This study investigates the adsorption and reduction of NO2 on biochar (BCC) and silver-modified biochar (Ag-BCC) in a continuous flow. Ag-BCC showed a higher NO2 adsorption capacity (11.78 mg/g) than BCC (11.04 mg/g) at 200 °C, despite its lower surface area (345 vs. 402 m2/g). While neither material decomposed NO2 at 22 °C, Ag-BCC achieved a NO/NO2 ratio of 20% (vs. 9% for BCC) at 200 °C, highlighting the catalytic role of silver in NO2 conversion. Breakthrough curve modeling identified the Dose–Response model as optimal, accurately describing adsorption kinetics at all temperatures (22–200 °C). Adsorption rate constants decreased with increasing temperature, confirming exothermicity. Overall, the results highlight the enhanced performance of Ag-BCC for NO2 capture and conversion, underlining the potential of surface-modified biochars in the sustainable mitigation of air pollution.
The growing energy consumption and the need for a circular economy have driven considerable interest in the anaerobic digestion (AD) of organic waste, offering potential solutions through biogas and digestate production. AD processes not only have the capability to reduce greenhouse gas emissions but also contribute to the production of renewable methane. This comprehensive review aims to consolidate prior research on AD involving different feedstocks. The principles of AD are explored and discussed, including both chemical and biological pathways and the microorganisms involved at each stage. Additionally, key variables influencing system performance, such as temperature, pH, and C/N ratio are also discussed. Various pretreatment strategies applied to enhance biogas generation from organic waste in AD are also reviewed. Furthermore, this review examines the conversion of generated digestate into biochar through pyrolysis and its utilization to improve AD performance. The addition of biochar has demonstrated its efficacy in enhancing metabolic processes, microorganisms (activity and community), and buffering capacity, facilitating Direct Interspecies Electron Transfer (DIET), and boosting CH4 production. Biochar also exhibits the ability to capture undesirable components, including CO2, H2S, NH3, and siloxanes. The integration of digestate-derived biochar into the circular economy framework emerges as a vital role in closing the material flow loop. Additionally, the review discusses the environmental benefits derived from coupling AD with pyrolysis processes, drawing on life cycle assessment investigations. Techno-economic assessment (TEA) studies of the integrated processes are also discussed, with an acknowledgment of the need for further TEA to validate the viability of integrating the biochar industry. Furthermore, this survey examines the techno-economic and environmental impacts of biochar production itself and its potential application in AD for biogas generation, aiming to establish a more cost-effective and sustainable integrated system.
This study investigates the production of biochar from fresh wood shavings (B-WSF) and used wood shavings (B-WSU–animal litter) biomass through pyrolysis at 450 °C and explores its potential for NO2 adsorption at different temperatures from 22 °C to 250 °C. The biochars’ thermal stability, elemental composition, mineral content, textural properties, and surface chemistry were comprehensively analyzed using various techniques, including thermogravimetric analysis (TGA), ultimate analysis, proximate analysis, mineral composition analysis, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and NO2 adsorption experiments. The results indicate that biochars derived from WSF and WSU biomass possess high stability and exhibit significant changes in their elemental composition, surface functional groups, and textural properties compared to the raw biomass. The biochars demonstrated substantial NO2 adsorption capacities and reduction, with B-WSU biochar exhibiting higher adsorption capacity attributed to its higher specific surface area, mineral content, and functional groups. In addition, the results reveal distinct patterns in NO2 adsorption and NO release, with temperature playing a pivotal role in the process. At lower temperatures, NO2 adsorption on both biochars exhibits gradual increases, while higher temperatures facilitate immediate adsorption and subsequent reduction to NO. The adsorption of NO2 increased with increasing adsorption temperature, with B-WSU biochar achieving a maximum adsorption capacity of 43.54 mg/g at 250 °C, compared to 9.62 mg/g for B-WSF biochar. Moreover, XPS analysis revealed alterations in surface functional groups upon NO2 exposure, indicating enhanced surface oxidation and formation of nitrogen-containing species. In addition, differences in surface heterogeneity and mineral content influence NO2 adsorption behavior between the biochar samples. These findings highlight the potential of WSF biomass-derived biochar as an effective adsorbent for NO2 removal, offering insights into its application in air pollution mitigation strategies. The mechanism of NO2 adsorption involves chemisorption on oxygen-containing functional groups and physical adsorption, facilitated by the high specific surface area and pore volume of the biochar. Furthermore, the rich mineral content in B-WSU biochar explains its high adsorption capacity, demonstrating the potential for valorization of waste materials in the circular economy.
