[This corrects the article DOI: 10.1021/acssusresmgt.4c00258.].

In the original publication [...].

Graphite is a widely used fossil material valued for its versatility, thanks to its excellent thermal and electrical conductivity as well as high chemical stability. Producing graphitic carbon from biomass offers a promising alternative to fossil graphite, but the process requires extremely high temperatures-up to 3000 degrees C-leading to significant energy consumption. In this work, we report a greener and more sustainable low-temperature method (900 degrees C) for the synthesis of highly graphitized biomass carbon using pure boron as a catalyst and logging residues (LR) as a carbon source. The work focuses on the correlation between the structural transformation of the precursors into graphitic carbon and their corresponding electrochemical characteristics as electrodes for lithium-ion batteries (LIBs) and supercapacitors. The carbons were prepared in two steps, i.e., carbonization at 500 degrees C with boron, followed by activation with KOH at 900 degrees C. A control carbon, produced using the same method but without boron, was used for comparison. The physicochemical characterization results demonstrated the successful graphitization of the LR-based carbon. In addition, the carbon materials exhibited highly porous structures with specific surface areas (BET) of 2645 m2 g-1 for the boron-treated carbon (BCLR), and 3141 m2 g-1 for the control carbon (CLR). The CLR and BCLR electrodes tested in LIBs delivered specific capacities of 386 and 505 mAh g-1 at a 1 C rate at the end of 200 cycles, respectively. CLR and BCLR electrodes were also tested for supercapacitors, delivering specific capacitances of 87 and 144 F g-1 at a current rate of 1 A g-1, respectively. This work opens a gateway for a straightforward and cost-effective synthesis method for scaling up biomass-based carbon electrodes for LIBs and supercapacitors, facilitating sustainable precursors and an industrially viable approach.

To produce high-performance anode materials for lithium/sodium batteries via sustainable strategies is still one of the most essential tasks in battery research. A biomass-based carbon-tin oxide composite (BC/SnO2) is prepared through pyrolysis of birch tree waste using phosphoric acid as an activator and its electrochemical performance as a sustainable anode material in lithium-ion batteries (LIBs) and sodium-ion batteries (NIBs) is tested. The physicochemical characterization results proved that SnO2 has a remarkable impact on BC/SnO2 porosity, morphology, and physicochemical features. Due to these favorable properties, the BC/SnO2 anode exhibited far better performance for LIBs and NIBs than bare carbon (BC). Against Li metal, the BC/SnO2 anode delivered a specific capacity of 319 mA h g-1 while BC delivered only 93.2 mA h g-1 (at 1C) at the end of 120 cycles. The BC/SnO2 composite showed excellent rate performances at different current densities, exhibiting a capacity of 453 mA h g-1 at the end of 120 cycles. Upon testing against sodium metal, the BC/SnO2 composite exhibited better cycling stability than BC (233 mA h g-1 compared with 165 mA h g-1) at 100 mA g-1 for 120 cycles. A theoretical investigation of the interactions between BC and SnO2 was performed using the semi-empirical GFN1-xTB method. The stability of the mixed system at high temperatures was confirmed using molecular dynamic simulations. Finally, we analyzed the electronic properties of the BC/SnO2 composite and drew conclusions about the electrical conductivity. Therefore, our research strategy helps to produce sustainable high-specific capacity anode materials from biomass resources for building cost-effective metal-ion batteries.

Ouricuri endocarp was utilized as a biosorbent for the recovery of europium (Eu(III)) from aqueous solutions and rare earth elements (REEs) from authentic leachate derived from phosphogypsum, which encompasses various REEs. Various characterization techniques were applied to analyze the physicochemical and adsorptive properties of the biosorbent. The results indicate that the adsorption kinetic data conform well to the pseudo-first-order model, while the Liu model describes the equilibrium data well. Ouricuri endocarp and Eu interactions are favorable and spontaneous. The maximum adsorption capacity for Eu(III) is determined to be 22.9 mg/g according to the Liu model. Based on experimental results and adsorbent characteristics, the proposed adsorption mechanisms between ouricuri endocarp and Eu include ion exchange and electrostatic interactions as the primary mechanisms. The Eu(III) recovery is also feasible as a continuous flow process demonstrating inclined breakthrough curves and lower values of the length of the mass transfer zone. Ouricuri endocarp demonstrates its selectivity for recovering various REEs from authentic phosphogypsum leachate. It achieves a 98% recovery rate for Eu and approximately 60% for Ce, La, and Nd, affirming its efficacy under real-world conditions. Finally, concentration of REE was done by ashing loaded ouricuri endocarp, and a solid with around 34% (in weight) of REE is obtained.

