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The influence of surface chemistry on heterogeneous electron transfer at activated carbon (AC) electrodes was studied using scanning electrochemical microscopy (SECM) and conventional electrochemical measurements, which allow for measuring respectively the local and the overall electrode electron transfer rate constants. Using a thermal treatment in air and under argon, commercial activated carbons were either oxidized or defunctionalized. Both treatments lead to a slight decrease of the specific surface area of the material, without altering its pore size distribution and morphology. The nanogap voltammetry and approach curves obtained by SECM were used to characterize the rate constants at the interface between an aqueous solution of ferrocenemethanol (FcMeOH) and the AC electrodes. The heterogeneous electron transfer (HET) rate constant for the untreated AC was 3.4 10−2 ± 0.2 cm s−1 and was increased by about 2.5 and 1.5 times, after oxidizing and defunctionalizing the surface, respectively. SECM results showed that the heat treatment increases the conductivity of AC, and the oxidation of the surface increases the wettability and accessibility of the pores, which are assumed to promote the electron transfer. The local heterogeneous electron transfer rate constant values obtained by SECM are higher, by an order of magnitude, than the global ones obtained from conventional electrochemical macroelectrode measurements. The local information obtained by SECM is valuable for understanding the nanoscale interfacial mechanisms in porous carbon electrodes as a better understanding of the charge storage mechanism is key to improve their electrochemical performances. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract In this work, we report the use of pseudocapacitive RuO 2 in a porous carbon-based substrate as a composite electrode for high-performance capacitive deionization (CDI). RuO 2 was electrodeposited onto inexpensive activated carbon (AC) via cyclic voltammetry to optimize the composite electrode (denoted as RuO 2 (20)-AC) fabrication. The electrochemical measurements indicate that the composite electrode with a specific surface area of 576 m2/g and hydrophilicity yields an improved specific capacitance and good cycling stability. The notably enhanced performance is attributed to the presence of RuO 2 , which allows rapid Faradaic charge-transfer reactions as well as pseudocapacitive charge storage. These results confirm that incorporating RuO 2 onto an AC electrode effectively reduces the electrical resistance and enhances the charge efficiency. Furthermore, batch-mode CDI experiments were conducted at 1.2 V in a 5 mM NaCl solution. As evidenced, the RuO 2 (20)-AC composite has a promising salt adsorption capacity of 11.26 mg/g, which is 3.7-fold higher than that of pristine AC. Therefore, using the RuO 2 (20)-AC composite as the cathode, an enhanced desalination performance can be achieved through a mixed capacitive-Faradaic process, resulting from two removal mechanisms of capacitive electrosorption and pseudocapacitive redox reactions. This work provides an efficient strategy to utilize RuO 2 on porous carbon-based substrates to improve CDI performance. Highlights • RuO 2 /activated carbon composite electrodes were prepared for CDI. • Electrodeposited RuO 2 showed good pseudocapacitive charge storage. • The metallic conductivity of RuO 2 ensures rapid ion transport. • The composite had a superior salt electrosorption capacity. • The combination of capacitive electrosorption and Faradaic reactions enhanced the CDI performance. [ABSTRACT FROM AUTHOR]

Capacitive deionization (CDI) is an emerging technology that supplies deionized water to resolve the fresh water shortage. CDI electrodes are mainly made up of carbon materials, of which the deionization performance is closely related to their physical properties and structures. Hence, a rational design of electrode material structure is essentially significant. Functionalized graphene (fG) in particular has recently been regarded as characteristic CDI electrode material. However, preparation of fG based on graphene oxide usually results in serious secondary pollution due to usage of highly poisonous chemicals, and thus still cannot meet the demand of practical application. It is feasible that environmentally-friendly activated carbon (AC) and small amounts of fGs can be combined rationally, and used as CDI electrodes. Here, sono-assembled AC/m-phenylenediamine (mPEA) or p-phenylenediaminefG inter-connected network architecture has been constructed for the first time successfully. The specific capacitances of the AC/fG composites were found to be significantly higher than that of the AC electrode owing to mesoporous generation. Also, among all the samples, the AC composite with 5 wt % mPEA-fG exhibited an ultrahigh electrosorption capacity of 12.58 mg/g (or 0.22 mmol/g) in NaCl solution. These observations indicate that fG can serve as an efficient conductive bridge to decrease the aggregation of AC particles, and improve the electron transfer with the composite electrode. This work provides an effective strategy for the environmental and economical electrode architectures for general applications in CDI and energy storage. [ABSTRACT FROM AUTHOR]