In the context of sustainable solutions, this study examines the pyrolysis process applied to corn cobs, with the aim of producing biochar and assessing its effectiveness in combating air pollution. In particular, it examines the influence of different pyrolysis temperatures on biochar properties. The results reveal a temperature-dependent trend in biochar yield, which peaks at 400 °C, accompanied by changes in elemental composition indicating increased stability and extended shelf life. In addition, high pyrolysis temperatures, above 400 °C, produce biochars with enlarged surfaces and improved pore structures. Notably, the highest pyrolysis temperature explored in this study is 600 °C, which significantly influences the observed properties of biochars. This study also explores the potential of biochar as an NO2 adsorbent, as identified by chemical interactions revealed by X-ray photoelectron spectroscopy (XPS) analysis. This research presents a promising and sustainable approach to tackling air pollution using corn cob biochar, providing insight into optimized production methods and its potential application as an effective NO2 adsorbent to improve air quality.
Studies on the immobilization of oxindolimine-copper(II) or zinc(II) complexes [ML] in synthetic beidellite (BDL) clay were developed to obtain a suitable inorganic carrier capable of promoting the modified-release of metallopharmaceuticals. Previous investigations have shown that the studied metal complexes are promising antitumor agents, targeting DNA, mitochondria, and some proteins. They can bind to DNA, causing oxidative damage via formation of reactive oxygen species (ROS). In mitochondria they lead to a decrease in membrane potential, acting as decoupling agents, and therefore efficiently inducing apoptosis. Additionally, they inhibit human topoisomerase IB and cyclin dependent kinases, proteins involved in the cell cycle. BDL clays in the sodium form were synthesized under hydrothermal conditions and characterized by a set of physicochemical techniques while the BDL-[ML] hybrid materials were prepared by ion exchange method. The characterization of pristine clay and the obtained hybrids were performed by Infrared, Raman, electron paramagnetic resonance and energy dispersive X-ray spectroscopies, thermogravimetric analysis, scanning electron microscopy, X-ray powder diffraction, specific surface area, zeta potential and surface ionic charge measurements. The [ML] release assays under the same cell incubation conditions were performed monitoring metals by X-ray fluorescence. The BDL-[CuL] hybrid materials were stable and able to derail tumor HeLa cells, with corresponding IC50 values in the 0.11-0.41 mg mL-1 range. By contrast, the analogous hybrid samples of zinc(II) and the pristine BDL proved to be non-toxic facing the same cells. These results indicate a promising possibility of using synthetic beidellite as a carrier of such antitumor metal complexes.
Heat storage technologies are essential for increasing the use of solar energy in the household sector. Their development can be achieved by designing new storage materials; one way is to impregnate a porous matrix with hygroscopic salts. In this article, the possibility of using biochar-based composite sorbents to develop promising new heat storage materials for efficient thermal storage is explored. Biochar-based composites with defined salt loadings (5, 10, 15, and 20%) were produced by impregnating MgSO4 into a biochar matrix derived from corn cobs. The new materials demonstrated a high water sorption capacity of 0.24 g/g (20MgCC). After six successive charging-discharging cycles (dehydration/dehydration cycles), only a negligible variation of the heat released and the water uptake was measured, confirming the absence of deactivation of 20MgCC upon cycling. The new 20MgCC composite showed an energy storage density of 635 J/g (Tads = 30 °C and RH = 60%), higher than that of other composites containing a similar amount of hydrate salt. The macroporous nature of this biochar increases the available surface for salt deposition. During the hydration step, the water molecules effectively diffuse through a homogeneous layer of salt, as described by the intra-particle model applied in this work. The new efficient biochar-based composites open a low-carbon path for the production of sustainable thermal energy storage materials and applications.
