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Hydrogen evolution reaction (HER) activities of self-assembled monolayers (SAMs) of [Mo3S7(S2CNMe2)3] and several other MoSx molecular clusters are presented on planer Au electrode. Our study suggests that such Mo-S clusters are unstable under HER reaction conditions of a strongly acidic electrolyte. The [Mo3S7(S2CNEt2)3]I monolayer prepared from DMF showed greater stability among all the studied precursors. The X-ray photoelectron spectroscopy (XPS) analysis on a monolayer of [Mo3S7(S2CNMe2)3]I in THF assembled on Au/ITO suggested sulfur-rich composition with S:Mo ratio of 2.278. The Mo-S monolayer clusters resulting from [Mo3S7(S2CNMe2)3]I in THF showed a Tafel slope of 75.74 mV dec&minus, 1 and required a lower overpotential of 410 mV to reach a high HER catalytic current density of 100 mA cm&minus, 2 compared to the other studied precursors. Surface coverage of the Mo-S clusters on the Au surface was confirmed by cyclic voltammetry (CV) curves from K3Fe(CN)6 and anodization of Au surface. Further, the rotating ring-disk electrode (RRDE) measurements were performed for the monolayer of [Mo3S7(S2CNMe2)3]I prepared in THF to study its reaction kinetics. The HER catalytic activity of such monolayer Mo-S clusters can further be improved by controlling the sulfur vacancy.

Oxygen reduction reaction (ORR) was studied on a silver polycrystalline electrode in different NaOH concentrations with a help of rotating disc and rotating ring disc electrodes. Soluble reaction intermediate was detected at all alkaline concentrations, but its concentration increased with an increase of the level of impurities. ORR is not NaOH concentration dependent at low concentrations (0.1 and 1 M). In 11 M NaOH ORR onsets at more positive potentials in the region where underpotential silver oxide formation shows less reversible behaviour. The nonlinear frequency response analysis spectra show significant qualitative difference with NaOH concentration indicating a high capability of this method for kinetic mechanism investigations.

The oxidation of Cu(II) complexes with tetra, penta and hexaglycine in borate buffer aqueous solution, by dissolved oxygen is strongly accelerated by sulfite. The formation of Cu(III) complexes with maximum absorbances at 250 nm (e = 9000 mol-1 L cm-1) and 365 nm (e = 7120 mol-1 L cm-1) was also characterized by using rotating ring-disk voltammetry, whose anodic and cathodic components were observed in voltammograms recorded in solutions containing Cu(II). Voltammograms, obtained at various rotation speeds, showed that the Cu(III) species electrochemically generated is not stable over the entire time window of the experiment and in solutions containing tetraglycine the overall limiting current is controlled by the kinetics of an equilibrium involving Cu(II) species.The calculated first order rate constant of the decomposition was 4.37x10-3 s-1. Electrochemical experiments carried out in Cu(II) solutions after the addition of relatively small amounts of sulfite demonstrated that the Cu(III) species formed in the chemical reaction is the same as the one collected at the ring electrode when Cu(II) is oxidized at the disk electrode in ring-disk voltammetry. The concentration of Cu(III) complexes is proportional to the amount of added sulfite and the results indicated that indirect analytical methods for sulfite may be developed by means of spectrophotometric or amperometric detection of the chemically generated product. A oxidação de complexos de Cu(II) com tetra, penta e hexaglicina, em solução aquosa de tampão borato, pelo oxigênio dissolvido é fortemente acelerada por sulfito. A formação de complexos de Cu(III) com máximos de absorbância em 250 nm (e = 9000 mol-1 L cm-1) e 365 nm (e = 7120 mol-1 L cm-1) foi também caracterizada usando-se voltametria com eletrodo rotativo disco-anel, na qual componentes anódicos e catódicos foram observados em voltamogramas registrados em solução contendo Cu(II). Voltamogramas, obtidos com várias velocidades de rotação, mostraram que a espécie de Cu(III) gerada eletroquimicamente não é estável em toda a janela de tempo do experimento, e em solução contendo tetraglicina a corrente limite é controlada pela cinética de um equilíbrio envolvendo espécies de Cu(II). O valor calculado da constante de decomposição de primeira ordem foi 4,37x10-3 s-1. Experimentos eletroquímicos realizados em solução de Cu(II) após a adição de quantidades relativamente pequenas de sulfito demonstraram que a espécie de Cu(III), formada na reação química, é a mesma que foi coletada no eletrodo anel quando Cu(II) é oxidado no eletrodo disco. A concentração dos complexos de Cu(III) é proporcional à quantidade de sulfito adicionada e os resultados indicaram a possibilidade de desenvolvimento de um método analítico indireto para sulfito, com detecção espectrofotométrica ou amperométrica do produto quimicamente gerado.