Improved Operation of Chloralkaline Reversible Cells with Mixed Metal Oxide Electrodes Made Using Microwaves.

This study focuses on the synthesis of mixed metal oxide anodes (MMOs) with the composition Ti/RuO2Sb2O4Ptx (where x = 0, 5, 10 mol) using hybrid microwave irradiation heating. The synthesized electrodes were characterized using scanning electron microscopy, X-ray energy-dispersive analysis, X-ray diffraction, cyclic voltammetry, and electrochemical impedance spectroscopy. These electrodes were then evaluated in both bulk electrolytic and fuel cell tests within a reversible chloralkaline electrochemical cell. The configurations using the electrodes Ti/(RuO2)0.7-(Sb2O4)0.3 and Ti/(RuO2)66.5-(Sb2O4)28.5-Pt5 presented lower onset potential for oxygen and chlorine evolution reactions and reduced resistance to charge transfer compared to the Ti/(RuO2)63-(Sb2O4)27-Pt10 variant. These electrodes demonstrated notable performance in reversible electrochemical cells, achieving Coulombic efficiencies of up to 60% when operating in the electrolytic mode at current densities of 150 mA cm-2. They also reached maximum power densities of 1.2 mW cm-2 in the fuel cell. In both scenarios, the presence of platinum in the MMO coating positively influenced the process. Furthermore, a significant challenge encountered was crossover through the membranes, primarily associated with gaseous Cl2. This study advances our understanding of reversible electrochemical cells and presents possibilities for further exploration and refinement. It demonstrated that the synergy of innovative electrode synthesis strategies and electrochemical engineering can lead to promising and sustainable technologies for energy conversion.

Recent advances on modified reticulated vitreous carbon for water and wastewater treatment - A mini-review.

Recently, modifications on reticulated vitreous carbon (RVC) have attracted attention as a promising strategy to produce low-cost, stable, and highly active electrodes leading to significant advances in the water/wastewater treatment field compared with raw RVC. Modified RVC materials have been used as cathode, anode, and membrane. Improvements on physical and electrocatalytic properties are achieved by RVC modification via diverse strategies, including the deposition of metal oxides, the introduction of surface functional groups, and the formation of composites, which were used to remove organic contaminants and pathogens from water matrices, as summarized in this mini-review. This mini-review mainly focused on papers published from 2015 to 2020 that reported modified RVC electrodes to eliminate pollutants and pathogens from water matrices by electrochemical advanced oxidation processes. Likewise, news challenges and opportunities are discussed, and perspectives for the ongoing and future studies in this research field are also given.

Improved 4-nitrophenol removal at Ti/RuO2-Sb2O4-TiO2 laser-made anodes.

In this study, binary and ternary mixed metal oxide anodes of Ti/RuO2-Sb2O4 and Ti/RuO2-Sb2O4-TiO2 were prepared using two different heating methods: conventional furnace and alternative CO2 laser heating. The produced anodes were physically and electrochemically characterized by using different techniques. The main difference found in the laser-made anodes was their more compact morphology, without the common deep cracks found in anodes made by typical thermal decomposition, which showed an important correlation with the prolonged accelerated service life. The correlation between the physicochemical properties of the anodes with their performance towards the 4-nitrophenol oxidations is discussed. The results demonstrated that the ternary anode (Ti/RuO2-Sb2O4-TiO2) is very promising, presenting a kinetic 5.7 times faster than the respective binary anode and the highest removal efficiency when compared with conventionally made anodes. Also, the lowest energy consumption per unit of mass of contaminant removed is seen for the laser-made Ti/RuO2-Sb2O4-TiO2 anode, which evidences the excellent cost-benefit of this anode material. Finally, some by-products were identified, and a degradation route is proposed. Graphical abstract.

A Comparative Study of the Catalytic Performance of Pt-Based Bi and Trimetallic Nanocatalysts Towards Methanol, Ethanol, Ethylene Glycol, and Glycerol Electro-Oxidation.

Carbon-supported platinum is used as an anode and cathode electrocatalyst in low-temperature fuel cells fueled with low-molecular-weight alcohols in fuel cells. The cost of Pt and its low activity towards the complete oxidation of these fuels are significant barriers to the widespread use of these types of fuel cells. Here, we report on the development of PtRhNi nanocatalysts supported on carbon made using a reduction chemistry method with different atomic rates. The catalytic activity of the developed catalysts towards the electro-oxidation of methanol, ethanol, ethylene glycol, and glycerol in acidic media was studied. The obtained catalysts performances were compared with both commercial Pt/C and binary Pt75Ni25/C catalyst. The nanostructures were characterized, employing inductively coupled plasma optical emission spectrometer, X-ray diffraction, scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The binary catalyst presents a mean particle size of around 2 nm. Whereas the ternary catalysts present particles of similar size and with some large alloy and core-shell structures. The alcohol oxidation onset potential and the current density measured after 3600 s of chronoamperometry were used to classify the catalytic activity of the catalysts towards the oxidation of methanol, ethanol, ethylene glycol, and glycerol. The best PtRhNi/C catalyst composition (i.e., Pt43Rh43Ni14/C) presented the highest activity for alcohols oxidation compared with all catalysts studied, indicating the proper tuning composition influence in the catalytic activity. The enhanced activity of Pt43Rh43Ni14/C can be attributed to the synergic effect of trimetallic compounds, Pt, Ni, and Rh.

