Supercapacitors and triboelectric nanogenerators based on electrodes of greener iron nanoparticles/carbon nanotubes composites.

The development of supporting materials based on carbon nanotubes (CNTs) impregnated with iron nanoparticles via a sustainable and green synthesis employing plant extract of Punica granatum L. leaves was carried out for the iron nanoparticle modification and the following impregnation into the carbon nanotubes composites (CNT-Fe) that were also coated with polypyrrole (CNT-Fe + PPy) for use as electrode for supercapacitor and triboelectric nanogenerators. The electrochemical characterization of the materials by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) assays revealed that the CNT-Fe + PPy gave rise to better performance due to the association of double-layer capacitance behavior of carbon derivative in association with the pseudocapacitance contribution of PPy resulting in an areal capacitance value 202 mF/ cm2 for the overall composite. In terms of the application of electrodes in triboelectric nanogenerators, the best performance for the composite of CNT-Fe + PPy was 60 V for output voltage and power density of 6 µW/cm2. The integrated system showed that the supercapacitors can be charged directly by the nanogenerator from 0 to 42 mV in 300 s. The successful green synthesis of iron nanoparticles on CNT and further PPy coating provides a feasible method for the design and synthesis of high-performance SCs and TENGs electrode materials. This work provides a systematic approach that moves the research front forward by generating data that underpins further research in self-powered electronic devices.

Enhanced biobased carbon materials made from softwood bark via a steam explosion preprocessing step for reactive orange 16 dye adsorption.

The growing textile industry produces large volumes of hazardous wastewater containing dyes, which stresses the need for cheap, efficient adsorbing technologies. This study investigates a novel preprocessing method for producing activated carbons from abundantly available softwood bark. The preprocessing involved a continuous steam explosion preconditioning step, chemical activation with ZnCl2, pyrolysis at 600 and 800 °C, and washing. The activated carbons were subsequently characterized by SEM, XPS, Raman and FTIR prior to evaluation for their effectiveness in adsorbing reactive orange 16 and two synthetic dyehouse effluents. Results showed that the steam-exploded carbon, pyrolyzed at 600 °C, obtained the highest BET specific surface area (1308 m2/g), the best Langmuir maximum adsorption of reactive orange 16 (218 mg g-1) and synthetic dyehouse effluents (>70 % removal) of the tested carbons. Finally, steam explosion preconditioning could open up new and potentially more sustainable process routes for producing functionalized active carbons.

Synthesis of sustainable mesoporous sulfur-doped biobased carbon with superior performance sodium diclofenac removal: Kinetic, equilibrium, thermodynamic and mechanism.

Over the last years, the strategy of employing inevitable organic waste and residue streams to produce valuable and greener materials for a wide range of applications has been proven an efficient and suitable approach. In this research, sulfur-doped porous biochar was produced through a single-step pyrolysis of birch waste tree in the presence of zinc chloride as chemical activator. The sulfur doping process led to a remarkable impact on the biochar structure. Moreover, it was shown that sulfur doping also had an important impact on sodium diclofenac (S-DCF) removal from aqueous solutions due to the introduction of S-functionalities on biochar surface. The adsorption experiments suggested that General and Liu models offered the best fit for the kinetic and equilibrium studies, respectively. The results showed that the kinetic was faster for the S-doped biochar while the maximum adsorption capacity values at 318 K were 564 mg g-1 (non-doped) and 693 mg g-1 (S-doped); highlighting the better affinity of S-doped biochar for the S-DCF molecule compared to non-doped biochar. The thermodynamic parameters (ΔH0, ΔS0, ΔG0) suggested that the S-DCF removal on both adsorbents was spontaneous, favourable, and endothermic.

Synthesis, Characterization, and Adsorption Properties of Nitrogen-Doped Nanoporous Biochar: Efficient Removal of Reactive Orange 16 Dye and Colorful Effluents.

In this work, nitrogen-doped porous biochars were synthesized from spruce bark waste using a facile single-step synthesis process, with H3PO4 as the chemical activator. The effect of nitrogen doping on the carbon material's physicochemical properties and adsorption ability to adsorb the Reactive Orange 16 dye and treat synthetic effluents containing dyes were evaluated. N doping did not cause an important impact on the specific surface area values, but it did cause an increase in the microporosity (from 19% to 54% of micropores). The effect of the pH showed that the RO-16 reached its highest removal level in acidic conditions. The kinetic and equilibrium data were best fitted by the Elovich and Redlich-Peterson models, respectively. The adsorption capacities of the non-doped and doped carbon materials were 100.6 and 173.9 mg g-1, respectively. Since the biochars are highly porous, pore filling was the main adsorption mechanism, but other mechanisms such as electrostatic, hydrogen bond, Lewis acid-base, and π-π between mechanisms were also involved in the removal of RO-16 using SB-N-Biochar. The adsorbent biochar materials were used to treat synthetic wastewater containing dyes and other compounds and removal efficiencies of up to 66% were obtained. The regeneration tests have demonstrated that the nitrogen-doped biochar could be recycled and reused easily, maintaining very good adsorption performance even after five cycles. This work has demonstrated that N-doped biochar is easy to prepare and can be employed as an efficient adsorbent for dye removal, helping to open up new solutions for developing sustainable and effective adsorption processes to tackle water contamination.

