Hydrogen redox reactions in 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide on platinum single crystal electrodes

Hydrogen oxidation and the subsequent proton reduction are studied on platinum single crystal electrodes in purified 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid. The hydrogen redox reaction shows some dependence of the surface orientation. The highest reversibility is observed with Pt(111) whereas the reaction in electrodes with {100} sites is less reversible and with a slow kinetics. Adsorption states are observed in the presence of hydrogen along with the main oxidation reaction. Also, it is possible to detect protons after oxidation of water and H2O2.APS is grateful to the National University of Colombia (ESP-2011-02) for the scholarship “Estudiantes sobresalientes de posgrado”, and to COLCIENCIAS (567-2012) for the national doctoral scholarship. MFS acknowledges support from the National University of Colombia (Research Project 19030). JMF acknowledges support from Generalitat Valenciana (Feder) (PROMETEO/2009/045) through project PROMETEO/2009/045

IR and electrochemical synthesis and characterization of thin films of PEDOT grown on platinum single crystal electrodes in [EMMIM]Tf2N ionic liquid

Thin films of PEDOT synthesized on platinum single electrodes in contact with the ionic liquid 1-ethyl-2,3-dimethylimidazolium triflimide ([EMMIM]Tf2N) were studied by cyclic voltammetry, chronoamperometry, infrared spectroscopy and atomic force microscopy. It was found that the polymer grows faster on Pt(111) than on Pt(110) or Pt(100) and that the redox reactions associated with the PEDOT p-doping process are much more reversible in [EMMIM]Tf2N than in acetonitrile. Finally, the ion exchange and charge carriers’ formation during the p-doping reaction of PEDOT were studied using in situ FTIR spectroscopy.APS acknowledges the scholarship “Estudiantes sobresalientes de posgrado” at the “Universidad Nacional de Colombia (UNAL)” and COLCIENCIAS National Doctoral Scholarship (567). MFS acknowledges support of UNAL (Research Project 19030). JMF thanks MINECO (Spain) support through project CTQ2013-44083-P and Generalitat Valenciana (Feder) through project PROMETEOII/2014/013

Interaction of water with methanesulfonic acid on Pt single crystal electrodes

The electrochemical behavior of methanesulfonic acid on platinum single crystal electrode surfaces is investigated by cyclic voltammetry and infrared spectroscopy measurements. The results are compared with the voltammetric profiles of perchloric and trifluoromethanesulfonic acids. The differences are interpreted in terms of the effect of the anion on the structure of water. No adsorbed species are detected by infrared spectroscopy.APS acknowledges the scholarship “Estudiantes sobresalientes de posgrado” at the UNC and COLCIENCIAS National Doctoral Scholarship (567). MFS acknowledges the support of UNC (Research Project 19030). JMFwould like to thankGeneralitat Valenciana (Feder) through project PROMETEOII/2014/013

Role of the interfacial water structure on electrocatalysis: Oxygen reduction on Pt(1 1 1) in methanesulfonic acid

Most of electrocatalytic reactions occur in an aqueous environment. Understanding the influence of water structure on reaction dynamics is fundamental in electrocatalysis. In this work, the role of liquid water structure on the oxygen reduction at Pt(1 1 1) electrode is analyzed in methanesulfonic (MTSA) and perchloric acids. This is because these different anions can exert a different influence on liquid water structure. Results reveal a lower ORR electrode activity in MTSA than in HClO4 solutions and they are discussed in light of anion's influence on water structural ordering. From them, the existence of an outer-sphere, rate determining, step in the ORR mechanism is suggested.This work has been carried out under MINECO project CTQ2013-44083-P (Spain). APSR acknowledges the scholarship “Estudiantes sobresalientes de posgrado” at the UNAL and COLCIENCIAS National Doctoral Scholarship (567). MFS acknowledges the support of UNAL (Research Project 19030)

An Aza-Fused pi-Conjugated Microporous Framework Catalyzes the Production of Hydrogen Peroxide

