Effect of Fillers Modification with ILs on Fillers Textural Properties: Thermal Properties of SBR Composites.

In this work, we present the effect of graphene nanoplatelets (GnPs) modification with ionic liquids (ILs). The textural properties of graphene nanoplatelets (GnPs) used as styrene-butadiene rubber's filler and the thermal properties of the composites obtained with the use of the mentioned fillers were investigated. GnPs were modified with 1-butylpyridinium bromide (BPyBr) and 4-methyl-1-butylpyridinium bromide (BmPyBr) through two different ways. One strategy has been to deposit the filler modifier from the solution. The second one involved the modification of the filler with ionic liquids in bulk during the preparation of elastomer blends. Settlement of the proposed ionic liquids onto the GnPs' surface led to significant changes in the textural characteristics. BPyBr has restricted the filler's microporosity, whereas BmPyBr has caused the formation of a more opened filler structure without the increase in its average pore size. GnPs modified with ILs led to reducing the temperature of vulcanization of SBR compounds and affected the thermal stability of the composites.

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.

Carbonaceous Materials Porosity Investigation in a Wet State by Low-Field NMR Relaxometry.

The porosity of differently wetted carbonaceous material with disordered mesoporosity was investigated using low-field 1H NMR relaxometry. Spin−spin relaxation (relaxation time T2) was measured using the CPMG pulse sequence. We present a non-linear optimization method for the conversion of relaxation curves to the distribution of relaxation times by using non-specialized software. Our procedure consists of searching for the number of components, relaxation times, and their amplitudes, related to different types of hydrogen nuclei in the sample wetted with different amounts of water (different water-to-carbon ratio). We found that a maximum of five components with different relaxation times was sufficient to describe the observed relaxation. The individual components were attributed to a tightly bounded surface water layer (T2 up to 2 ms), water in small pores especially supermicropores (2 < T2 < 7 ms), mesopores (7 < T2 < 20 ms), water in large cavities between particles (20−1500 ms), and bulk water surrounding the materials (T2 > 1500 ms). To recalculate the distribution of relaxation times to the pore size distribution, we calculated the surface relaxivity based on the results provided by additional characterization techniques, such as thermoporometry (TPM) and N2/−196 °C physisorption.

Low Metal Loading (Au, Ag, Pt, Pd) Photo-Catalysts Supported on TiO2 for Renewable Processes.

Photo-catalysts based on titanium dioxide, and modified with highly dispersed metallic nanoparticles of Au, Ag, Pd and Pt, either mono- or bi-metallic, have been analyzed by multiple characterization techniques, including XRD, XPS, SEM, EDX, UV-Vis and N2 adsorption/desorption. Mono-metallic photo-catalysts were prepared by wet impregnation, while bi-metallic photocatalysts were obtained via deposition-precipitation (DP). The relationship between the physico-chemical properties and the catalyst's behavior for various photo-synthetic processes, such as carbon dioxide photo-reduction to liquid products and glucose photo-reforming to hydrogen have been investigated. Among the tested materials, the catalysts containing platinum alone (i.e., 0.1 mol% Pt/TiO2) or bi-metallic gold-containing materials (e.g., 1 wt% (AuxAgy)/TiO2 and 1 wt% (AuxPtz)/TiO2) showed the highest activity, presenting the best results in terms of productivity and conversion for both applications. The textural, structural and morphological properties of the different samples being very similar, the main parameters to improve performance were function of the metal as electron sink, together with optoelectronic properties. The high activity in both applications was related to the low band gap, that allows harvesting more energy from a polychromatic light source with respect to the bare TiO2. Overall, high selectivity and productivity were achieved with respect to most literature data.

Potential Valorization of Waste Tires as Activated Carbon-Based Adsorbent for Organic Contaminants Removal.

The present study investigates the potential of waste tires to produce a valuable adsorbent material for application in wastewater treatment. In the first stage, the pyrolysis of ground rubber tire was explored using non-isothermal and isothermal thermogravimetric analysis experiments. The effect of operating parameters, such as heating rate and pyrolysis temperature, on the pyrolysis product yields was considered. The slow pyrolysis of ground rubber tire was taken up in a large-scale fixed-bed reactor for enhanced char recovery. Four pyrolysis temperatures were selected by thermogravimetric data. The product yields were strongly influenced by the pyrolysis temperature; at higher temperatures, the formation of more gases and liquid was favored, while at lower pyrolysis temperatures, more char (solid fraction) was formed. The produced chars were characterized in terms of mineral composition, textural properties, proximate analysis, and structural properties to identify the relationships between the pyrolysis temperature and the char properties. In a second step, a series of activated chars were prepared, starting from the pyrolytic chars via chemical and/or physical activation methods. Then, the activated chars were characterized and tested as adsorbents for atrazine and ibuprofen. Adsorption experiments in aqueous media were carried out in a small-scale batch reactor system. Chemical activation seems appropriate to significantly reduce the inorganic compounds initially present in ground rubber tire and contribute to an important increase in the surface area and porosity of the chars. Adsorption experiments indicated that chemically activated chars exhibit high aqueous adsorption capacity for atrazine.

