Sustainable Chemistry

This study explores the development of a water-based hybrid thermoelectric (TE) material composed of Sb₂Te₃ nanoparticles (NPs) and polyethylene oxide (PEO). Sb₂Te₃ NPs were synthesized via the microwave-assisted colloidal route, where X-ray diffraction confirmed the purity and quality of the Sb₂Te₃ NPs. Key properties, including the Seebeck coefficient (S), electrical conductivity (σ), power factor (PF), and long-term stability, were studied. X-ray photoelectron spectroscopy (XPS) analysis revealed that exposure to water and oxygen leads to NP oxidation, which can be partially mitigated by hydrochloric acid (HCl) treatment, though this does not halt ongoing oxidation. Scanning electron microscopy (SEM) images displayed a percolation network of NPs within the PEO matrix. While the initial σ was high, a decline occurred over eight weeks, resulting in similar conductivity among all samples. The effect of surface treatments, such as 1,6-hexanedithiol (HDT), was demonstrated to enhance long-term stability. The results highlight both the challenges and potential of Sb₂Te₃/PEO hybrids for TE applications, especially regarding oxidation and durability, and underscore the need for improved synthesis and processing techniques to optimize their performance. This study provides valuable insights for the design of next-generation hybrid TE materials and emphasizes the importance of surface chemistry control in polymer–inorganic nanocomposites. Full article

Antimony (Sb), bismuth (Bi), and arsenic (As) are common contaminants of copper (Cu) electrolyte and anodes, necessitating strict control of their concentrations. The purification of Cu electrolytes is required and demands the application of appropriate techniques. This paper presents the methodology of selective precipitation, applied for Sb, Bi, and As recovery from the acidic eluate of a Cu electrolyte purification plant. An important aspect was the change in solution type from chloride to sulfate, prior to arsenic sequestration. A facile precipitation method, preceded by a reduction in As(V) and Sb(V), was applied. The primary objectives are focused on the preparation of three distinct concentrates: antimony oxychloride, bismuth oxychloride, and iron(III) arsenate(V), emphasizing optimal recovery and purity. The processes were performed in a specially designed, cascade-lined pilot scale installation, with a daily capacity of approximately 2.5 m³. In total, 22 m³ of eluate was processed, yielding 191 kg of Sb concentrate, 97 kg of Bi concentrate, and 163 kg of scorodite. The recovery of Sb was as high as 98%, with antimony content up to 50% in the concentrate. The recovery of bismuth varied from 60 to 99%, depending on the process parameters. The elimination of arsenic from the eluate was close to 100%. Full article

This study evaluated the extraction of oils from the seeds of bacupari (Garcinia brasiliensis Mart.) and leiteira (Tabernaemontana catharinensis), using carbon dioxide (CO₂) in the supercritical state. The effects of temperature (40, 50, and 60 °C) and pressure (20, 24, and 28 MPa) on the yield and extraction kinetics were investigated. The results indicated that, within the studied limits, temperature had a negligible influence on the process, while pressure had a greater impact on the yields owing to its effect on the density of supercritical CO₂ and the solubility of the extracted compounds. The maximum yields obtained were 14.8% for bacupari and 15.2% for leiteira, with most of the oil extracted within the first 30 min, indicating initial rapid extraction. Chemical composition analysis revealed relevant bioactive compounds in bacupari, including oleic acid (35%) and delta-tocopherol (19.6%). In leiteira, the main compounds identified were hexanedioic acid (29.2%) and stigmast-5-ene (7.95%). These results suggest the potential application of these oils in the pharmaceutical, cosmetic, and food sectors, while also highlighting the feasibility of using supercritical CO₂ as an extraction method for these plant matrices. Full article

The substitution of hazardous, environmentally persistent solvents (NMP and DMAc) with more sustainable alternatives (ETAc and GBL) in fabricating flat sheet polyactic acid (PLA) membranes via nonsolvent-induced phase separation for air filtration applications was the focus of this study. The polymer-solvent affinity was first evaluated using Hansen solubility parameters, confirming suitable Relative Energy Difference (RED) values (<1) for all solvent candidates. Dope solutions prepared with biodegradable solvents demonstrated higher viscosity compared to those prepared with environmentally persistent solvents. These biodegradable solvent systems also exhibited slower precipitation rates during membrane formation. This resulted in spongelike cross-sectional morphologies, contrasting with the combined fingerlike and spongelike structures observed in membranes fabricated with environmentally persistent NMP and DMAc. Thermal analysis revealed that membranes fabricated with biodegradable solvents exhibited superior thermal stability with higher glass transition temperatures (Tg = 54.39–55.34 °C) compared to those made with environmentally persistent solvents (Tg = 49.97–50.71 °C). Membranes fabricated with ethyl acetate (ETAc) showed the highest hydrophobicity (contact angle = 115.1 ± 9°), airflow rate (12.7 ± 0.28 LPM at 0.4 bar) and maintained filtration efficiency at values greater than 95% for 0.3 μm aerosols. Full article