Adsorption of Omeprazole on Biobased Adsorbents Doped with Si/Mg: Kinetic, Equilibrium, and Thermodynamic Studies.

This paper proposes an easy and sustainable method to prepare high-sorption capacity biobased adsorbents from wood waste. A biomass wood waste (spruce bark) was employed to fabricate a composite doped with Si and Mg and applied to adsorb an emerging contaminant (Omeprezole) from aqueous solutions, as well as synthetic effluents loaded with several emerging contaminants. The effects of Si and Mg doping on the biobased material's physicochemical properties and adsorptive performance were evaluated. Si and Mg did not influence the specific surface area values but impacted the presence of the higher number of mesopores. The kinetic and equilibrium data presented the best fitness by the Avrami Fractional order (AFO) and Liu isotherm models, respectively. The values of Qmax ranged from 72.70 to 110.2 mg g-1 (BP) and from 107.6 to 249.0 mg g-1 (BTM). The kinetic was faster for Si/Mg-doped carbon adsorbent, possibly due to different chemical features provoked by the doping process. The thermodynamic data showed that the adsorption of OME on biobased adsorbents was spontaneous and favorable at four studied temperatures (283, 293, 298, 303, 308, 313, and 318 K), with the magnitude of the adsorption correspondent to a physical adsorption process (ΔH° < 2 kJ mol-1). The adsorbents were applied to treat synthetic hospital effluents and exhibited a high percentage of removal (up to 62%). The results of this work show that the composite between spruce bark biomass and Si/Mg was an efficient adsorbent for OME removal. Therefore, this study can help open new strategies for developing sustainable and effective adsorbents to tackle water pollution.

Activated carbons with extremely high surface area produced from cones, bark and wood using the same procedure.

Activated carbons have been previously produced from a huge variety of biomaterials often reporting advantages of using certain precursors. Here we used pine cones, spruce cones, larch cones and a pine bark/wood chip mixture to produce activated carbons in order to verify the influence of the precursor on properties of the final materials. The biochars were converted into activated carbons with extremely high BET surface area up to ∼3500 m2 g-1 (among the highest reported) using identical carbonization and KOH activation procedures. The activated carbons produced from all precursors demonstrated similar specific surface area (SSA), pore size distribution and performance to electrodes in supercapacitors. Activated carbons produced from wood waste appeared to be also very similar to "activated graphene" prepared by the same KOH procedure. Hydrogen sorption of AC follows expected uptake vs. SSA trends and energy storage parameters of supercapacitor electrodes prepared from AC are very similar for all tested precursors. It can be concluded that the type of precursor (biomaterial or reduced graphene oxide) has smaller importance for producing high surface area activated carbons compared to details of carbonization and activation. Nearly all kinds of wood waste provided by the forest industry can possibly be converted into high quality AC suitable for preparation of electrode materials.

Cellulose Fiber Rejects as Raw Material for Integrated Production of Pleurotus spp. Mushrooms and Activated Biochar for Removal of Emerging Pollutants from Aqueous Media.

Cellulose fiber rejects from industrial-scale recycling of waste papers were dried and de-ashed using a combined cyclone-drying and sieving process. The upgraded fiber reject was used as a component of substrates for the cultivation of Pleurotus ostreatus and Pleurotus eryngii mushrooms. Acetic acid (AA) and acid whey (AW) were used to adjust the pH of fiber reject-based substrates. Spent substrate (SMS) was used for the production of activated biochar using H3PO4 and KOH as activating agents and pyrolysis temperatures of 500, 600, and 700 °C. The effectiveness of the biochars in removing pollutants from water was determined using acetaminophen and amoxicillin. By using a feeding rate of 250 kg/h and a drying air temperature of 70 °C, the moisture content of the raw fiber rejects (57.8 wt %) was reduced to 5.4 wt %, and the ash content (39.2 wt %) was reduced to 21.5 wt %. Substrates with 60 and 80 wt % de-ashed cellulose fiber were colonized faster than a birch wood-based control substrate. The adjustment of the pH of these two substrates to approximately 6.5 by using AA led to longer colonization times but biological efficiencies (BEs) that were higher or comparable to that of the control substrate. The contents of ash, crude fiber, crude fat, and crude protein of fruit bodies grown on fiber reject-based substrates were comparable to that of those grown on control substrates, and the contents of toxic heavy metals, that is, As, Pb, Cd, and Hg, were well below the up-limit values for food products set in EC regulations. Activated biochar produced from fiber reject-based SMS at a temperature of 700 °C resulted in a surface area (BET) of 396 m2/g (H3PO4-activated biochar) and 199 m2/g (KOH-activated biochar). For both activated biochars, the kinetics of adsorption of acetaminophen and amoxicillin were better described using the general order model. The isotherms of adsorption were better described by the Freundlich model (H3PO4-activated biochar) and the Langmuir model (KOH-activated biochar).