Water pollutants such as synthetic dyes can cause significant problems for human health and ecosystems due to their chemical properties and environmental interactions. Contamination of surface and underground water caused by the discharge of synthetic dyes is a widespread problem that arises primarily from industrial activities such as textile manufacturing, leather processing, paper production, and plastics industries. Since adsorption is one of the most efficient and reliable methods to remove pollutants from water, in this work, pine tree logging residues (LR) were used to produce boron/sulfur chemically modified biochars with superior adsorption performance and recyclability. The biochars were produced using a two-step pyrolysis procedure with potassium hydroxide as a chemical activator. The specific surface areas (B.E.T.) of the biochars were 2645 m2 g-1 for the boron-treated biochar (LR-Boron), 2524 m2 g- 1 for the sulfur-treated (LR-Sulfur), and 3141 m2 g- 1 for the control biochar (LR-Control, without boron or sulfur), respectively. The LR-Boron biochar showed an exceptional degree of graphitization of (ID/IG=0.45), while the LR-Sulfur biochar displayed an ID/IG= 1.02; for comparison, the LR-Control exhibited an ID/IG= 0.81, showing that the sample subjected to boron treatment created carbon- rich in graphitic structures. The three biochars were evaluated as adsorbents for removing reactive black-5 azo dye (RB-5) from water and mixtures of several dyes in synthetic aqueous effluents. The adsorption data showed that all carbons exhibited outstanding RB-5 removal performance. Kinetic measurements were well fitted by the Avrami fractional order model, and the LR-sulfur carbon displayed the fastest adsorption kinetics. Isotherm measurements were well fitted by the Liu model, with a theoretical Qmax of around 1419 mg g- 1 (LR-Control), 1586 mg g-1 (LR-Boron), and 1766 mg g-1 (LR-Sulfur) at 316 K. The presence of sulfur-functional groups on the LR-Sulfur biochar surface was probably the reason for the superior adsorption performance of this biochar. Both sulfur and boron-treated biochars exhibited higher regeneration potentials, maintaining around 60-67 % removal capacity after 7 cycles compared to 35 % for the LR-Control biochar. Thermodynamic adsorption studies showed that the adsorption process was endothermic, favorable, and compatible with physical adsorption. All produced biochars were highly efficient for removal of pollutants from concentrated synthetic effluents.

Due to its sustainable approach, biomass is the subject of much research focused on the synthesis of multifunctional materials including electrodes for batteries and supercapacitors. In this work, sawdust from the processing of birch logs was used to produce a highly porous carbon material (CBW) that is employed for the construction of electrodes for aluminum batteries (ABs) and supercapacitors (SCs). A multitude of characterizations indicated that CBW is built in with highly disordered amorphous carbons and an extremely high specific surface area of 3029 m2 g-1 which is predominant with microporous features. The chemical analysis of CBW indicated the presence of a significant amount of oxygen functionalities. As a cathode of AB, CBW achieved discharge capacities 115, 74, 54, 50, 47, 43, and 29 mAh g-1 at current rates 0.1, 1.0, 2.0, 3.0, 4.0, 5.0, and 10.0 A g-1, respectively. Similarly, SC with CBW symmetric electrodes exhibited capacitances 143, 94, 87, 79, 74, 69, 65, and 51 F g-1 at current rates 0.1, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, and 10.0 A g-1, respectively. The electrochemical characterization revealed that CBW is promising for ABs and SCs, and controlling the porosity type could further enhance the performance.