Rare earth elements (REEs) make up integral components in personal electronics, healthcare instrumentation, and modern energy technologies. REE leaching with organic acids is an environmentally friendly alternative to traditional extraction methods. Our previous study demonstrated that batch ultrasound-assisted organic acid leaching of REEs can significantly decrease environmental impacts compared to traditional bioleaching. The batch method is limited to small volumes and is unsuitable for industrial implementation. This study proposes a novel approach to increase reaction volume using a continuous ultrasound-assisted organic acid leaching method. Laboratory experiments showed that continuous ultrasound-assisted leaching increased the leaching rate (µg/h) 11.3–24.5 times compared to our previously reported batch method. Techno-economic analysis estimates the cost of the continuous approach using commercially purchased organic acids is $9465/kg of extracted REEs and $4325/kg of extracted REEs, using gluconic acid and citric acid, respectively. The sensitivity analysis reveals that substituting commercially purchased organic acids with microbially produced biolixiviant can reduce the process cost by approximately 99% while minimally increasing energy consumption. Environmental assessment shows that most of the emissions stemmed from the energy required to power the ultrasound reactor. We concluded that increased leaching capacity using a continuous ultrasound-assisted approach is feasible, but process modifications are needed to reduce the environmental impact. Full article

The confectionery industry produces effluents with diverse and complex compositions and high organic loads, which are typically not treated by conventional treatment plants. In this context, the Fenton process presents itself as an advanced chemical treatment alternative due to its ease of application, cost-effectiveness, and ability to improve the degradability of challenging effluents. This study addressed the question: How can Fenton’s reagent be applied as a pretreatment to reduce the organic load in real effluents from the food industry? The research evaluated this chemical pretreatment for effluents from a starch-based gummy candy production process, aiming to reduce the organic load and aid subsequent conventional treatments. Parameters such as COD, total dissolved solids (TDS), temperature, pH, electrical conductivity, dissolved oxygen, and degrees Brix (°Bx) were monitored before and after 2 and 4 h of pretreatment. The results showed that Fenton pretreatment reduced COD by more than 31%, with efficiency influenced by effluent composition and concentration. This removal can reduce discharge rates and operating costs, providing an economic advantage. The process proved to be a promising pretreatment option, contributing to the initial removal of pollutants and improving the performance of wastewater treatment systems, thus supporting sustainable industrial practices. Full article

Bimetallic mesoporous photocatalysts were synthesized via a wet impregnation method using SBA-15 as a support, and characterized by UV–visible diffuse reflectance spectroscopy, low-angle X-ray diffraction and N₂ physisorption. Among the tested materials, the Ti/Mn combination exhibited the highest photocatalytic activity in azo dye degradation. To understand this enhanced performance, catalysts with varying Mn loads and calcination ramps were evaluated. Additionally, experiments with radical scavengers (isopropanol, chloroform) and under N₂ insufflation were conducted to identify the active radical species. Catalysts prepared with low Mn content and higher calcination ramps showed the greatest activity, which significantly decreased with isopropanol, indicating hydroxyl radicals as the main reactive species. In contrast, samples with higher Mn content and quicker heating displayed reduced activity in the presence of chloroform, suggesting superoxide radical involvement. Spectroscopic analyses (XPS, UV–Vis DRS) revealed that increasing Mn load promotes the formation of Mn²⁺ over Mn⁴⁺ species and lowers the band gap energy. These findings highlight the direct correlation between synthesis parameters, surface composition and optical properties, providing a strategy for fine-tuning the performance of a photocatalyst. Full article

Aluminothermic reduction is gaining renewed interest as an alternative processing route for the circular economy. Aluminium is produced electrochemically in the Hall–Héroult process with minimal CO₂ emissions if electricity is sourced from non-fossil fuel energy sources. The Al₂O₃ product from the aluminothermic reduction process can be recycled via hydrometallurgy, with leaching as the first step. NaAlO₂ is a water-leachable compound that forms a pathway for recycling Al₂O₃ with hydrometallurgy. In this work, a suitable slag formulation is applied in the aluminothermic reduction of manganese ore to form a Na₂O-based slag of high Al₂O₃ solubility to effect good alloy–slag separation. The synergistic effect of added chromium metal as a collector metal is illustrated with an increased alloy yield at 68%, from 43% without added Cr. The addition of small amounts of carbon reductant to MnO₂-containing ore ensures rapid pre-reduction to MnO. This approach negates the need for a pre-roasting step. The alloy and slag chemical analyses are compared to the thermochemistry-predicted phase chemistry. The alloy consists of 57% Mn, 18% Cr, 18% Fe, 3.4% Si, 1.5% Al, and 2.2% C. The formulated slag exhibits high Al₂O₃ solubility, enabling effective alloy–slag separation, even at an Al₂O₃ content of 55%. Full article