Tomato pomace was slowly pyrolyzed at 350 and 550 °C (under an N2 flow of 50 L/h) at a rate of 6 °C/min and a residence time of 1:30 h to produce two biochars named B350 and B550, respectively. In addition, the two biochars were chemically activated with ΚΟΗ (at a ratio of 1:10 w/v) at 800 °C to produce two new materials named BA350 and BA550. The four biochars produced were characterized physically and chemically (pH, yield, calorific value). They were also analyzed by scanning electron microscopy (SEM), Brunauer–Emmett–Teller (B.E.T), elemental analysis (EA), and thermogravimetric analysis (TGA). The results showed that as the pyrolysis temperature increased (350 to 550 °C), the specific surface area (SSA) increased. The latter was also significantly increased by the activation process. EA showed a variation in the mineral content of the produced biochars, resulting in a different content of the biochars after activation. The parameters studied showed that biochars from tomato waste could be used as an organic amendment to improve soil fertility in agricultural. In addition, because of their ability to absorb water, they could be used as a water reservoir in soils in arid areas.
The increased production of biogas through the anaerobic digestion (AD) process has raised several concerns regarding the management of liquid digestate, which can present some environmental risks if not properly handled. Among the different techniques to treat AD digestate, microalgae and cyanobacteria cultivation has emerged as a sustainable approach to valorizing digestate while producing valuable biomass for production of biofuels and high value bioproducts. However, the intrinsic parameters of the liquid digestate can strongly limit the microalgae or cyanobacteria growth as well as limit the uptake of residual nutrients. In this study, the detoxification potential of activated carbon (AC) was evaluated on agro-industrial liquid digestate prior to Spirulina platensis cultivation. Different doses of AC, ranging from 5 to 100 g/L, were tested during adsorption experiments in order to determine the adsorption capacity as well as the removal efficiency of several compounds. Experimental results showed the high reactivity of AC, especially towards phosphate (PO4-P), total phenol (TP) and chemical oxygen demand (COD). At a dosage of 50 g/L, the AC pretreatment successfully achieved 54.7%, 84.7% and 50.0% COD, TP and PO4-P removal, corresponding to adsorption capacity of 94.7 mgDCO/g, 17.9 mgTP/g and 8.7 mgPO4-P/g, respectively. Even if the AC pretreatment did not show significant effects on Spirulina platensis growth during toxicity assays, the AC adsorption step strongly participated in the digestate detoxification by removing hardly biodegradable molecules such as phenolic compounds.
The formation of 2:1 and 1:1 phyllosilicates in Fe–Si–O–H systems occurs in various geological and engineering settings; however, the identification and characterization of these minerals is very challenging due to the limited amount that is accessible, the very small particle size, and often the large degree of heterogeneity of these samples. To overcome these drawbacks, the synthesis of iron-rich phyllosilicates was attempted in this study with an initial Fe/Si molar ratio ranging from 0.50 to 2.33. The synthesis was performed at 150°C under hydrothermal conditions over a period of 7 days. Synthesis products were characterized by X-ray diffraction and fluorescence, by infrared, Raman, and Mössbauer spectroscopies, and by transmission electron microscopy. Results revealed that the stability field of the 2:1 clay mineral was wider than that of the 1:1 clay mineral. The 2:1 clay mineral was less sensitive to redox conditions compared to the 1:1 clay mineral. In addition, a heterogeneity of phases formed (iron oxides, nontronite, cronstedtite, or greenalite) was identified.
This Special Issue (SI) contains the successful submissions [...].
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.
