Surface Acid–Base Properties of Anion-Adsorbed Species at Pt(111) Electrode Surfaces in Contact with CO2-Containing Perchloric Acid Solutions

Carbonate and bicarbonate adsorption on Pt(111) electrodes from CO2-saturated acidic solutions is investigated by cyclic voltammetry and Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). Spectroscopic results show carbonate and bicarbonate adsorption even at pH = 1, where bulk concentration of these anions is negligible. Moreover, analysis of the potential dependence of band intensities corresponding to adsorbed carbonate and bicarbonate reveals an effect of the electrode potential on the surface acid–base equilibrium. In this regard, increasing potentials favor bicarbonate deprotonation, leading to carbonate formation. A tentative thermodynamic analysis is given to rationalize these trends.Support from MINECO (Spain) through project CTQ2013-44083-P is greatly acknowledged. RMH thankfully acknowledges support from Generalitat Valenciana under the Santiago Grisolía Program (GRISOLIA/2013/008)

Simultaneous characterization of porous and non-porous electrodes in microbial electrochemical systems

Adequate electrochemical characterization of electrode material/biofilms is crucial for a comprehensive understanding and comparative performance of bioelectrochemical systems (BES). However, their responses are greatly affected by the metabolic activity and growth of these living entities and/or the interference of electrode wiring that can act as an electroactive surface for growth or constitute a source of contamination by corrosion. This restricts the meaningful comparison of the performance of distinct electrode materials in BES. This work describes a methodology for simultaneous electrochemical control and measurement of the microbial response on different electrode materials under the same physicochemical and biological conditions. The method is based on the use of a single channel potentiostat and one counter and reference electrodes to simultaneously polarize several electrode materials in a sole bioelectrochemical cell. Furthermore, various strategies to minimize wiring corrosion are proposed. The proposed methodology, then, will enable a more rigorous characterization of microbial electrochemical responses for comparisons purposes.The authors thank the MINECO and FEDER (RYC-2017-23618) for financial support. This investigation has received funding from the European Union's Horizon 2020 research and innovation programme under the grant agreements No. 642190 (Project “iMETLAND”; http://www.imetland.eu) and No. 826244 (Project “ELECTRA”; http://www.electra.site). Amanda Prado de Nicolás was funded by the “Formación de Personal Investigador (FPI)” PhD fellowship programme from the University of Alcalá

ATR-SEIRAS study of CO adsorption and oxidation on Rh modified Au(111-25 nm) film electrodes in 0.1 M H2SO4

Rh modified Au(111-25 nm) electrodes, prepared by electron beam evaporation and galvanostatic deposition, were employed to study adsorption and electro-oxidation of CO on Rh in 0.1 M sulfuric acid solution by in situ attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS). The results of ATR-SEIRAS experiments were compared with those obtained by infrared reflection absorption spectroscopy on three low-index Rh single crystal surfaces. The Rh film deposited on Au(111-25 nm) electrode consists of 3D clusters forming a highly stepped [n(111) × (111)]-like surface with narrow (111) terraces. When CO was dosed at the hydrogen adsorption potential region, CO adsorbed in both atop (COL) and bridge (COB) configurations, as well as coadsorbed water species, were detected on the Rh film electrode. A partial interconversion of spectroscopic bands due to the CO displacement from bridge to atop sites was found during the anodic potential scan, revealing that there is a potential-dependent preference of CO adsorption sites on Rh surfaces. Our data indicate that CO oxidation on Rh electrode surface in acidic media involves coadsorbed water and follows the nucleation and growth model of a Langmuir-Hinshelwood type reaction.The work was supported by the Research Center Jülich, the University of Bern, Swiss National Science Foundation (200020_144471, 200021-124643), the Spanish Ministerio de Economía y Competitividad (project CTQ2013-44083-P) and University of Alicante. QX acknowledges fellowships of the Research Center Jülich; IP acknowledges support by COST Action TD 1002; and AK acknowledges the financial support by CTI Swiss Competence Centers for Energy Research (SCCER Heat and Electricity Storage)

Hybrid Innovative Learning

El proyecto HYBRID INNOVATIVE LEARNING ha intentado abordar algunos de los retos docentes y académicos que plantean los escenarios generados por el COVID19 en el ámbito de la enseñanza superior y más específicamente en un contexto interdisciplinar relacionado entre otros con los estudios urbanos y medioambientales, políticas públicas, turismo e identidades dentro de las ciencias sociales. Estos retos están en conexión con inquietudes y aspiraciones metodológicas docentes previas de los miembros de este equipo que durante años han tratado de introducir en la tarea docente diferentes formas de promoción de la participación, aprendizaje activo y dialógico

Real-time monitoring of electrochemically active biofilm developing behavior on bioanode by using EQCM and ATR/FTIR

In the current study, the relationship between current and biomass and bio-adhesion mechanism of electrogenic biofilm on electrode were investigated using EQCM and ATR-SEIRAS linking electrochemistry. The results indicated that cellular biomass of biofilm on QCM-crystal surface showed maximum value of 6.0 μg/cm2 in initial batch and 11.5 μg/cm2 in the second batch on mature biofilm, producing a similar maximum current density of 110 μA/μg. Especially, the optimum cell biomass linking high electricity production ratio (110 μA/μg) occurred before maximum biomass coming, implying that over-growth mature biofilm is not an optimum state for enhancing power output of MFCs. On the other hand, the spectra using ATR-SEIRAS technique linking electrochemistry obviously exhibited water structure adsorption change at early biofilm formation and meanwhile the water adsorption accompanied the adsorbed bacteria and the bound cells population on the electrode increased with time. Meanwhile, the direct contact of bacteria and electrode via outer-membrane protein can be confirmed via a series spectra shift at amide I and amide II modes and water movement from negative bands displacing by adsorbed bacteria. Our study provided supplementary information about the interaction between the microbes and electrode beyond traditional electrochemistry.This work was supported by project from the National Natural Science Foundation of China (No. 21375107) and University of Alicante through Project CTQ2013-44083-P

Real-time monitoring of electrochemically active biofilm developing behavior on bioanode by using EQCM and ATR/FTIR

In the current study, the relationship between current and biomass and bio-adhesion mechanism of electrogenic biofilm on electrode were investigated using EQCM and ATR-SEIRAS linking electrochemistry. The results indicated that cellular biomass of biofilm on QCM-crystal surface showed maximum value of 6.0 μg/cm2 in initial batch and 11.5 μg/cm2 in the second batch on mature biofilm, producing a similar maximum current density of 110 μA/μg. Especially, the optimum cell biomass linking high electricity production ratio (110 μA/μg) occurred before maximum biomass coming, implying that over-growth mature biofilm is not an optimum state for enhancing power output of MFCs. On the other hand, the spectra using ATR-SEIRAS technique linking electrochemistry obviously exhibited water structure adsorption change at early biofilm formation and meanwhile the water adsorption accompanied the adsorbed bacteria and the bound cells population on the electrode increased with time. Meanwhile, the direct contact of bacteria and electrode via outer-membrane protein can be confirmed via a series spectra shift at amide I and amide II modes and water movement from negative bands displacing by adsorbed bacteria. Our study provided supplementary information about the interaction between the microbes and electrode beyond traditional electrochemistry.This work was supported by project from the National Natural Science Foundation of China (No. 21375107) and University of Alicante through Project CTQ2013-44083-P