Synthesis and performance of binder-free porous carbon electrodes in electrochemical capacitors.

Porous binder-free carbon electrodes were obtained by impregnating cellulose filter papers with phenolic resin through soft-salt template synthesis and thermal pyrolysis. These self-standing electrodes were used directly in a supercapacitor device. To understand the impacts of filter paper (FP) thickness on carbon filter paper (CFP) morphology, porosity, and surface functionalities, five different materials were examined. The CFP electrode thickness was adjusted linearly with the FP thickness to produce electrodes ranging from 100 to ∼800 µm. As the thickness of the CFP increased, there was an increase in the specific surface area and oxygen-based functionalities. Electrochemical testing in a 1 M KOH aqueous electrolyte demonstrated that electrode thickness played a key role in electrochemical capacitor (EC) performance, i.e., capacitance enhances linearly when the electrode becomes thinner. For low thicknesses (<280 µm), the capacitance and rate capability decreased slightly with increasing thickness; for high thicknesses, the performance drastically degraded despite the high specific surface area and oxygen surface functionalities. This effect was amplified at high regimes, indicating that high electrode thicknesses and fiber diameters limited electrolyte diffusion in the applied synthesis conditions. Thus, the high material porosity was inaccessible to ion adsorption. Consequently, thinner electrodes showed the highest capacitance (197 F g-1 at 0.1 A g-1) and rate capability (81%) values, exceeding those of their traditional binder-electrode counterparts prepared under similar conditions. Finally, for alkali metal hydroxide solutions, 1 M KOH exhibited a cation match with the salt template (KCl), while CsOH achieved additional capacitance retention (88% at 10 A g-1). Complex ion adsorption mechanisms were observed through a quartz crystal microbalance.

How to Quantify the Adsorption of Cyanuric Acid on Activated Carbon Used from Swimming Pool Disinfection?

The physical and chemical characteristics of an adsorbent are key factors determining its efficiency in relation to a particular adsorbate molecule. The adsorption of cyanuric acid (cya) on activated carbon (AC) has not been extensively explored in terms of its basic phenomenon and specific surface interactions. Cya is an important molecule in the swimming pool industry, as it protects free chlorine from UV light degradation. A proper characterization of AC will be beneficial for swimming pool product suppliers to determine the criteria while purchasing it to remove excess cya accumulated in pools. A detailed investigation of the physicochemical properties of activated carbon was conducted to assess its potential to adsorb cya from water. The effect of the adsorption capacity under various pH conditions was studied and it was found that acidic pH favors the adsorption process. With the help of temperature-programmed desorption coupled with mass spectrometry (TPD-MS) and X-ray photoelectron spectroscopy (XPS), the surface chemistry was well analyzed for a proper understanding of the adsorbent-adsorbate interaction. While conventional pool test equipment gives inconsistent readings of the cya concentration, a UV-vis spectroscopy-based methodology has been developed to accurately measure traces of cya in water. This method can be helpful to validate the accuracy of pool-testers for research and development purposes. The batch adsorption experiments revealed that cya adsorption on activated carbon follows pseudo-second-order kinetics, which confirms that the adsorption mechanism is chemisorption, which in fact, depends highly on the surface chemistry of the AC and the reaction pH.

Enhanced Performance of KVPO4F0.5O0.5 in Potassium Batteries by Carbon Coating Interfaces.

Potassium vanadium oxyfluoride phosphate of composition KVPO4F0.5O0.5 was modified by a carbon coating to enhance its electrochemical performance. Two distinct methods were used, first, chemical vapor deposition (CVD) using acetylene gas as a carbon precursor and second, an aqueous route using an abundant, cheap, and green precursor (chitosan) followed by a pyrolysis step. The formation of a 5 to 7 nm-thick carbon coating was confirmed by transmission electron microscopy and it was found to be more homogeneous in the case of CVD using acetylene gas. Indeed, an increase of the specific surface area of one order of magnitude, low content of C sp2, and residual oxygen surface functionalities were observed when the coating was obtained using chitosan. Pristine and carbon-coated materials were compared as positive electrode materials in potassium half-cells cycled at a C/5 (C = 26.5 mA g-1) rate within a potential window of 3 to 5 V vs K+/K. The formation by CVD of a uniform carbon coating with the limited presence of surface functions was shown to improve the initial coulombic efficiency up to 87% for KVPFO4F0.5O0.5-C2H2 and to mitigate electrolyte decomposition. Thus, performance at high C-rates such as 10 C was significantly improved, with ∼50% of the initial capacity maintained after 10 cycles, whereas a fast capacity loss is observed for the pristine material.