• La-0.5% was less affected by the presence of competing anions than La-1.5%. • Chemisorption and electrosorption mechanisms in La-0.5% reduced the interference by other anions. • Charge and hydration played the major role in selectivity. • Hydroxyls from the La(III) clusters were exchanged by the studied anions. Here it is reported the electrosorption of fluoride in the presence of competing anions of environmental relevance (chloride, nitrate, sulfate, phosphate and arsenate) by two activated carbon electrodes impregnated with La(III), La-0.5% and La-1.5% (w/w %). The electrosorption kinetics were evaluated using equimolar initial concentrations (0.263 mM of each studied anion) in both binary solutions (F− vs. anion) and in a complex mixture comprising all anions simultaneously. For La-0.5%, the presence of nitrate and chloride did not significantly modify its fluoride removal (q = ∼19.25 µmol g−1), while these same anions decreased the fluoride removal of La-1.5% from 32.85 to 17.2 and 13.95 µmol g−1, for nitrate and chloride, respectively. In general, the divalent anions competed the most during the kinetics, decreasing the fluoride removal in both carbons; the lowest capacity values were 5.75 and 4 µmol g−1 for La-0.5% and La-1.5%, respectively. The increases in the pH of the solution corroborated that all anions anchored to the modified surface by a ligand-exchange mechanism involving the exposed hydroxyls from the La(III) clusters. The discussion of the results was not centered on the charge and the hydrated radius of the anions, but it was also expanded to other thermodynamic parameters that also denote selectivity, such as the hydration energies and mass-transport parameters. Electrochemical impedance spectroscopy was performed as a characterization technique in two electrolytes: 0.1 M NaF and the working solution, 0.263 mM NaF (5 ppm F− solution). The information obtained from the latter correlated the most with the electrosorption performance of the electrodes. [ABSTRACT FROM AUTHOR]

Abstract: An oxygen plasma treatment was employed to modify the surface of carbon electrodes used in capacitive deionization (CDI). X-ray photoelectron spectroscopy analysis of samples showed that oxygen plasma is mainly attaching oxygenated groups on the PTFE binder used in these electrodes. By functionalizing the binder it can increase the hydrophilicity of the electrode surface and increase the available specific surface area. 2.5min of plasma treatment resulted in the largest improvement of CDI performance of electrodes. Thermodynamic study of CDI performance showed that the modified electrodes followed Langmuir and Freundlich isotherms resulting from the increased interaction between the enhanced electrodes and water. The kinetic study showed that the CDI process followed a pseudo-first order adsorption kinetics. The calculated adsorption rate constants suggested that plasma modification can accelerate ion adsorption of electrodes. [Copyright &y& Elsevier]

Capacitive deionization (CDI) is an emerging technology as a sustainable low energy process for desalination of brackish water. Activated carbon electrodes are often used in the CDI devices. Electrosorption capacity was found to be improved on asymmetric electrode configuration using activated carbon cloth doped with fluorine due to redistribution of electric potential. This led to improvement in desalination performance up to 12.4 mg/g for a desalination cycle of 6 min employing an asymmetric fluorinated electrode as cathode (ACC//F-ACC). A relatively high charge efficiency of 77 % was obtained representing 92 % charge efficiency neglecting the leakage currents. Furthermore, the ion adsorption rate was found to improve substantially due to an increased surface conductivity of the fluorinated electrode confirmed by Mott-Schottky analysis. Energy consumption during desalination of 1000 ppm sodium chloride solution of 0.71kWh/m3 for symmetric electrode configuration was found to reduce by 36 % upon employing asymmetric configuration. This study shows some of the benefits of asymmetric configuration to achieve an optimal operation of CDI device, as well as improvements related to energy consumption. Image, graphical abstract [ABSTRACT FROM AUTHOR]