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/page/policy/articlesonrequest/index.html"[EN] In order to produce hydrogen peroxide in small-scale electrochemical plants, selective catalysts for the oxygen reduction reaction (ORR) toward the desired species are required. Here, we report about the synthesis, characterization, ORR electrochemical behavior, and reaction mechanism of an aza-fused pi-conjugated microporous polymer, which presents high selectivity toward hydrogen peroxide. It was synthesized by polycondensation of 1,2,4,5-benzenetetramine tetrahydrochloride and triquinoyl octahydrate. A cobalt-modified version of the material was also prepared by a simple postsynthesis treatment with a Co(II) salt. The characterization of the material is consistent with the formation of a conductive robust porous covalent laminar polyaza structure. The ORR properties of these catalysts were investigated using rotating disk and rotating disk ring arrangements. The results indicate that hydrogen peroxide is almost exclusively produced at very low overpotentials on these materials. Density functional theory calculations provide key elements to understand the reaction mechanism. It is found that, at the relevant potential for the reaction, half of the nitrogen atoms of the material would be hydrogenated. This hydrogenation process would destabilize some carbon atoms in the lattice and would provide segregated charge. On the destabilized carbon atoms, molecular oxygen would be chemisorbed with the aid of charge transferred from the hydrogenated nitrogen atoms and solvation effects. Due to the low destabilization of the carbon sites, the resulting molecular oxygen chemisorbed state, which would have the characteristics of a superoxide species, would be only slightly stable, promoting the formation of hydrogen peroxide.This work has been financially supported by the MCINN-FEDER (projects CTQ2016-76221-P, MAT2013-46753-C2-1-P, and MAT2014-52305-P) and Generalitat Valenciana (project PROMETEO/2014/013).Briega-Martos, V.; Ferre Vilaplana, A.; De La Peña, A.; Segura, J.; Zamora, F.; Feliu, J.; Herrero, E. (2017). An Aza-Fused pi-Conjugated Microporous Framework Catalyzes the Production of Hydrogen Peroxide. ACS Catalysis. 7(2):1015-1024. https://doi.org/10.1021/acscatal.6b03043S101510247

Stark effect or coverage dependence? Disentangling the EC-SEIRAS vibrational shift of sulfate on Au(111)

Infrared spectroscopy is a widely employed analytical tool in (electrochemical) surface science as the spectra contain a wealth of information about the interaction of interfacial adsorbates with their environment. Separating and quantifying individual contributions, for example, of co-adsorbates, the substrate or electric field effects, on the overall spectral response, however, is often non-trivial as the various interactions manifest themselves in similar spectral behavior. Here, we present an experimental approach to differentiate between and quantify potential-induced coverage dependence and field-related Stark effects observed in a sulfate band shift of 93.5 ± 1.5 cm−1/V in electrochemical infrared spectra of the showcase sulfate/Au(111) interface. In combination with a simple linear model equation used to describe the potential-induced peak shift of the sulfate stretch vibration, we determine the coverage dependence contribution to be 15.6 ± 1.2 cm−1/θSO and the Stark effect to amount to 75.6 ± 2.7 cm−1/V. Our work provides a novel route to gain fundamental insight into interfacial adsorbate interactions in electrochemical surface science.J.H.K.P. and K.F.D. gratefully acknowledge financial support by the Max Planck Graduate Center with the Johannes Gutenberg University Mainz (MPGC). U.E.Z. is grateful for financial support from the Alexander von Humboldt Foundation. J.M.F. thanks MCINN-FEDER (Spain) for support through Project No. CTQ2016-76221-P. K.F.D. acknowledges generous support through the Emmy Noether Program of the Deutsche Forschungsgemeinschaft (No. DO1691/1-1) and through the “Plus 3” Program of the Boehringer Ingelheim Foundation

Electrochemical reduction of CO2 in water-acetonitrile mixtures on nanostructured Cu electrode

This communication studies the CO2 reduction reaction in H2O/CH3CN mixtures on nanostructured copper. It was found that the nanostructured copper electrode presents a well-defined voltammogram in acetonitrile, where it can be seen three signals related to adsorbed or surface attached (thin films) species. Also, it was found that the current density of CO2 reduction in mixtures H2O/CH3CN on nanostructured copper electrodes with a mole fraction around 0.25 is higher than those observed with mole fractions lower than 0.15 or higher than 0.35. Finally, nanostructured Cu electrodes show higher catalytic activity towards the CO2 reduction than copper electrode.APSR acknowledges the scholarship “Estudiantes sobresalientes de posgrado” at the “Universidad Nacional de Colombia (UNAL)” and COLCIENCIAS National Doctoral Scholarship (567). MFS acknowledges the support of UNAL (Research Project 19030)