Preparation and Characterization of Pulp and Paper Mill Sludge-Activated Biochars Using Alkaline Activation: A Box-Behnken Design Approach.

This study utilized pulp and paper mill sludge as a carbon source to produce activated biochar adsorbents. The response surface methodology (RSM) application for predicting and optimizing the activated biochar preparation conditions was investigated. Biochars were prepared based on a Box-Behnken design (BBD) approach with three independent factors (i.e., pyrolysis temperature, holding time, and KOH:biomass ratio), and the responses evaluated were specific surface area (SSA), micropore area (S micro), and mesopore area (S meso). According to the RSM and BBD analysis, a pyrolysis temperature of 800 °C for 3 h of holding and an impregnation ratio of 1:1 (biomass:KOH) are the optimum conditions for obtaining the highest SSA (885 m2 g-1). Maximized S micro was reached at 800 °C, 1 h and the ratio of 1:1, and for maximizing S meso (569.16 m2 g-1), 800 °C, 2 h and ratio 1:1.5 (445-473 m2 g-1) were employed. The biochars presented different micro- and mesoporosity characteristics depending on pyrolysis conditions. Elemental analysis showed that biochars exhibited high carbon and oxygen content. Raman analysis indicated that all biochars had disordered carbon structures with structural defects, which can boost their properties, e.g., by improving their adsorption performances. The hydrophobicity-hydrophilicity experiments showed very hydrophobic biochar surfaces. The biochars were used as adsorbents for diclofenac and amoxicillin. They presented very high adsorption performances, which could be explained by the pore filling, hydrophobic surface, and π-π electron-donor-acceptor interactions between aromatic rings of both adsorbent and adsorbate. The biochar with the highest surface area (and highest uptake performance) was subjected to regeneration tests, showing that it can be reused multiple times.

Shiitake cultivation as biological preprocessing of lignocellulosic feedstocks - Substrate changes in crystallinity, syringyl/guaiacyl lignin and degradation-derived by-products.

Formulation of substrates based on three hardwood species combined with modulation of nitrogen content by whey addition (0-2%) was investigated in an experiment designed in D-optimal model for their effects on biological preproceesing of lignocellulosic feedstock by shiitake mushroom (Lentinula edodes) cultivation. Nitrogen loading was shown a more significant role than wood species for both mushroom production and lignocellulose degradation. The fastest mycelial colonisation occurred with no nitrogen supplementation, but the highest mushroom yields were achieved when 1% whey was added. Low nitrogen content resulted in increased delignification and minimal glucan consumption. Delignification was correlated with degradation of syringyl lignin unit, as indicated by a significant reduction (41.5%) of the syringyl-to-guaiacyl ratio after cultivation. No significant changes in substrate crystallinity were observed. The formation of furan aldehydes and aliphatic acids was negligible during the pasteurisation and fungal cultivation, while the content of soluble phenolics increased up to seven-fold.

Combustion of Biosolids in a Bubbling Fluidized Bed, Part 1: Main Ash-Forming Elements and Ash Distribution with a Focus on Phosphorus.

This is the first in a series of three papers describing combustion of biosolids in a 5-kW bubbling fluidized bed, the ash chemistry, and possible application of the ash produced as a fertilizing agent. This part of the study aims to clarify whether the distribution of main ash forming elements from biosolids can be changed by modifying the fuel matrix, the crystalline compounds of which can be identified in the raw materials and what role the total composition may play for which compounds are formed during combustion. The biosolids were subjected to low-temperature ashing to investigate which crystalline compounds that were present in the raw materials. Combustion experiments of two different types of biosolids were conducted in a 5-kW benchscale bubbling fluidized bed at two different bed temperatures and with two different additives. The additives were chosen to investigate whether the addition of alkali (K2CO3) and alkaline-earth metal (CaCO3) would affect the speciation of phosphorus, so the molar ratios targeted in modified fuels were P:K = 1:1 and P:K:Ca = 1:1:1, respectively. After combustion the ash fractions were collected, the ash distribution was determined and the ash fractions were analyzed with regards to elemental composition (ICP-AES and SEM-EDS) and part of the bed ash was also analyzed qualitatively using XRD. There was no evidence of zeolites in the unmodified fuels, based on low-temperature ashing. During combustion, the biosolid pellets formed large bed ash particles, ash pellets, which contained most of the total ash content (54%-95% (w/w)). This ash fraction contained most of the phosphorus found in the ash and the only phosphate that was identified was a whitlockite, Ca9(K,Mg,Fe)(PO4)7, for all fuels and fuel mixtures. With the addition of potassium, cristobalite (SiO2) could no longer be identified via X-ray diffraction (XRD) in the bed ash particles and leucite (KAlSi2O6) was formed. Most of the alkaline-earth metals calcium and magnesium were also found in the bed ash. Both the formation of aluminum-containing alkali silicates and inclusion of calcium and magnesium in bed ash could assist in preventing bed agglomeration during co-combustion of biosolids with other renewable fuels in a full-scale bubbling fluidized bed.