Polyoxometalates (POMs), Metals Organic-Frameworks (MOFs), Perovskites and Metal Oxides are promising crystalline materials that have received increasing attention due to their impressive photocatalytic performances. However, these catalysts are generally produced in powdered form limiting their reuse and recyclability. A recent solution consisted of associating them with an acrylate polymer via a simple, green and rapid photo -polymerization process under visible light irradiation. The obtained shaped photocomposites exhibited at the same time an excellent polymer robustness, stability and malleability while maintaining remarkable photo -catalytic properties. The fruitful incorporation of the different crystallites into polymer matrixes are already reported in the literature in our previous works and the chemical mechanisms were also given. However, in order to select the most performant photocatalytic system, which could be probably applied in future technological environmental applications, it is important to compare the photocatalytic efficiency of the different and recently developed photocomposites. Moreover, a comparison with the benchmark catalyst TiO2 is also provided for a better evaluation of their performance. Markedly, some of the reported catalysts were significantly better than TiO2. The absorption properties, the reusability and the thermal properties as well as the mechanical stabilities were taken into account during the in-depth comparison. The MIL-100(Fe)/polymer composite was selected as the most efficient photocatalytic system, which is also reusable during 10 successive catalytic cycles with an observed little decrease in the pollutants final degradation percentages starting from the 8th cycle. Moreover, this Fe-based MOF immobilized photocatalyst is characterized by interesting mechanical and thermal stabilities as well as a good absorption property allowing its application under visible light irradiation.
In the present work a remarkably simple procedure for the elaboration of wet cellulose film containing manganese oxide nanoparticles was developed. The films were produced using a mold made by 3D printing using cellulose dissolved in an ionic liquid, which allows the production of thin and homogeneous films of different shapes, types and designs which cannot be made using conventional techniques. Thanks to this possibility, the final catalytic object can be implemented in specific reactors. Manganese oxide nanoparticles were prepared as a colloidal solution by a redox/sol-gel procedure and then deposited on the cellulose films by wet impregnation. The catalytic film obtained was tested in the decomposition of a dye, indigo carmine (IC), in the absence of light. The influence of the pH of the solution on the decomposition rate was investigated. IC total decomposition was measured after 1-h reaction at pH below 3. At pH = 2, no deactivation of the catalyst was observed even after four decomposition cycles. This work provides a new strategy to design cellulose-based catalysts for dye removal from wastewater.
Advanced oxidation processes are considered as a promising technology for the removal of persistent organic pollutants from industrial wastewaters. In particular, the heterogeneous electro-Fenton (HEF) process has several advantages such as allowing the working pH to be circumneutral or alkaline, recovering and reusing the catalyst and avoiding the release of iron in the environment as a secondary pollutant. Among different iron-containing catalysts, studies using clay-modified electrodes in HEF process are the focus in this review. Fe(III)/Fe(II) within the lattice of clay minerals can possibly serve as catalytic sites in HEF process. The description of the preparation and application of clay-modified electrodes in the degradation of model pollutants in HEF process is detailed in the review. The absence of mediators responsible for transferring electrons to structural Fe(III) and regenerating catalytic Fe(II) was considered as a milestone in the field. A comprehensive review of studies investigating the use of electron transfer mediators as well as the mechanism behind electron transfer from and to the clay mineral structure was assembled in order to uncover other milestones to be addressed in this study area.
In the present work, hydrothermal carbonization of olive pomace was investigated for different conversion media at various temperatures. The produced hydrochars were characterized using different analytical techniques. The experiments show that the use of olive mill wastewater (OMW) as a carbonization media increased hydrochar recovery compared to the distilled water. Such results indicate the possible recovery of the OMW organic matter into hydrochar. However, the proximate analysis shows that hyrochars prepared in OMW media has higher volatile matter contents and low fixed carbon and ash contents compared to the hydrochar prepared in water media. Furthermore, morphological differences were observed with specific formation of carbon micro-spheres detected when using distilled water as reaction medium. These characterizations may guide for suitable applications for both hydrochars.