The Effect of Pt Loading on Catalytic Activity of Pb0.25@Ptx/C Nanocomposites Toward Ethanol Oxidation.

Here, we study the influence of the Pt loading and the particle size of Pb0.25@Ptx/C catalysts on their specific activity toward ethanol oxidation in acid media. High angle annular dark field-scanning transmission electron microscopy and electron energy loss spectroscopy data indicate the formation of Pb0.25@Ptx/C core-shell structures, which are well dispersed on carbon support, with spherical shapes and small particle sizes (2.9-6.6 nm). Cyclic voltammetry experiments confirm characteristic profiles of polycrystalline Pt for Pb0.25@Ptx/C structures. The specific activity of the catalysts toward ethanol oxidation reaction greatly depends on the Pt content on Pb core, and consequently, depends on the size of the nanoparticles. The optimum activity occurs with the lowest Pt load in the shell and smaller particle size. Enhancements in specific activity result from the higher number of nanoparticles available for the ethanol oxidation reaction and the tensile strain effect of Pt atoms on the surface expanded in Pb0.25@Pt0.75/C. The lower activity observed for the catalysts with loads of 35 and 50% wt. (Pb0.25@Pt1.5 and Pb0.25@Pt2.25/C, respectively) in comparison to Pt/C, could be explain by the larger particle sizes obtained at these catalysts. Moreover, the Pb0.25@Pt0.75/C catalyst has high electrochemical stability and should be more stable in direct ethanol fuel cells systems than monolithic Pt catalysts. This is because the Pt shell in Pb0.25@Pt0.75/C exhibits lower chemical potential (p < 0) than at Pt/C and at the other core-shell catalysts studied; thus, reducing its tendency to dissolve. The developed core-shell nanostructure is thus a potential candidate as high-performance anode catalyst for application in direct ethanol fuel cells.

Synthesis of Ni-SiO2/C Supported Platinum Catalysts for Improved Electrochemical Activity Towards Ethanol Oxidation.

A series of Pt/Ni-SiO2/C catalysts with different mass proportions of Ni-SiO2/C (0:100, 30:70, 50:50, 70:30 and 100:0) were prepared and studied towards ethanol electrochemical oxidation in acid medium. The support silica particles were initially synthesized via sol-gel and then modified with NiCl2. The Ni deposited on the silica surface plays a role promoting nucleation sites for the reduction of platinum. Pt was further chemically reduced onto Ni-SiO2 using formic acid and loaded onto carbon Vulcan XC-72 R. The Pt/Ni-SiO2/C catalysts were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, temperature-programmed reduction, X-ray photoelectron spectroscopy, transmission electron microscopy and inductively coupled plasma-optical emission spectroscopy. The physical characterizations reveal the formation of oxide-metal composite and strong interaction between Pt and the Ni-SiO2 composite. The Pt/Ni-SiO2/C catalyst with meso/macroporous structure exhibits higher electrocatalytic activity towards ethanol oxidation and better stability, after 48 h of electrolysis, than a commercial Pt/C catalyst. These improved features could be due to presence of Ni-SiO2 composite that promotes corrosion resistance of the support and prevents the aggregation of Pt nanoparticles and their detachment from the support. The low poisoning of the Pt/Ni-SiO2/C catalyst is probably due to the enhanced oxygen content on the composite surface. The high electrocatalytic activity and enhanced electrochemical stability of the Pt/Ni-SiO2/C catalyst make it promising for further fuel cell applications.

Methanol Electro-Oxidation on Carbon-Supported PtRu Nanowires.

One of the key objectives in fuel cell technology is to improve the alcohol oxidation efficiency of Pt-based catalysts. A series of carbon-supported PtRu nanowires with different concentrations of Pt and Ru were prepared for application in methanol oxidation in acid media. The physicochemical properties and electrocatalytic activity of these catalysts during methanol oxidation are function on their structure, morphology and composition. A Pt60Ru40/C catalyst shows the best behaviour towards methanol electro-oxidation allowing decrease the onset potential approximately 0.2 V respect to others PtRu/C synthesised nanowires. The structural modification of Pt by Ru and synergetic character of RuPt are main factors that could contribute to reduction of energy necessary for electro-oxidation process. The Pt and PtRu nanowires have different sizes and distribution on the substrate. The average crystallite sizes, found by XRD, are in the 4.6-5.9 nm range and the lattice parameter is between 0.3903-0.3908 nm. Small differences with the values of the Pt/C catalyst were found. The XPS results show a prevailing presence of metallic Pt and Ru4+ species.

