Application of Viscose-Based Porous Carbon Fibers in Food Processing-Malathion and Chlorpyrifos Removal.

The increasing usage of pesticides to boost food production inevitably leads to their presence in food samples, requiring the development of efficient methods for their removal. Here, we show that carefully tuned viscose-derived activated carbon fibers can be used for malathion and chlorpyrifos removal from liquid samples, even in complex matrices such as lemon juice and mint ethanol extract. Adsorbents were produced using the Design of Experiments protocol for varying activation conditions (carbonization at 850 °C; activation temperature between 670 and 870 °C; activation time from 30 to 180 min; and CO2 flow rate from 10 to 80 L h-1) and characterized in terms of physical and chemical properties (SEM, EDX, BET, FTIR). Pesticide adsorption kinetics and thermodynamics were then addressed. It was shown that some of the developed adsorbents are also capable of the selective removal of chlorpyrifos in the presence of malathion. The selected materials were not affected by complex matrices of real samples. Moreover, the adsorbent can be regenerated at least five times without pronounced performance losses. We suggest that the adsorptive removal of food contaminants can effectively improve food safety and quality, unlike other methods currently in use, which negatively affect the nutritional value of food products. Finally, data-based models trained on well-characterized materials libraries can direct the synthesis of novel adsorbents for the desired application in food processing.

How Well Do Our Adsorbents Actually Perform?-The Case of Dimethoate Removal Using Viscose Fiber-Derived Carbons.

Growing pollution is making it necessary to find new strategies and materials for the removal of undesired compounds from the environment. Adsorption is still one of the simplest and most efficient routes for the remediation of air, soil, and water. However, the choice of adsorbent for a given application ultimately depends on its performance assessment results. Here, we show that the uptake of and capacity for dimethoate adsorption by different viscose-derived (activated) carbons strongly depend on the adsorbent dose applied in the adsorption measurements. The specific surface areas of the investigated materials varied across a wide range from 264 m2 g-1 to 2833 m2 g-1. For a dimethoate concentration of 5 × 10-4 mol L-1 and a high adsorbent dose of 10 mg mL-1, the adsorption capacities were all below 15 mg g-1. In the case of high-surface-area activated carbons, the uptakes were almost 100% under identical conditions. However, when the adsorbent dose was reduced to 0.01 mg mL-1, uptake was significantly reduced, but adsorption capacities as high as 1280 mg g-1 were obtained. Further, adsorption capacities were linked to adsorbents' physical and chemical properties (specific surface area, pore size distribution, chemical composition), and thermodynamic parameters for the adsorption process were evaluated. Based on the Gibbs free energy of the adsorption process, it can be suggested that physisorption was operative for all studied adsorbents. Finally, we suggest that a proper comparison of different adsorbents requires standardization of the protocols used to evaluate pollutant uptakes and adsorption capacities.

Viscose-Derived Activated Carbons Fibers as Highly Efficient Adsorbents for Dimethoate Removal from Water.

Extensive use of pesticides resulting in their accumulation in the environment presents a hazard for their non-target species, including humans. Hence, efficient remediation strategies are needed, and, in this sense, adsorption is seen as the most straightforward approach. We have studied activated carbon fibers (ACFs) derived from viscose fibers impregnated with diammonium hydrogen phosphate (DAHP). By changing the amount of DAHP in the impregnation step, the chemical composition and textural properties of ACFs are effectively tuned, affecting their performance for dimethoate removal from water. The prepared ACFs effectively reduced the toxicity of treated water samples, both deionized water solutions and spiked tap water samples, under batch conditions and in dynamic filtration experiments. Using the results of physicochemical characterization and dimethoate adsorption measurements, multiple linear regression models were made to reliably predict performance towards dimethoate removal from water. These models can be used to quickly screen among larger sets of possible adsorbents and guide the development of novel, highly efficient adsorbents for dimethoate removal from water.

Comparative Behavior of Viscose-Based Supercapacitor Electrodes Activated by KOH, H2O, and CO2.

Activated carbons derived from viscose fibers were prepared using potassium hydroxide, carbon dioxide, or water vapor as activation agents. The produced activated carbon fibers were analyzed via scanning electron microscopy and energy dispersive X-ray spectroscopy, and their porosity (specific surface area, total pore volume, and pore size distribution) was calculated employing physisorption experiments. Activated carbon fibers with a specific surface area of more than 2500 m2 g-1 were obtained by each of the three methods. Afterwards, the suitability of these materials as electrodes for electrochemical double-layer capacitors (supercapacitors) was investigated using cyclic voltammetry, galvanostatic measurements, and electrochemical impedance spectroscopy. By combining CO2 and H2O activation, activated carbon fibers of high purity and excellent electrochemical performance could be obtained. A specific capacitance per electrode of up to 180 F g-1 was found. In addition, an energy density per double-layer capacitor of 42 W h kg-1 was achieved. These results demonstrate the outstanding electrochemical properties of viscose-based activated carbon fibers for use as electrode materials in energy storage devices such as supercapacitors.

Viscose-derived activated carbons as adsorbents for malathion, dimethoate, and chlorpyrifos-screening, trends, and analysis.

