Spectroscopic characterization and investigation of the dynamic of charge compensation process of supramolecular films derived from tetra-2-pyridyl-1,4-pyrazine ligand

This work describes the infrared spectroscopy characterization and the charge compensation dynamics in supramolecular film FeTPPZFeCN derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) with hexacyanoferrate, as well as the hybrid film formed by FeTPPZFeCN and polypyrrole (PPy). For supramolecular film, it was found that anion flux is greater in a K+ containing solution than in Li+ solution, which seems to be due to the larger crystalline ionic radius of K+. The electroneutralization process is discussed in terms of electrostatic interactions between cations and metallic centers in the hosting matrix. The nature of the charge compensation process differs from others modified electrodes based on Prussian blue films, where only cations such as K+ participate in the electroneutralization process. In the case of FeTPPZFeCN/PPy hybrid film, the magnitude of the anions’s flux is also dependent on the identity of the anion of the supporting electrolyte.Este trabalho descreve a caracterização espectroscópica por infravermelho e o estudo da dinâmica de compensação de cargas do filme supramolecular FeTPPZFeCN derivado do ligante tetra-2-piridil-1,4-pirazina (TPPZ) com hexacianoferrato, bem como o filme híbrido envolvendo FeTPPZFeCN e uma matriz de polipirrol (PPy). Para o filme supramolecular, foi observado um aumento no fluxo de ânion em solução contendo K+ em relação ao Li+, que parece estar relacionado ao tamanho do raio iônico cristalino do K+. O processo de eletroneutralização é discutido em termos de interação eletrostática entre cátions e centros metálicos na matriz hospedeira. A natureza do processo de compensação de carga difere de outros eletrodos modificados derivados do azul da Prússia, onde somente cátions tais como K+ participam no processo de eletroneutralização. No caso do filme híbrido FeTPPZFeCN/PPy, a magnitude do fluxo de ânions é também dependente da identidade do ânion em diferentes eletrólitos de suporte.FAPESPConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)SP

Macroporous MnO2 electrodes obtained by template assisted electrodeposition for electrochemical capacitors

Macroporous MnO2 electrodes prepared by template-assisted electrodeposition using spherical polystyrene colloidal particles are studied. The wettability of such electrodes by a LiClO4 aqueous electrolyte is measured by the contact angle technique. Cyclic voltammetry experiments are performed in order to evaluate the use of these electrodes for electrochemical capacitor applications. The specific capacity obtained is about 60% higher than that obtained for flat MnO2 surfaces showing that, in spite of the wettability being lower, some penetration of the electrolyte into the pores must occur, increasing the electroactive area with respect to the flat electrode. Furthermore, the macroporous electrode showed excellent electrochemical stability, with neither a capacitance decrease nor a loss of morphology, after 1000 cycles

Challenges and opportunities in the bottom-up mechanochemical synthesis of noble metal nanoparticles

Mechanochemistry is a promising alternative to solution-based protocols across the chemical sciences, enabling different types of chemistries in solvent-free and environmentally benign conditions. The use of mechanical energy to promote physical and chemical transformations has reached a high level of refinement, allowing for the design of sophisticated molecules and nanostructured materials. Among them, the synthesis of noble metal nanoparticles deserves special attention due to their catalytic applications. In this review, we discuss the recent progress on the development of mechanochemical strategies for the controlled synthesis of noble metal nanostructures. We start by covering the fundamentals of different preparation routes, namely top-down and bottom-up approaches. Next, we focus on the key examples of the mechanochemical synthesis of non-supported and supported metal nanoparticles as well as hybrid nanomaterials containing noble metals. In these examples, in addition to the principles and synthesis mechanisms, their performances in catalysis are discussed. Finally, a perspective of the field is given, where we discuss the opportunities for future work and the challenges of mechanochemical synthesis to produce well-defined noble metal nanoparticles.Peer reviewe

Kinetic and Thermodynamic Studies on the Adsorption of Reactive Red 239 by Carra Sawdust Treated with Formaldehyde

In this study, carra sawdust pre-treated with formaldehyde was used to adsorb reactive red 239 (RR239). The effects of several experimental conditions, including the concentration of dye, sorbent dosage, temperature, ionic strength, stirring speed and solution pH, on the kinetics of the adsorption process have been studied, and the experimental data were fitted to pseudo-second-order model. A study of the intra-particle diffusion model indicates that the mechanism of dye adsorption using carra sawdust is rather complex and is most likely a combination of external mass transfer and intra-particle diffusion. The experimental data obtained at equilibrium were analyzed using the Langmuir and Freundlich isotherm models, and the results indicated that at this concentration range, both models can be applied for obtaining the equilibrium parameters. The maximum dye uptake obtained at 298 K was found to be 15.1 mg g(-1). In contrast to the usual systems, the reactive dye studied in the present work is strongly attached to the sawdust even after several washes with water, allowing it to be discarded as a solid waste.FAPESP [2010/08646-9, 2012/02117-0, 2009/53199-3]FAPESPINCT in Bioanalytics (FAPESP) [08/57805-2]INCT in Bioanalytics (FAPESP)CNPq [490116/2007-8]CNP