ZSM-5 zeolite is a multifunctional material highly efficient for adsorbing ions. Our ZSM-5 was synthesized by employing a nucleating gel as a structure-directing agent, followed by homogenization and hydrothermal treatment. The as-prepared ZSM-5 was physicochemically characterized to assess its properties. Next, the as-prepared zeolite was employed as an adsorbent to remove rare earth elements, REEs from synthetic solutions and real phosphogypsum leachate under batch mode operation. As expected, the ZSM-5 adsorbent was discovered to be highly microporous with abundant surface functionalities, which could positively impact REE adsorption. The adsorption data indicated a high affinity between ZSM-5 and all three REEs with rapid kinetics and high adsorption capacities. The modeling study suggested that the adsorption kinetic data were well fitted by Avrami-fractional order, and Liu described the equilibrium data. The maximum adsorption capacity for Ce3+, La3+, and Nd3+ were 99.42 mg g−1, 96.43 mg g−1, 118.10 mg g−1, respectively. Further, the thermodynamic analysis revealed that the interaction between ZSM-5 and Ce3+, La3+, and Nd3+ was favorable, spontaneous, and endothermic. The efficiency of ZSM-5 adsorbent was also studied in recovering several REEs from leachate of phosphogypsum wastes, and the data results proved its potency to do so. The findings reported in this work support the idea that ZSM-5 can be successfully used as an adsorbent to recover REEs from synthetic and real samples.

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.

In this study,vine pruning wastes(VPW)were used as raw material to develop an alternative activated carbon(VPW-AC)for adsorbing and concentrating rare earth elements cerium(Ce(Ⅲ))and lanthanum(La(Ⅲ))from synthetic and real leachate solutions.The Ce and La adsorption studies evaluated the effects of VPW-AC dosage,pH,contact time,rare earth initial concentration,and temperature.The VPW-AC adsorbent was subjected to many physicochemical characterization methods to correlate and under-stand its adsorptive performance.The characterization data indicate a carbonaceous adsorbent with a specific surface area of 467 m2/g.Zeta potential indicates a material with a negatively charged surface at a pH higher than 3.1,which is extremely beneficial to cations removal.For both rare earths elements(REEs),the adsorption capacity increases with the increase of the pH,reaching its maximum at pH 4-6.The kinetic data are well fitted by Avrami-fractional order,while the Liu model agreeably fits equilibrium data.The maximum adsorption capacities for Ce(Ⅲ)and La(Ⅲ)are 48.45 and 53.65 mg/g at 298 K,respectively.The thermodynamic studies suggest that the adsorption process is favorable,spontaneous,and exothermic for both REEs.Pore filling,surface complexation,and ion exchange are the dominant mechanisms.Finally,the VPW-AC was subjected to the recovery of REEs from real phosphogypsum leachate,and it is proved that it can be successfully used to recover REEs in a real process.

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 degrees 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 degrees C, obtained the highest BET specific surface area (1308 m(2)/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.

AbstractThis study employed lignin-sulfonated (LS) to develop biobased carbon materials (LS-Cs) through a sulfur-doping approach to enhance their physicochemical properties, adsorption capabilities, and energy storage potentials. Various characterization techniques, including BET surface area analysis, SEM imaging, XPS, Raman spectroscopy, and elemental composition (CHNS), were employed to assess the quality of the LS-Cs adsorbent and electrode samples. Response Surface Methodology (RSM) was utilized for optimizing the two main properties (specific surface area, ABET, and mesopore area, AMESO) by evaluating three independent factors (i.e., activation temperature, ZnCl2:LS ratio, and sulfur content). According to the statistical analysis, ABET and AMESO were affected by ZnCl2 and sulfur content, while the pyrolysis temperature did not affect the responses in the studied conditions. It was found that increasing the ZnCl2 and sulfur contents led to an increment of the ABET and AMESO values. The LS-C materials exhibited very high ABETvalues up to 1993 m2 g−1 and with predominantly mesoporous features. The S-doping resulted in LS-Cs with high sulfur contents in their microstructures up to 15% (wt%). The LS-C materials were tested as adsorbents for sodium diclofenac (DCF) adsorption and reactive orange 16 dye (RO-16) and as electrodes for supercapacitors. The LS-Cs exhibited excellent adsorption capacity values for both molecules (197–372 mg g−1) for DCF, and (223–466 mg g−1) for RO-16. When tested as electrodes for supercapacitors, notably, LS-C3, which is a doped sample with sulfur, exhibited the best electrochemical performance, e.g. high specific capacitance (156 F/g at 50 mV/s), and delivered an excellent capacitance after 1000 cycles (63 F/g at 1 A/g), which denotes the noteworthy capacitive behavior of the S-doped electrode. Thus, the present work suggests an eco-friendly resource for developing effective, productive carbon materials for adsorbent and electrodes for SC application. However, further studies on the complete application of these materials as adsorbents and electrodes are needed for a deeper understanding of their behavior in environmental and energy storage applications.