Link between Alkali Metals in Salt Templates and in Electrolytes for Improved Carbon-Based Electrochemical Capacitors.

Various alkali metal (Li+, Na+, K+, Rb+, and Cs+) chlorides with Pluronic F127 were used as a soft-salt template for tuning the textural and structural properties of carbon. Highly conductive metal hydroxide solutions, where the cations are the same as those in the salt template, have been used as electrolytes. By increasing the size of the cation in the template, the textural properties of carbon, such as the specific surface area, micropore volume, and pore size, were remarkably enhanced. It directly translates to an increase in the specific capacitance of the electrode material. For a constant current charge/discharge at 0.1 A g-1, the electrode composed of LiCl-T and operating with 1 mol L-1 LiOH demonstrates the capacitance of 124 F g-1, whereas CsCl-T with the same electrolyte has a capacitance of 216 F g-1. Moreover, the materials show the highest capacitance retention (up to 75%) vs. the current regime applied when the cation used during synthesis matches the cation present in the electrolyte (i.e., LiCl-T with LiOH). Interestingly, capacitance normalized by specific surface area has been found to be the highest when LiOH solution is applied as an electrolyte. Thus, for this metric, the size of ions seems to be a crucial parameter. The importance of mesoporosity is highlighted as well by using materials with a similar fraction of micropores and with or without mesopores. Briefly, the presence of mesopore fraction proved to be essential for improved capacity retention (69% vs. 30%). Besides textural properties, the graphitization degree impacts the electrochemical performance as well. It increases among the samples, in accordance with cation-π binding energy, e.g., LiCl-T is the most "graphitic-like" material and CsCl-T is the most disordered. Thus, the more graphitic-like materials demonstrate higher rate capability and cycle stability.

Olive mill wastewater: From a pollutant to green fuels, agricultural and water source and bio-fertilizer - Hydrothermal carbonization.

Hydrothermal carbonization (HTC) is considered as a promising technique for wastes conversion into carbon rich materials for various energetic, environmental and agricultural applications. In this work, the HTC of olive mill wastewater (OMWW) was investigated at different temperatures (180-220 °C) and both, the solid (i.e., hydrochars) and the final process liquid derived from the thermal conversion process were deeply analyzed. Results showed that the solid yield was affected by the temperature, i.e., decrease from 57% to 25% for temperatures of 180 °C and 220 °C, respectively. Furthermore, the hydrochars presented an increasing fixed carbon percentage with the increase of the carbonization temperature, suggesting that decarboxylation is the main reaction driving the HTC process. The decrease in the O/C ratio promoted an increase of the high heating value (HHV) by 32% for hydrochar prepared at 220 °C. The process liquids were sampled and their organic contents were analyzed using GC-MS technique. Acids, alcohols, phenols and sugar derivatives were detected and their concentrations varied with carbonization temperatures. The assessment of the physico-chemical properties of the generated HTC by-products suggested the possible application of the hydrochars for energetic insights while the liquid fraction could be practical for in agricultural field.

Palladium nanoparticles embedded in mesoporous carbons as efficient, green and reusable catalysts for mild hydrogenations of nitroarenes.