The present study focuses on the valorisation of winery industry wastes through slow pyrolysis of exhausted grape marc (EGM). The optimal pyrolysis parameters were firstly identified by small scale experiments carried out using thermogravimetric analysis. Nine pyrolysis temperatures were tested and their influence on the decomposition of the EGM residue and biochar yield was evaluated. Then, biochar production was conducted in a pilot plant at three chosen temperatures (450, 500 and 550 °C) at which the biochar was shown to be stable. The effects of biochar application to soil with respect to plant (ryegrass) growth was also evaluated. Pyrolysis of EGM at the 450–550 °C temperature range has been shown to generate thermally stable and nutrient-rich biochars, but only the biochar produced at 450 °C showed a marked benefit effect of ryegrass growth.
Biochars produced from exhausted grape marc waste were considered a potential source for agriculture biofertilization. Results indicated that the biochar application did not show a significant effect on ryegrass fresh weight increase. The pyrolysis temperature influenced the fresh and dry matter yield since it interferes with phosphorus bioavailability for plant growth. Potassium intakes were positively affected but not statistically significant. The % of soil stable aggregates decreased after 60 days. In the short term, there is no significant effect on soil structural stability. Biochar incorporation led to domination of large macro-aggregates, which are instables compared with small macro-aggregates. A dose of 15 t ha −1 considerably reduced the leached soil and thus improved water retention by changing soil porosity. Soil pH and electric conductivity markedly increased for all treatments after 60 days of incubation. Biochar extract had a significant inhibitory effect on Fusarium oxysporum and Phytophthora sp . The use of exhausted grape marc waste to produce a biochar has shown a good potential for carbon and water sequestration in soil.
Adding water to the synthesis medium leads to the formation of hybrids with low polycondensation, high crystallinity and high thermal stability.
The impact of synthesis conditions on the structure and the radionuclide adsorption capacity of silylated clay minerals was evaluated in this study. Two green solvents were selected in this work, phenoxypropanol and glycerol, and various synthesis temperatures (30, 60 and 90 degrees C) were tested for the preparation of 3-aminopropyltriethoxysilane (APTES)-functionalized Laponites. The resulting adsorbents exhibit various extent and location of the grafting reaction as a function of the used solvent and temperature. These modifications of the reactivity of the materials also impact adsorption and desorption properties of Co2+ and Sr2+. However, the two ions are well adsorbed whatever the synthesis conditions, and even in bisolute experiments, the adsorption capacity is not systematically proportional to the amount of loaded APTES, highlighting the specific impact of the synthesis conditions. Finally, the very limited desorption in saline solutions suggests that the synthesized adsorbents display suitable properties for the removal of radionuclides from aqueous solutions.
In this study, silylated Laponites® (LAP) were synthetized with various loads of 3-aminopropyltriethoxysilane (APTES) to evaluate their adsorption properties of 133Cs, 59Co, and 88Sr during single-solute and competitive experiments. The increase in the initial load of APTES increased the adsorbed amount of APTES in the resulted grafted clay. The characterization of LAP-APTES exhibited a covalent binding between APTES and LAP and emphasized the adsorption sites of APTES for each tested load. In comparison with raw LAP, LAP-APTES displayed significantly higher adsorption properties of Co2+, Cs+, and Sr2+. The competitive adsorption of these three contaminants provides a deeper understanding of the affinity between adsorbate and adsorbent. Therefore, Co2+ displayed a strong and specific adsorption onto LAP-APTES. Except for Cs+, the adsorption capacity was improved with increasing the load of APTES. Finally, the desorption behavior of the three contaminants was tested in saline solutions. Cs+ and Sr2+ were significantly released especially by inorganic cations displaying the same valence. Conversely, desorption of Co2+ was very low whatever the saline solution. LAP-APTES, therefore, presented suitable adsorption properties for the removal of radionuclides especially for Co2+, making this material suitable to improve the decontamination of radioactive wastewaters.