ZSM-5 zeolite is a multifunctional material highly efficient for adsorbing ions. Our ZSM-5 was synthesized by employing a nucleating gel as a structure -directing agent, followed by homogenization and hydrothermal treatment. The as -prepared ZSM-5 was physicochemically characterized to assess its properties. Next, the asprepared zeolite was employed as an adsorbent to remove rare earth elements, REEs from synthetic solutions and real phosphogypsum leachate under batch mode operation. As expected, the ZSM-5 adsorbent was discovered to be highly microporous with abundant surface functionalities, which could positively impact REE adsorption. The adsorption data indicated a high affinity between ZSM-5 and all three REEs with rapid kinetics and high adsorption capacities. The modeling study suggested that the adsorption kinetic data were well fitted by Avrami-fractional order, and Liu described the equilibrium data. The maximum adsorption capacity for Ce 3+ , La 3+ , and Nd 3+ were 99.42 mg g -1 , 96.43 mg g -1 , 118.10 mg g -1 , respectively. Further, the thermodynamic analysis revealed that the interaction between ZSM-5 and Ce 3+ , La 3+ , and Nd 3+ was favorable, spontaneous, and endothermic. The efficiency of ZSM-5 adsorbent was also studied in recovering several REEs from leachate of phosphogypsum wastes, and the data results proved its potency to do so. The findings reported in this work support the idea that ZSM-5 can be successfully used as an adsorbent to recover REEs from synthetic and real samples.

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, sulphur-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 318K 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.

Herein, a novel sulfur-doped carbon material has been synthesized via a facile and sustainable single-step pyrolysis method using lignin-sulfonate (LS), a by-product of the sulfite pulping process, as a novel carbon precursor and zinc chloride as a chemical activator. The sulfur doping process had a remarkable impact on the LS-sulfur carbon structure. Moreover, it was found that sulfur doping also had an important impact on sodium diclofenac removal from aqueous solutions due to the introduction of S-functionalities on the carbon material’s surface. The doping process effectively increased the carbon specific surface area (SSA), i.e., 1758 m2 g−1 for the sulfur-doped and 753 m2 g−1 for the non-doped carbon. The sulfur-doped carbon exhibited more sulfur states/functionalities than the non-doped, highlighting the successful chemical modification of the material. As a result, the adsorptive performance of the sulfur-doped carbon was remarkably improved. Diclofenac adsorption experiments indicated that the kinetics was better described by the Avrami fractional order model, while the equilibrium studies indicated that the Liu model gave the best fit. The kinetics was much faster for the sulfur-doped carbon, and the maximum adsorption capacity was 301.6 mg g−1 for non-doped and 473.8 mg g−1 for the sulfur-doped carbon. The overall adsorption seems to be a contribution of multiple mechanisms, such as pore filling and electrostatic interaction. When tested to treat lab-made effluents, the samples presented excellent performance.

Edible white-rot fungi are commonly cultivated on wood-based substrates and selectively degrade lignin to a larger extent during their growth. Spent mushroom substrate (SMS) is produced in huge amounts by the mushroom industry and today there is a lack of proven methods to valorize this kind of biomass waste, which in most cases is landfilled or used as fuel. This study demonstrates that birch wood-based SMS from the cultivation of oyster mushrooms can be converted into high-quality activated carbon (AC) with an extremely high surface area of about 3000 m2/g. These activated carbons showed good performance when used in electrodes for supercapacitors, with energy storage parameters nearly identical to AC produced from high-quality virgin birch wood. Moreover, AC produced from SMS showed high potential as an adsorbent for cleaning reactive orange-16 azo dye from aqueous solutions as well as contaminants from synthetic effluents and from real sewage water. The kinetics of adsorption were well represented by the Avrami fractional order model and isotherms of adsorption by the Liu model. The theoretical maximum reactive orange-16 adsorption capacities were approximately 519 mg/g (SMS-based carbon) and 553 mg/g (virgin birch-based carbon). The removal of contaminants from synthetic effluents made of different dyes and inorganic compounds was around 95% and 83% depending on the effluent composition. The removal of contaminants from raw sewage water was around 84%, and from treated sewage water was around 68%. Overall, the results showed that activated carbon prepared from waste generated during cultivation of white-rot fungi is as good as activated carbon prepared from high-quality virgin wood.