Does the photocatalytic activity of nanoparticles protect the marine mussel Mytilus galloprovincialis from polycyclic aromatic hydrocarbon toxicity?

In the present study, five NPs (containing ZnO, Au-ZnO, Cu-ZnO, TiO2, and Au-TiO2) were characterized using dynamic light scattering and transmission electron microscopy, in order to observe their behavior under environmental change. The applicability of NPs for degradation of three polycyclic aromatic hydrocarbons (PAHs), including benzo(a)pyrene, fluoranthene, and benzanthracene, using UV irradiation showed the high photocatalytic efficiency of doped NPs for the removal of the study pollutants. To predict the environmental impact and interaction between NPs and PAHs on marine organisms, Mytilus galloprovincialis mussels were exposed to concentrations of each chemical (50 and 100 µg/L) for 14 days. The mussel's response was determined using the oxidative stress biomarker approach. Measured biomarkers in the mussel's digestive gland showed possible oxidative mechanisms in a concentration-dependent manner occurring after exposure to PAHs and NPs separately. Overall, this finding provides an interesting combination to remove PAHs in water, and the incorporation of chemical element into the crystallographic structure of NPs and the combination of two different NPs to form a binary hybrid NPs are promising materials.

Development of novel and ecological keratin/cellulose-based composites for absorption of oils and organic solvents.

Keratin/cellulose cryogels were successfully fabricated using chicken feathers (CF) and cardboard (C) from environmental waste for the first time, to be exploited in oil/solvent absorption. The keratin/cellulose-based composites were obtained by combining the dissolution of CF and C waste in 1-butyl-3-methylimidazolium chloride (Bmim-Cl+) ionic liquid green solvent via regeneration, simply by the freeze-drying method. The characterization analysis of the synthesized keratin/cellulose-based composites was performed using Fourier transform infrared spectrometry, X-ray diffractometry, scanning electron microscopy, and thermogravimetry. The as-prepared cryogel can absorb various oils and organic solvents. Moreover, its sorption capacity can reach up to 6.9-17.7 times the weight of the initial cryogel. This kind of CF/C cryogel revealed good and fast absorption efficiency. It could also be reused by simple absorption/distillation and absorption/desorption methods. Through the kinetic analysis, it was found that the pseudo-second-order model was more appropriate for the keratin/cellulose cryogel oil absorption process. Besides, owing to its low cost, good absorption capacity, and excellent reusability, this cryogel has potential for spill cleanup of oils and organic solvents.

Preparation and Properties of SBR Composites Containing Graphene Nanoplatelets Modified with Pyridinium Derivative.

The goal of this work was to study the effect of graphene nanoplatelets (GnPs) modified with ionic liquid (IL) on properties of styrene-butadiene rubber (SBR) composites. GnPs were decorated with IL or were modified in bulk directly during rubber mix preparation. The ionic liquid used was 1-butyl-4-methylpyridinium tetrafluoroborate (BMPFB). The textural properties were studied to confirm surface modification of GnPs with BMPFB. In these investigations, the impact of the concentration of GnPs and the effect of the method of GnPs' modification with IL on elastomers properties are described. Some thermal measurements (e.g., differential scanning calorimetry and thermogravimetry) were conducted to characterize the thermal stability or the vulcanization process of the investigated samples. Complementary experimental techniques were used to investigate the properties of the obtained elastomers, specifically tensile testing, and electrical and barrier property measurements. The deposition of IL on the GnPs' surface positively influenced the mechanical and barrier properties of elastomers. However, samples containing graphene nanoplatelets modified from solution were characterized by less electrical conductivity. SEM analysis was additionally performed to investigate GnPs' dispersion within SBR composites.

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.

Self-Photopolymerization of Poly(disulfide) Oligomers.

Base catalyst and oxidant are usually necessary to promote the polymerization of poly(disulfide) oligomers through oxidative coupling of the terminal SH groups into S-S bonds. In this study, we prove that self-polymerization of bifunctional (disulfide) oligomer films can take place in a matter of minutes under UVC irradiation (254 nm, 10.5 mW cm-2). The resulting insoluble polymer is characterized using solid-state NMR, 1H T2 NMR relaxation measurements, thermal analysis, and Fourier-transform infrared spectroscopy and proves to have similar composition as a model poly(disulfide) prepared under oxidative conditions, but distinct physical properties. These differences are explained by a change in polymer architecture due to a higher ratio of cyclization relative to linear polymerization. Homolytic photocleavage of internal S-S bonds creates thiyl groups close to each other, driving an increased kinetic feasibility for the cyclization reaction by radical coupling. The subsequent formation of mechanically interlocked macrocycles (polycatenane network) is proposed to account for film properties analogous to those of a cross-linked polymer.