The release and accumulation of pesticides in the environment require the development of novel sustainable technologies for their removal. While adsorption is a classical approach, the design of new materials with enhanced adsorption properties could rationalize the remediation routes and decrease potential risks for their non-target organisms, including humans. More importantly, the use of adsorbents and their synthesis should be implemented in a sustainable and environmentally friendly manner. In this contribution, we studied the adsorption of organophosphorus pesticides (OPs) dimethoate, malathion, and chlorpyrifos on viscose fiber-derived activated carbon fibers (ACFs). The most efficient adsorption was found for chlorpyrifos, followed by malathion and dimethoate, while material properties were correlated with OP uptake. These ACFs are extremely efficient for chlorpyrifos adsorption, with experimentally observed adsorption capacitances reaching 240 mg g-1. Detailed analysis suggests that chlorpyrifos is physisorbed on ACF surfaces and that increased surface hydrophilicity reduces the uptake. Studied ACFs have great potential for practical application. They can reduce OPs' concentrations to such levels that no acute neurotoxic effects of the studied OPs in spiked tap water samples are seen, even for starting concentrations up to 104 times higher than the allowed ones. Finally, this study presents possible guidance for developing even more efficient and environmentally friendly adsorbents for chlorpyrifos, the most toxic among studied OPs.

Pore Development during the Carbonization Process of Lignin Microparticles Investigated by Small Angle X-ray Scattering.

Application of low-cost carbon black from lignin highly depends on the materials properties, which might by determined by raw material and processing conditions. Four different technical lignins were subjected to thermostabilization followed by stepwise heat treatment up to a temperature of 2000 °C in order to obtain micro-sized carbon particles. The development of the pore structure, graphitization and inner surfaces were investigated by X-ray scattering complemented by scanning electron microscopy and FTIR spectroscopy. Lignosulfonate-based carbons exhibit a complex pore structure with nanopores and mesopores that evolve by heat treatment. Organosolv, kraft and soda lignin-based samples exhibit distinct pores growing steadily with heat treatment temperature. All carbons exhibit increasing pore size of about 0.5-2 nm and increasing inner surface, with a strong increase between 1200 °C and 1600 °C. The chemistry and bonding nature shifts from basic organic material towards pure graphite. The crystallite size was found to increase with the increasing degree of graphitization. Heat treatment of just 1600 °C might be sufficient for many applications, allowing to reduce production energy while maintaining materials properties.

Tailoring of carbonized polypyrrole nanotubes core by different polypyrrole shells for oxygen reduction reaction selectivity modification.

By using methyl orange template, polypyrrole nanotubes were obtained by the oxidative polymerization of pyrrole. The nanotubes were carbonized in inert atmosphere to nitrogen-enriched carbon nanotubes. These were subsequently coated with 20 wt% of polypyrrole prepared in the absence or the presence of anionic dyes (methyl orange or Acid Blue 25). The morphology of all the samples was examined by the electron microscopies, FTIR and Raman spectroscopies. Moreover, X-ray photoelectron spectroscopy and elemental analysis were used to prove the chemical structure and the successful coating process. Electron paramagnetic resonance analysis was used to calculate the spin concentrations. Significant impact of coating method is evidenced with neat polypyrrole coating providing a two-fold capacitance increase compared to uncoated nanotubes, while coating in the presence of Acid Blue 25 decreasing it slightly. With respect to oxygen reduction reaction, coatings irreversibly transformed in the first few cycles in the presence of the products of O2 reduction, presumably hydrogen peroxide, altering the oxygen reduction mechanism. This transformation allows the tailoring of the polymeric shell, over ORR active carbonaceous core, and tuning of the catalyst selectivity and optimization of materials performance for a given application - from alkaline fuel cells to hydrogen peroxide generation.

Electrically-Conductive Sub-Micron Carbon Particles from Lignin: Elucidation of Nanostructure and Use as Filler in Cellulose Nanopapers.

Carbon particles were produced from kraft lignin through carbonization of perfectly spherical, sub-micron beads obtained by aerosol flow. The structure of the resulting carbon particles was elucidated and compared to that derived from commercially available technical lignin powder, which is undefined in geometry. In addition to the smaller diameters of the lignin beads (<1 µm) compared to those of the lignin powder (100 µm), the former displayed a slightly higher structural order as revealed by X-ray diffraction and Raman spectroscopy. With regard to potential application in composite structures, the sub-micron carbon beads were clearly advantageous as a filler of cellulose nanopapers, which displayed better mechanical performance but with limited electrical conductivity. Compression sensing was achieved for this nanocomposite system.

Carbon Microparticles from Organosolv Lignin as Filler for Conducting Poly(Lactic Acid).

Carbon microparticles were produced from organosolv lignin at 2000 °C under argon atmosphere following oxidative thermostabilisation at 250 °C. Scanning electron microscopy, X-ray diffraction, small-angle X-ray scattering, and electro-conductivity measurements revealed that the obtained particles were electrically conductive and were composed of large graphitic domains. Poly(lactic acid) filled with various amounts of lignin-derived microparticles showed higher tensile stiffness increasing with particle load, whereas strength and extensibility decreased. Electric conductivity was measured at filler loads equal to and greater than 25% w/w.