The reduction of nitroarenes is the most efficient route for the preparation of aromatic primary amines. These reductions are generally performed in the presence of heterogeneous transition metal catalysts, which are rather efficient but long and tedious to prepare. In addition, they contain very expensive metals that are in most cases difficult to reuse. Therefore, the development of efficient, easily accessible and reusable Pd catalysts obtained rapidly from safe and non-toxic starting materials was implemented in this report. Two bottom-up synthesis methods were used, the first consisted in the impregnation of a micro/mesoporous carbon support with a Pd salt solution, followed by thermal reduction (at 300, 450 or 600 °C) while the second involved a direct synthesis based on the co-assembly and pyrolysis (600 °C) of a mixture of a phenolic precursor, glyoxal, a surfactant and a Pd salt. The obtained composites possess Pd nanoparticles (NPs) of tunable sizes (ranging from 1-2 to 7.0 nm) and homogeneously distributed in the carbon framework (pores/walls). It turned out that they were successfully used for mild and environment-friendly hydrogenations of nitroarenes at room temperature under H2 (1 atm) in EtOH in the presence of only 5 mequiv. of supported Pd. The determinations of the optimal characteristics of the catalysts constituted a second objective of this study. It was found that the activity of the catalysts was strongly dependent on the Pd NPs sizes, i.e., catalysts bearing small Pd NPs (1.2 nm obtained at 300 °C and 3.4 nm obtained at 450 °C) exhibited an excellent activity, while those containing larger Pd NPs (6.4 nm and 7.0 nm obtained at 600 °C, either by indirect or direct methods) were not active. Moreover, the possibility to reuse the catalysts was shown to be dependent on the surface chemistry of the Pd NPs: the smallest Pd NPs are prone to oxidation by air and their surface was gradually covered by a PdO shell decreasing their activity during reuse. A good compromise between intrinsic catalytic activity (i.e. during first use) and possibility of reuse was found in the catalyst made by impregnation followed by reduction at 450 °C since the hydrogenation could be performed in only 2 h in EtOH or even in water. The catalyst was quantitatively recovered after reaction by filtration, used at least 7 times with no loss of efficiency. Advantageously, almost Pd-free primary aromatic amines were obtained since the Pd leaching was very low (<0.1% of the introduced amount). Compared to numerous reports from the literature, the catalysts described here were both easily accessible from eco-friendly precursors and very active for hydrogenations under mild and "green" reaction conditions.

Diblock Copolymer Core-Shell Nanoparticles as Template for Mesoporous Carbons: Independent Tuning of Pore Size and Pore Wall Thickness.

Latex templating using core-shell particles represents a unique opportunity to design mesoporous carbons with a high level of control on textural properties. This new class of organic colloid templates is synthesized by polymerization-induced self-assembly (PISA) in which a solvophilic poly(hydroxyethyl acrylate) (PHEA) homopolymer is chain extended with a solvophobic polystyrene (PS) via a photomediated reversible-addition-fragmentation-transfer (RAFT) polymerization. The resultant PHEA-b-PS diblock copolymer nanoparticles exhibit a PS core stabilized by a PHEA shell, with two blocks characterized by a low molecular weight dispersity (1.1-1.3) and an adjustable degree of polymerization (DP). The core-shell structured nanoparticles are used as soft template for the formation of mesostructured carbons from phloroglucinol and glyoxylic acid in methanol solution. A micro- and mesostructured cellular foam is obtained having uniform, interconnected, and narrowly distributed mesopores ranging between 15 and 30 nm in diameter, a specific surface area up to 719 m2 g-1, and a total pore volume of (0.4-1.3) cm3 g-1. The mesopore size can be controlled by adjusting the diameter of the PS core (16-29 nm), while the wall thickness can be tailored independently by varying the size of the solvated PHEA shell (5-25 nm). An increase of PHEA block's DP from 25 to 85 gradually extends the stabilizing shell dimension, thus increasing the wall thickness up to 10 nm, and causing the shift from interconnected to isolated mesopores. By comparison, much thinner walls (2-3 nm) are obtained with conventional latex templates such as polystyrene nanoparticles or colloidal silica. Decreasing PHEA DP to 17 induces the formation of copolymer vesicles that can be used as template to create mesoporous carbons with nonspherical mesopores.

Reusable magnetic Pd x Co y nanoalloys confined in mesoporous carbons for green Suzuki-Miyaura reactions.

We report herein Pd x Co y nanoalloys confined in mesoporous carbons (Pd x -Co y @MC) prepared by an eco-friendly one-pot approach consisting in the co-assembly of readily available and non-toxic carbon precursors (phloroglucinol, glyoxal) with a porogen template (pluronic F-127) and metallic salts (H2PdCl4 and Co(NO3)2·6H2O) followed by thermal annealing. Three Pd x Co y @MC materials with different alloy compositions were prepared (C1: x/y = 90/10; C2: x/y = 75/25; C3 and C4: x/y = 50/50). The nanoalloys were uniformly distributed in the carbon framework and the particle sizes depended on the alloy composition. These composites were then used for Suzuki-Miyaura reactions using either H2O or a 1 : 1 H2O/EtOH mixture as solvent. The Pd50Co50@MC catalyst C3 proved to be the most efficient catalyst (in terms of efficiency and magnetic recovery) affording the coupling products in good to excellent yields. After reaction, C3 was recovered quantitatively by simple magnetic separation and reused up to six times without loss of efficiency. The amount of palladium lost in the reaction mixture after magnetic separation was very low (ca. 0.1 % wt of the amount initially used).