Carbonaceous adsorbents derived from textile cotton waste for the removal of Alizarin S dye from aqueous effluent: kinetic and equilibrium studies.

Recycling cotton waste derived from the textile industry was used as a low-cost precursor for the elaboration of an activated carbon (AC) through carbonization and zinc chloride chemical activation. The AC morphological, textural, and surface chemistry properties were determined using different analytical techniques including Fourier transform infrared, temperature programmed desorption-mass spectroscopy, nitrogen manometry and scanning electron microscopy. The results show that the AC was with a hollow fiber structure in an apparent diameter of about 6.5 µm. These analyses indicate that the AC is microporous and present a uniform pore size distributed centered around 1 nm. The surface area and micropore volume were 292 m2.g-1 and 0.11 cm3.g-1, respectively. Several types of acidic and basic oxygenated surface groups were highlighted. The point of zero charge (pHPZC) of theca was 6.8. The AC performance was evaluated for the removal of Alizarin Red S (ARS) from aqueous solution. The maximum adsorption capacity was 74 mg.g-1 obtained at 25 °C and pH = 3. Kinetics and equilibrium models were used to determine the interaction nature of the ARS with the AC. Statistical tools were used to select the suitable models. The pseudo-second order was found to be the most appropriate kinetic model. The application of two and three isotherm models shows that Langmuir-Freundlich (n = 0.84, K = 0.0014 L.mg-1, and q = 250 mg.g-1) and Sips (n = 0.84, K = 0.003 L.mg-1, and q = 232.6 mg.g-1) were the suitable models. The results demonstrated that cotton waste can be used in the textile industry as a low-cost precursor for the AC synthesis and the removal of anionic dye from textile wastewater.

Thermodynamic study of seven micropollutants adsorption onto an activated carbon cloth: Van't Hoff method, calorimetry, and COSMO-RS simulations.

The thermodynamic of the adsorption of seven organic pollutants, namely benzotriazol, bisphenol A, caffeine, carbamazepine, diclofenac, ofloxacin, and pentachlorophenol, was studied on a microporous-activated carbon fabric. The isosteric adsorption quantities (Gibbs energy, enthalpy, and entropy variations) at high coverage ratio (around 1 mmol/g) have been determined from the adsorption isotherms at three temperatures (13, 25, and 40 °C). The adsorption heats at very low coverage (about 10-5 mmol/g) have been measured by flow micro calorimetry. The experimental adsorption energies were correlated to the adsorbate-adsorbent and the adsorbate-solvent interaction energies calculated by simulations using the COSMO-RS model. The main role of the van der Waals forces in the adsorption of the studied molecules was established. The bulkier the adsorbate is, the lower the adsorption Gibbs energy variation at high coverage deduced from the isotherms. The heterogeneity of the adsorption sites was brought out by calorimetric measurements. At high coverage, a physisorption phenomenon was observed. At very low coverage, high values of the adsorption heats were found (ranging from -58 to -110 kJ/mol), except for pentachlorophenol characterized by an athermal adsorption controlled by Pi-anions interactions.

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.

One-pot laser-assisted synthesis of porous carbon with embedded magnetic cobalt nanoparticles.

A novel one-pot laser-assisted approach is reported herein for the synthesis of ordered carbons with embedded cobalt nanoparticles. The process is based on a UV pulsed laser exposure of an ethanolic solution consisting of green carbon precursors, a structure directing agent and a cobalt salt. Very short irradiation times (5 to 30 min) are only required to polymerize and cross-link carbon precursors (i.e. phloroglucinol and glyoxylic acid) independent of a catalyst presence. The influence of three metallic salts (acetate, nitrate and chloride) on the phenolic resin and carbon characteristics (structure, texture and particle size/distribution) was systematically studied. When exposed to UV laser, the metallic salt exhibited a strong influence on the particle size and distribution in the carbon matrix rather than on the textural carbon properties. Using cobalt acetate, very small (3.5 nm) and uniformly dispersed particles were obtained by this simple, fast and green one-pot synthesis approach. An original combined (13)C CP-MAS and DP-DEC solid state NMR spectroscopy analysis allowed to determine the structure of phenolic resins as well as the location of the cobalt salt in the resin. Complementarily, the (1)H solid-state and relaxation NMR provided unique insights into the rigidity (cross-linking) of the phenolic resin and dispersion of the cobalt salt. The magnetic properties of cobalt nanoparticles were found to be size-dependent: large Co nanoparticles (∼50 nm) behave as bulk Co whereas small Co nanoparticles are superparamagnetic.