ministry of Science (projects TED2021-129894B-I00 and PDC2021-120884-I00), Generalitat Valenciana (projects GVA-THINKINAZUL/2021/015, MFA/2022/058 and CIPROM/2021/62) and European Union (NextGenerationEU PRTR-C17.I1) is gratefully acknowledged. A.G.-Q. acknowledges funding received from his Marie Skłodowska-Curie Postdoctoral Fellowship (Grant Number MSCA-IF-EF-ST 2020/101018277)

Enhancement of the electrochemical performance of SWCNT dispersed in a Silica Sol-Gel matrix by reactive Insertion of a Conducting Polymer

The electroassisted encapsulation of Single-Walled Carbon Nanotubes was performed into silica matrices (SWCNT@SiO2). This material was used as the host for the potentiostatic growth of polyaniline (PANI) to yield a hybrid nanocomposite electrode, which was then characterized by both electrochemical and imaging techniques. The electrochemical properties of the SWCNT@SiO2-PANI composite material were tested against inorganic (Fe3+/Fe2+) and organic (dopamine) redox probes. It was observed that the electron transfer constants for the electrochemical reactions increased significantly when a dispersion of either SWCNT or PANI was carried out inside of the SiO2 matrix. However, the best results were obtained when polyaniline was grown through the pores of the SWCNT@SiO2 material. The enhanced reversibility of the redox reactions was ascribed to the synergy between the two electrocatalytic components (SWCNTs and PANI) of the composite material. (C) 2014 Elsevier Ltd. All rights reserved.This work was financed by the following research projects: MAT2010-15273 of the Spanish Ministerio de Economia y Competitividad and CIVP16A1821 of the Fundacion Ramon Areces and PROMETEO 2013/038 of the Generalitat Valenciana. Alonso Gamero-Quijano is grateful to Generalitat Valenciana (Santiago Grisolia Program) for the funding of his research fellowship. David Salinas-Torres is grateful to Ministerio de Economia y Competitividad for the funding of his research fellowship.Gamero-Quijano, A.; Huerta, F.; Salinas Torres, D.; Morallón, E.; Montilla, F. (2014). Enhancement of the electrochemical performance of SWCNT dispersed in a Silica Sol-Gel matrix by reactive Insertion of a Conducting Polymer. Electrochimica Acta. 135:114-120. https://doi.org/10.1016/j.electacta.2014.04.172S11412013

Visualization of Diffusion within Nanoarrays

The direct experimental characterization of diffusion processes at nanoscale remains a challenge that could help elucidate processes in biology, medicine and technology. In this report, two experimental approaches were employed to visualize ion diffusion profiles at the orifices of nanopores (radius (ra) of 86 ± 6 nm) in array format: (1) electrochemically assisted formation of silica deposits based on surfactant ion transfer across nanointerfaces between two immiscible electrolyte solutions (nanoITIES); (2) combined atomic force - scanning electrochemical microscopy (AFM-SECM) imaging of topography and redox species diffusion through the nanopores. The nature of the diffusion zones formed around the pores is directly related to the interpore distance within the array. Nanopore arrays with different ratios of pore center-to-center separation (rc) to pore radius (ra) were fabricated by focused ion beam (FIB) milling of silicon nitride (SiN) membranes, with 100 pores in a hexagonal arrangement. The ion diffusion profiles determined by the two visualization methods indicated the formation of overlapped or independent diffusion profiles at nanopore arrays with rc/ra ratios of 21 ± 2 and 91 ± 7, respectively. In particular, the silica deposition method resulted in formation of a single deposit encompassing the complete array with closer nanopore arrangement, whereas individual silica deposits were formed around each nanopore within the more widely spaced array. The methods reveal direct experimental evidence of diffusion zones at nanopore arrays and provide practical illustration that the pore-pore separation within such arrays has a significant impact on diffusional transport as the pore size is reduced to the nanoscale. These approaches to nanoscale diffusion zone visualization open up possibilities for better understanding of molecular transport processes within miniaturized systems

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