The role of formic acid/formate equilibria in the oxidation of formic acid on Pt(111)

[EN] The formic acid oxidation reaction has been studied in concentrated perchloric acid solutions (up to 9.14M (60%)) on the Pt (111) surface to explore the relationships between interfacial properties and kinetics. It is found that, as the concentration of perchloric acid in the supporting electrolyte increases, the current markedly decreases, making it possible to detect adsorbed formate on the surface by voltammetric methods. With the aid of DFT calculations, it is shown that the diminution in current is the result of two opposing factors: the reduction in the concentration of free formate in solution and electrode charge effects which encourage the adsorption of formate in a particular configuration. Additionally, the electrochemical behavior under highly acidic conditions suggests the formation of clathrate structures and emphasizes the relevance of the water structure effect in electrode adsorption processes.This work has been financially supported by the Ministerio de Economia, Industria y Competitividad through the project CTQ2016-76221-P. CBR also thanks his Postdoctoral fellowship to Generalitat Valenciana (APOSTD/2017/010).Busó-Rogero, C.; Ferre-Vilaplana, A.; Herrero, E.; Feliu, JM. (2019). The role of formic acid/formate equilibria in the oxidation of formic acid on Pt(111). Electrochemistry Communications. 98:10-14. https://doi.org/10.1016/j.elecom.2018.11.011S10149

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

The Role of Adsorption in the Electrocatalysis of Hydrazine on Platinum Electrodes

Hydrazine oxidation on platinum single-crystal electrodes has been studied in acidic solution containing different electrolytes. It will be shown that the hydrazinium cation is adsorbed on platinum through an anodic reaction. Moreover, in the presence of chloride, this adsorption process is favored owing to the formation of an ionic pair with adsorbed chloride. In spite of the enhanced adsorption of hydrazine species in the presence of chloride, higher overpotentials are measured in these media, which reveals that the oxidation of hydrazine not only requires adsorption, but also that the adsorption mode of the species facilitates the formation of the transition state to yield the final product.This work has been financially supported by the MINECO (Spain) and Generalitat Valenciana through projects CTQ2016-76221-P and PROMETEOII/2014/013, respectively

Pseudo-single crystal electrochemistry on polycrystalline electrodes : visualizing activity at grains and grain boundaries on platinum for the Fe2+/Fe3+ redox reaction

The influence of electrode surface structure on electrochemical reaction rates and mechanisms is a major theme in electrochemical research, especially as electrodes with inherent structural heterogeneities are used ubiquitously. Yet, probing local electrochemistry and surface structure at complex surfaces is challenging. In this paper, high spatial resolution scanning electrochemical cell microscopy (SECCM) complemented with electron backscatter diffraction (EBSD) is demonstrated as a means of performing ‘pseudo-single-crystal’ electrochemical measurements at individual grains of a polycrystalline platinum electrode, while also allowing grain boundaries to be probed. Using the Fe2+/3+ couple as an illustrative case, a strong correlation is found between local surface structure and electrochemical activity. Variations in electrochemical activity for individual high index grains, visualized in a weakly adsorbing perchlorate medium, show that there is higher activity on grains with a significant (101) orientation contribution, compared to those with (001) and (111) contribution, consistent with findings on single-crystal electrodes. Interestingly, for Fe2+ oxidation in a sulfate medium a different pattern of activity emerges. Here, SECCM reveals only minor variations in activity between individual grains, again consistent with single-crystal studies, with a greatly enhanced activity at grain boundaries. This suggests that these sites may contribute significantly to the overall electrochemical behavior measured on the macroscale

Conducting fabrics of polyester coated with polypyrrole and doped with graphene oxide

Polyester (PES) has been coated with polypyrrole (PPy) to produce conducting fabrics. Graphene oxide (GO) has been used in different concentrations (10, 20 and 30% weight) as counter ion to neutralize the positive charges of the PPy structure. Fourier transform infrared spectroscopy with attenuated total reflection (FTIR-ATR), energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS) of the PPy/GO powders corroborated the incorporation of GO as counter ion due to the presence of O in the EDX spectrum, as well as an excess of C, arising from GO contribution. The doping level (N+/N) decreased with the GO content. Field emission scanning electron microscopy (FESEM) showed the formation of the PPy/GO coating and the incorporation of GO in the composite. Electrochemical impedance spectroscopy (EIS) in solid state and solution, cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM) were used to test the electrical properties and electroactivity of the fabrics. There was a decrease in the electrical properties and electroactivity as the GO content increased. The conductivity of the fabrics could be tuned by varying the GO content.Spanish Ministerio de Ciencia e Innovación (contract CTM2011-23583) for the financial support. Conselleria d'Educació, Formació i Ocupació (Generalitat Valenciana) for the Programa VALi+D Postdoctoral Fellowship. C2011-UMINHO-2C2T-01 FCT funding from Programa Compromisso para a Ciência 2008, Portugal. XPS studies were performed at CEMUP (University of Porto, Portugal) facilities. Electron Microscopy Service of the UPV (Universitat Politècnica de València) is gratefully acknowledged for help with FESEM and EDX characterization