Using Polymeric Ionic Liquids as an Active Binder in Supercapacitors

Electrodes in batteries and supercapacitors generally contain inert binders to maintain their structural integrity during operation but do not participate in the storage of energy. In this paper, we demonstrate that poly ionic liquids can function as structural binders while simultaneously improving the energy storage capability of supercapacitors. Specifically, we show that when the ionic liquid N-butyl-N-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide is used as electrolyte and poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide is employed as electrode binder the permissible operating voltage of the device is enhanced to 4.0 V. This results in a substantially increased overall specific energy (80% greater) and represents a step toward the development of devices with long cycle lives and high energy densities

Lithium intercalation in nanostructured thin films of a mixed-valence layered vanadium oxide using an ionic liquid electrolyte

AbstractNanostructured thin films of a mixed-valence, layered vanadium oxide were prepared using layer-by-layer deposition. The thin films were characterized by electronic (UV–vis) spectroscopy, quartz crystal microbalance, profilometry and scanning electron microscopy techniques. The highest charge capacity was obtained for films that consisted of 25 bilayers. The electrochemical characterization of the films was performed in conventional organic solvent and ionic liquid (IL) based electrolytes. The results revealed better performance, in terms of stability during consecutive charge/discharge cycles, when ILs were employed. This can be attributed to several factors, including reduced mechanical stress caused by insertion of more than 1 mol of Li+ per mol of V5+ in the film structure, decrease of crystallinity in the electrode material during the first few charge/discharge cycles and/or formation of a more compatible SEI. Nanostructured thin films of layered vanadium oxide prepared using layer-by-layer deposition showed potential for applications in lithium microbatteries

Four Phosphonium-based Ionic Liquids. Synthesis, Characterization and Electrochemical Performance as Electrolytes for Silicon Anodes

Herein, we describe the synthesis, characterization and electrochemical performance of four phosphonium-based ionic liquids (ILs) as electrolytes, Physicochemical properties such as viscosity, density, ionic conductivity, and thermal stability of ILs and conventional organic solvent ethylene carbonate (EC)/diethyl carbonate (DEC) were experimentally determined at different temperatures. All ILs showed thermal stability greater than 300 degrees C, surpassing the stability of the conventional organic solvent, whose flash points were 145 and 23 degrees C for EC and DEC, respectively. Nevertheless, at room temperature, all ILs are much more viscous than EC/DEC. The composite Si -[P-2224][FSI] (triethyl-n-butylphosphonium bis(fluoromethylsulfonyl)imide) and Si-EC/DEC anodes exhibit initial specific capacities at 0.15 A/g of 2409 and 2631 mAh/g, respectively. This demonstrates that despite the inferior transport properties of ILs, short alkyl-substituted phosphonium ILs like [P-2224][FSI] are potentially competitive for the new generation of electrolytes for LIBs. NMR, DSC, TGA, and galvanostatic discharged/charged were used as characterization techniques.Peer reviewe

In situ-formed nitrogen-doped carbon/silicon-based materials as negative electrodes for lithium-ion batteries

The development of negative electrode materials with better performance than those currently used in Li-ion technology has been a major focus of recent battery research. Here, we report the synthesis and electrochem-ical evaluation of in situ-formed nitrogen-doped carbon/SiOC. The materials were synthesized by a sol-gel pro-cess using 3-(aminopropyl)triethoxysilane (APTES), sodium citrate and glycerol. The electrochemical performance of pyrolyzed materials was studied using poly(acrylic acid) binder and commercial organic elec-trolyte. Our reported approach enables changes in both the amount of nitrogen and the morphology as a func-tion of the molar ratio of APTES:citrate and reaction time. Spherical-shaped NC/SiOC composite electrodes deliver a delithiation capacity of 622 mAh/g at 0.1 A/g and an initial coulombic efficiency of-63%, while in the large bulk material, respective values of 367 mAh/g and-55% were obtained. After 1000 charge/dis-charge cycles at 1.6 A/g, the latter material exhibits 98% of the initial capacity once it returned to lower cur-rent cycling. Overall, our results indicate that NC/SiOC materials are quite promising for electrochemical applications since both their large capacity and stability demonstrate superior performance compared to tradi-tional graphite. Moreover, our synthesis is simple and, more importantly, environmentally friendly chemicals, such as sodium citrate and glycerol, are used.Peer reviewe

Tandem X-ray absorption spectroscopy and scattering forin situtime-resolved monitoring of gold nanoparticle mechanosynthesis

Current time-resolvedin situapproaches limit the scope of mechanochemical investigations possible. Here we develop a new, general approach to simultaneously follow the evolution of bulk atomic and electronic structure during a mechanochemical synthesis. This is achieved by coupling two complementary synchrotron-based X-ray methods: X-ray absorption spectroscopy (XAS) and X-ray diffraction. We apply this method to investigate the bottom-up mechanosynthesis of technologically important Au micro and nanoparticles in the presence of three different reducing agents, hydroquinone, sodium citrate, and NaBH4. Moreover, we show how XAS offers new insight into the early stage generation of growth species (e.g.monomers and clusters), which lead to the subsequent formation of nanoparticles. These processes are beyond the detection capabilities of diffraction methods. This combined X-ray approach paves the way to new directions in mechanochemical research of advanced electronic materials.Peer reviewe