Edible white-rot mushrooms are organisms that are cultivated at an industrial scale using wood-based substrates. The mushroom industry has an estimated annual production of 34 Mt of edible mushrooms, and approximately 70 wt% of the substrate is left as waste known as spent mushroom substrate (SMS). The huge volumes of SMS generated by mushroom farms hinder proper recycling, meaning that combustion or open-field burning are common disposal practices. This paper shows a concept that could help reduce the environmental impact of the mushroom industry. SMS from the cultivation of shiitake mushroom was used as a carbon precursor for the production of nitrogen-doped activated biochar that was used to remove reactive orange-16 (RO-16) azo dye from water, as well as contaminants from two synthetic effluents and real sewage water. Melamine was used as a nitrogen dopant and phosphoric acid as an activating agent. Samples without the addition of melamine were used for comparison. The doping/impregnation process was carried out in one-step, followed by pyrolysis at 700 and 900 degrees C for 1 h. BET, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used for the characterization of the biochars. The specific surface area of the doped samples was slightly lower, i.e., 1011 m2/g (SMS-700 degrees C), 810 m2/g (SMS-700 degrees C + N), 1095 m2/g (SMS900 degrees C), and 943 m2/g (SMS-900 degrees C + N). Raman spectroscopic analysis showed that the N-doped biochars had more defective carbon structures than the non-doped ones. XPS analysis showed that doping with melamine led to the formation of N-functionalities on the surface of the biochar particles. The kinetics of adsorption were well represented by the Avrami model. The adsorption isotherms were well-fitted by the Liu model. The maximum adsorption capacities (qmax) of RO-16 were much higher for the N-doped biochars, i.e., 120 mg/g (SMS-700 degrees C), 216 mg/g (SMS-700 degrees C + N), 168 mg/g (SMS-900 degrees C), and 393 mg/g (SMS-900 degrees C + N). N-doped biochar samples were more effective for the removal of contaminants from synthetic effluents and sewage water. Ndoped biochar produced at 900 degrees C showed good recyclability. This work concludes that SMS is a valuable waste that could be used for the production of activated carbon and that N-doping helped to improve the adsorption performance to a great extent.

Heteroatom doping is a highly effective strategy that can be used to modify carbonaceous adsorbents to improve their chemical reactivity and increase their adsorptive properties. Herein, a simple method is reported for the preparation of nitrogen-doped biochar using a natural and abundant biowaste from birch trees and melamine as a nitrogen dopant for the adsorption of Acid red 18 (AR-18) dye from water. The doped biochars were also characterized for their performance during the treatment of synthetic effluents. The physicochemical characterization results showed that the N-doping process provoked remarkable chances on the biochar morphology, pore structure, and surface functionalities. N-doped biochar showed abundant nitrogen functional groups with 5.4 % of N in its structure while non-doped carbon showed traces with 0.47 %. Moreover, the specific surface area of doped biochar was dominated by mesopores (86.4 %) while non-doped was dominated by micropores (67.8 %). Raman analysis showed that the incorporation of N created more defects in the biochar structure. The adsorption experiments showed that the N-doping boosted the biochar adsorptive performance. The maximum adsorption capacity of the doped biochar was 545.2 mg g-1, while the non-doped exhibited 444.5 mg g-1, i.e., an increase of 22.6 %. The kinetic and equilibrium studies showed that Avrami fractional order and Liu models were the most suitable for describing the experimental AR-18 dye adsorption dat a. The equilibrium parameters were found to obey a nonlinear relationship with the temperature. Since the biochars are highly porous, pore filling was the main adsorption mechanism, however; AR-18 dye removal suggests that interactions such as electrostatic, hydrogen bonds, Lewis acid-base, and 7C-7C between the adsorbent and the dye are involved. The thermodynamic studies showed that the removal of the AR-18 dye from the solution is dependent on temperature, exothermic, and spontaneous. The N-doped biochar showed excellent removal performances of contaminants from synthetic effluents confirming their high efficiency for color removal. This research shows that N-doping is an efficient strategy to design effective, low-cost, and sustainable adsorbents to remediate dye contamination in wastewater.