Oxidation mechanism of formic acid on the bismuth adatom-modified Pt(111) surface

In order to improve catalytic processes, elucidation of reaction mechanisms is essential. Here, supported by a combination of experimental and computational results, the oxidation mechanism of formic acid on Pt(111) electrodes modified by the incorporation of bismuth adatoms is revealed. In the proposed model, formic acid is first physisorbed on bismuth and then deprotonated and chemisorbed in formate form, also on bismuth, from which configuration the C-H bond is cleaved, on a neighbor Pt site, yielding CO2. It was found computationally that the activation energy for the C-H bond cleavage step is negligible, which was also verified experimentally.This work has been financially supported by the MINECO (Spain) (project CTQ2013-44083-P) and Generalitat Valenciana (project PROMETEOII/2014/013).Perales Rondón, JV.; Ferre Vilaplana, A.; Feliu, J.; Herrero, E. (2014). Oxidation mechanism of formic acid on the bismuth adatom-modified Pt(111) surface. Journal of the American Chemical Society. 136(38):13110-13113. https://doi.org/10.1021/ja505943hS13110131131363

Trimesic acid on Cu in ethanol: Potential-dependent transition from 2-D adsorbate to 3-D metal-organic framework

We report the potential-dependent interactions of trimesic acid with Cu surfaces in EtOH. CV experiments and electrochemical surface-enhanced Raman spectroscopy show the presence of an adsorbed trimesic acid layer on Cu at potentials lower than 0 V vs Cu. The BTC coverage increases as the potential increases, reaching a maximum at 0 V. Based on molecular dynamics simulations, we report adsorption geometries and possible structures of the organic adlayer. We find that, depending on the crystal facet, trimesic acid adsorbs either flat or with one or two of the carboxyl groups facing the metal surface. At higher coverages, a multi-layer forms that is composed mostly of flat-lying trimesic acid molecules. Increasing the potential beyond 0 V activates the Cu-adsorbate interface in such a way that under oxidation of Cu to Cu2 +, a 3-D metal-organic framework forms directly on the electrode surface.PS gratefully acknowledges the Max Planck Graduate Center and the Studienstiftung des deutschen Volkes for the funding. KFD gratefully acknowledges the generous funding through the Emmy Noether program of the Deutsche Forschungsgemeinschaft (DO 1691/1-1)

Chronic obstructive pulmonary disease (COPD) as a disease of early aging: evidence from the epiChron cohort

Background: Aging is an important risk factor for most chronic diseases. Patients with COPD develop more comorbidities than non-COPD subjects. We hypothesized that the development of comorbidities characteristically affecting the elderly occur at an earlier age in subjects with the diagnosis of COPD. Methods and findings: We included all subjects carrying the diagnosis of COPD (n = 27,617), and a similar number of age and sex matched individuals without the diagnosis, extracted from the 727,241 records of individuals 40 years and older included in the EpiChron Cohort (Aragon, Spain). We compared the cumulative number of comorbidities, their prevalence and the mortality risk between both groups. Using network analysis, we explored the connectivity between comorbidities and the most influential comorbidities in both groups. We divided the groups into 5 incremental age categories and compared their comorbidity networks. We then selected those comorbidities known to affect primarily the elderly and compared their prevalence across the 5 age groups. In addition, we replicated the analysis in the smokers' subgroup to correct for the confounding effect of cigarette smoking. Subjects with COPD had more comorbidities and died at a younger age compared to controls. Comparison of both cohorts across 5 incremental age groups showed that the number of comorbidities, the prevalence of diseases characteristic of aging and network's density for the COPD group aged 56-65 were similar to those of non-COPD 15 to 20 years older. The findings persisted after adjusting for smoking. Conclusion: Multimorbidity increases with age but in patients carrying the diagnosis of COPD, these comorbidities are seen at an earlier age