Electrochemical and/or microbiological treatment of pyrolysis wastewater.

Electrochemical oxidation may be used as treatment to decompose partially or completely organic pollutants (wastewater) from industrial processes such as pyrolysis. Pyrolysis is a thermochemical process used to obtain bio-oil from biomasses, generating a liquid waste rich in organic compounds including aldehydes and phenols, which can be submitted to biological and electrochemical treatments in order to minimize its environmental impact. Thus, electrochemical systems employing dimensionally stable anodes (DSAs) have been proposed to enable biodegradation processes in subsurface environments. In order to investigate the organic compound degradation from residual coconut pyrolysis wastewater, ternary DSAs containing ruthenium, iridium and cerium synthetized by the 'ionic liquid method' at different calcination temperatures (500, 550, 600 and 700 °C) for the pretreatment of these compounds, were developed in order to allow posterior degradation by Pseudomonas sp., Bacillus sp. or Acinetobacter sp. bacteria. The electrode synthesized applying 500 °C displayed the highest voltammetric charge and was used in the pretreatment of pyrolysis effluent prior to microbial treatment. Regarding biological treatment, the Pseudomonas sp. exhibited high furfural degradation in wastewater samples electrochemically pretreated at 2.0 V. On the other hand, the use of Acinetobacter efficiently degraded phenolic compounds such as phenol, 4-methylphenol, 2,5-methylphenol, 4-ethylphenol and 3,5-methylphenol in both wastewater samples, with and without electrochemical pretreatment. Overall, the results indicate that the combination of both processes used in this study is relevant for the treatment of pyrolysis wastewater.

Electrochemical mineralization of cephalexin using a conductive diamond anode: A mechanistic and toxicity investigation.

The contamination of surface and ground water by antibiotics is of significant importance due to their potential chronic toxic effects to the aquatic and human lives. Thus, in this work, the electrochemical oxidation of cephalexin (CEX) was carried out in a one compartment filter-press flow cell using a boron-doped diamond (BDD) electrode as anode. During the electrolysis, the investigated variables were: supporting electrolyte (Na2SO4, NaCl, NaNO3, and Na2CO3) at constant ionic strength (0.1 M), pH (3, 7, 10, and without control), and current density (5, 10 and 20 mA cm-2). The oxidation and mineralization of CEX were assessed by high performance liquid chromatography, coupled to mass spectrometry and total organic carbon. The oxidation process of CEX was dependent on the type of electrolyte and on pH of the solution due to the distinct oxidant species electrogenerated; however, the conversion of CEX and its hydroxylated intermediates to CO2 depends only on their diffusion to the surface of the BDD. In the final stages of electrolysis, an accumulation of recalcitrant oxamic and oxalic carboxylic acids, was detected. Finally, the growth inhibition assay with Escherichia coli cells showed that the toxicity of CEX solution decreased along the electrochemical treatment due to the rupture of the ß-lactam ring of the antibiotic.

Morphological dependence of silver electrodeposits investigated by changing the ionic liquid solvent and the deposition parameters.

The low toxicity and environmentally compatible ionic liquids (ILs) are alternatives to the toxic and harmful cyanide-based baths used in industrial silver electrodeposition. Here, we report the successful galvanostatic electrodeposition of silver films using the air and water stable ILs 1-ethyl-3-methylimidazolium trifluoromethylsulfonate ([EMIM]TfO) and 1-H-3-methylimidazolium hydrogen sulphate ([HMIM(+)][HSO4(-)]) as solvents and AgTfO as the source of silver. The electrochemical deposition parameters were thoughtfully studied by cyclic voltammetry before deposition. The electrodeposits were characterized by scanning electron microscopy coupled with X-ray energy dispersive spectroscopy and X-ray diffraction. Molecular dynamics (MD) simulations were used to investigate the structural dynamic and energetic properties of AgTfO in both ILs. Cyclic voltammetry experiments revealed that the reduction of silver is a diffusion-controlled process. The morphology of the silver coatings obtained in [EMIM]TfO is independent of the applied current density, resulting in nodular electrodeposits grouped as crystalline clusters. However, the current density significantly influences the morphology of silver electrodeposits obtained in [HMIM(+)][HSO4(-)], thus evolving from dendrites at 15 mA cm(-2) to the coexistence of dendrites and columnar shapes at 30 mA cm(-2). These differences are probably due to the greater interaction of Ag(+) with [HSO4(-)] than with TfO(-), as indicated by the MD simulations. The morphology of Ag deposits is independent of the electrodeposition temperature for both ILs, but higher values of temperature promoted increased cluster sizes. Pure face-centred cubic polycrystalline Ag was deposited on the films with crystallite sizes on the nanometre scale. The morphological dependence of Ag electrodeposits obtained in the [HMIM(+)][HSO4(-)] IL on the current density applied opens up the opportunity to produce different and predetermined Ag deposits.