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This paper aims to understand the differences in the oxidation of ferrocene in several scenarios. The first scenario focuses the direct oxidation of ferrocene in an aqueous conventional support electrolyte and the second one is when ferrocene is directly placed in mineral oil, forming an oil phase and causing an oil/water interface. Additional experiments were also conducted in an emulsion, which was constituted by ferrocene in oil and mixed with conventional electrolytes and tetrabutylammonium chloride (TBAC). A Boron-Doped Diamond Electrode (BDD) was used as the working electrode. We observed an approximately 0.07 V shift when the ferrocene oxidation was conducted at the oil/water interface compared with the direct oxidation in the conventional aqueous phase. This potential shift was also calculated using the Density Functional Theory (DFT) as a theoretical tool. An additional comparison was conducted related to the interface and emulsions, finding that the ionic strength is the most determining factor in these types of electrochemical studies. Finally, Tafel plots indicated that the reaction mechanisms and reaction geometry are different when the electrode is placed at the interface versus directly in the aqueous phase. [ABSTRACT FROM AUTHOR]

In this work, we synthesize a sandwich-structured graphite-metallic silicon@C (MS-G@C) composite, which shows good electrochemical performance compared to metallic silicon or graphite-metallic silicon. The improved electrochemical performance may be ascribed to the sandwich structure of the composite with the carbon coating on metallic Si and to the metallic Si particles with high electronic conductivity according to the results of four probe tester measurement and a density functional theory study. When evaluated as an anode material for LIBs, the low cost MS-G@C anodes Exhibit 830 mA h g −1 at 0.5 C, 650 mA h g −1 at 1 C, and 251.2 mA h g −1 at 5 C, respectively, and after 100 cycles with an average capacity loss of only 0.02% per cycle at 0.5 C. The synthetic method presented in this paper is provided a facile and low-cost strategy for the large-scale production of silicon-based material as an anode in LIBs. [ABSTRACT FROM AUTHOR]

• Full characterization of NiII( tpa ) complexes gives information about its electronic structure which corelates with electrochemical behavior. • NiII( tpa ) complexes presented tunable redox potential for the NiII/NiI reduction. • NiII complex with more negative redox potential presented the high catalytic activity for CO 2 reduction. • Theoretical approach was useful for the analysis and description of electrochemical mechanisms. In this paper, we report the synthesis, characterization, as well as electrochemical, spectroelectrochemical, and density functional theory (DFT) calculations of a series of novel NiII complexes with a flexible tetradentate ligand, tris(2-pyridylmethyl)amine) ( tpa ). The complexes [NiII( tpa )(H 2 O)(MeCN)](BF 4) 2 , [NiII( tpa )(NO 3) 2 ], and [NiII( tpa )Cl 2 ] were studied for their ability to electrochemically reduce CO 2. These complexes were compared with the tris-chelate complex [Ni(bpy) 3 ](BF 4) 2 to understand the role of flexible tetradentate ligands containing a pyridinic ring in the electrochemical reduction of CO 2. Spectroelectrochemical experiments and theoretical studies were performed to rationalize the electrochemical reductions occurring and to predict the redox potential and pathway of CO 2 reduction. The electrochemical behavior of Ni(II) complexes with the ligand tris(2-pyridylmethyl)amine) was studied, in order to explore its ability to reduce electrochemically CO 2. Theoretical studies allowed to rationalize where the electrochemical reductions occur and predict redox potential and the pathway of CO 2 reduction. [Display omitted] [ABSTRACT FROM AUTHOR]