Optimization of the synthesis of Pd-Au nanoalloys confined in mesoporous carbonaceous materials.

Pd-Au nanoalloys confined in mesoporous carbonaceous materials were synthesized by a rapid one-pot microwave assisted approach. Green polymer resins based on phloroglucinol/glyoxylic acid or glyoxal were co-assembled in the presence of a template and metallic salts followed by microwave treatment between 40 and 80°C and subsequent thermal annealing, allowing simultaneous formation of mesoporous carbonaceous materials with in-situ confined Pd-Au nanoparticles. Several Pd-Au compositions were prepared (PdxAu100-x, where x=90; 80; 70 and 50) and their impact on the alloy structure and particle size/distribution evaluated. For Pd90Au10, homogeneously dispersed nanoalloy particles (∼8nm) are obtained in the carbonaceous framework. The increase in the Au content in the alloy gradually induces an increase in the particle size and agglomeration of the particles along with the formation of multiphased alloys, i.e., segregated Pd- and Au-rich nanoparticles. The particle agglomeration was avoided by decreasing the thermal annealing time. The homogeneity of the alloy structure was found to strongly depend by two parameters, the chelating/cross-linker agents and the microwave temperature, i.e., the chelating/cross-linker agents containing carboxylic groups and the higher temperatures inducing more heterogeneous structures. The hydrogen absorption in Pd90Au10 particles with different homogeneity degree was studied at room temperature up to 1bar. Generally, hydrogen absorbs in Pd-rich nanoalloys forming a hydride phase whereas Au-rich phases do not absorb hydrogen under the present conditions.

Direct synthesis of graphitic mesoporous carbon from green phenolic resins exposed to subsequent UV and IR laser irradiations.

The design of mesoporous carbon materials with controlled textural and structural features by rapid, cost-effective and eco-friendly means is highly demanded for many fields of applications. We report herein on the fast and tailored synthesis of mesoporous carbon by UV and IR laser assisted irradiations of a solution consisting of green phenolic resins and surfactant agent. By tailoring the UV laser parameters such as energy, pulse repetition rate or exposure time carbon materials with different pore size, architecture and wall thickness were obtained. By increasing irradiation dose, the mesopore size diminishes in the favor of wall thickness while the morphology shifts from worm-like to an ordered hexagonal one. This was related to the intensification of phenolic resin cross-linking which induces the reduction of H-bonding with the template as highlighted by 13C and 1H NMR. In addition, mesoporous carbon with graphitic structure was obtained by IR laser irradiation at room temperature and in very short time periods compared to the classical long thermal treatment at very high temperatures. Therefore, the carbon texture and structure can be tuned only by playing with laser parameters, without extra chemicals, as usually required.

Activation of few layer graphene by µW-assisted oxidation in water via formation of nanoballs - Support for platinum nanoparticles.

The functionalization of carbon nanomaterials in controlled and selective manner and in order to stabilize small metal nanoparticles is of high interest particularly in the catalysis field. We present the µ-waves assisted few layer graphene (FLG) oxidation in water, which results in a partial sheets exfoliation and formation of oxygen functionalized carbon nanoballs, supported on highly graphitized graphene sheets. This double morphology material allows homogenous anchoring of Pt nanoparticles, while the advantages of planar and highly crystallized FLG are preserved. For comparison, acid treated FLG (conventional heating) exhibits highly hydrophobic and inert surface with carboxylic groups as anchoring sides localized at the FLG edges. Despite similar oxygen content, the performed physicochemical analyses depict different nature and localization of the oxygen/defects functionalities introduced in water (in µ-waves) and acid treated FLGs. Finally, the addition of FLG during the preparation of Pt particles-carried out by µ-wave assisted polyol method yields small nanoparticles with average size of 1nm.