Iodine is an essential element for the synthesis of thyroid hormones. Iodine deficiency leads to a range of health consequences known as iodine deficiency disorders. To assess the iodine nutritional status of a population, urinary iodine (UI) is typically measured. This work introduces a novel and simple analytical method for determining UI using silver triangular nanoplates (AgTNPs) after interfering substances are removed via solid-phase extraction (SPE). The AgTNPs were synthesized and characterized using Transmission Electron Microscopy, UV–vis spectroscopy, and zeta potential measurements. The limit of detection of iodide of the AgTNPs assessed spectrophotometrically was 35.78 µg I⁻/L. However, urine samples interfered with the colorimetric reaction. Thus, an SPE methodology was developed and optimized to eliminate urine interferents that hinder AgTNP performance. A logistic regression analysis was conducted to validate the combined application of SPE and AgTNPs for the qualitative determination of UI. This work demonstrated that the developed SPE methodology eliminates these interferents and extracts iodide from the sample, allowing the accurate determination of UI using AgTNPs. This reliable sample preparation method was then used on actual human urine samples to accurately identify UI deficiency levels. The proposed methodology offers an effective and environmentally friendly approach for monitoring iodine status, without requiring highly complex equipment. Full article

This review sheds some light on the emerging niche of the reuse of spent adsorbents in electrochemical devices. Reuse and repurposing extend the adsorbent’s life cycle, remove the need for long-term storage, and generate additional value, making it a highly eco-friendly process. Main adsorbent-type materials are overviewed, emphasising desired properties for initial adsorption and subsequent conversion to electroactive material step. The effects of the most frequent regeneration procedures are compared to highlight their strengths and shortcomings. The latest efforts of repurposing and reuse in supercapacitors, fuel cells, and batteries are analysed. Reuse in supercapacitors is dominated by materials that, after a regeneration step, lead to materials with high surface area and good pore structure and is mainly based on the conversion of organic adsorbents to some form of conductive carbon adlayer. Additionally, metal/metal-oxide and layered-double hydroxides are also being developed, but predominantly towards fuel cell and battery electrodes with respectable oxygen reduction characteristics and significant capacities, respectively. Repurposed adsorbents are being adopted for peroxide generation as well as direct methanol fuel cells. The work puts forward electrochemical devices as a valuable avenue for spent adsorbents and as a puzzle piece towards a greener and more sustainable future. Full article

With increasing concerns about climate change and the depletion of fossil fuels, hemicellulose sugars from lignocellulosic biomass are gaining attention as sustainable feedstocks for producing biofuels and valuable chemicals. In this study, the extraction of hemicellulose sugars from corncob biomass was performed using hydrothermal pretreatment. Response Surface Methodology (RSM) with the Box–Behnken Design (BBD) was employed to optimize different parameters. The tested parameters included the corncob-to-water ratio (0.5:10, 1.5:10), time (30 to 90 min), and temperature (150 to 170 °C), to achieve the highest sugar yields (xylose, arabinose, and total sugars). The ANOVA results for the full quadratic polynomial model, which evaluates the effects of the three variables on xylose yield, indicate that the model is highly significant and provides a good fit to the data. This was evidenced by the minimal difference (0.003) between the predicted R² and the adjusted R². This study reports one of the highest recoveries of hemicellulosic sugars from corncobs and also evaluates degradation byproducts, offering a more efficient and comprehensive pretreatment approach that employs a lower temperature and a mild acid concentration (1%) compared with earlier research. The highest yields of xylose (103.49 mg/g), arabinose (26.75 mg/g), and total sugars (163.21 mg/g) were obtained at 160 °C and a corncob-to-water ratio of 0.5:10, after 90 min. Degradation products such as HMF and furfural in the hydrolysate were also analyzed by HPLC. The hydrolysate obtained from hydrothermal pretreatment contained oligomers that were converted into monomers through 1% H₂SO₄ hydrolysis. The highest yields after the acidic hydrolysis were 301.93 mg/g xylose, 46.96 mg/g arabinose, and 433.79 mg/g total sugars hydrolysis. Full article

This study investigates the potential of Pinus pinaster subsp. atlantica bark, a forestry by-product from northern Portugal, as a source of phenolic compounds with strong antioxidant properties. Microwave-assisted extraction (MAE) was used to optimize recovery, assessing the effects of solvent composition (water, ethanol, and 50:50 water–ethanol), extraction time (15 or 30 min), and temperature (90, 110, or 130 °C) using a one-variable-at-a-time approach. High-Performance Liquid Chromatography (HPLC) profiling characterized the polyphenol composition. The results showed that solvent choice strongly influenced extract composition and bioactivity, with hydroethanolic and ethanolic extracts exhibiting the highest antioxidant activities in DPPH, ABTS, and ORAC assays. Optimal conditions—50:50 water–ethanol, 130 °C, 15 min—yielded 11.13% (w/w) extract, 3.10 mg GAE/mL total phenolics, and 2.01 mg CE/mL condensed tannins, comparable to commercial extracts such as Pycnogenol^®. MAE proved effective, rapid, and solvent-efficient, enhancing phenolic recovery without degrading extract quality. These findings highlight the potential of P. pinaster bark extracts for biomedical, nutraceutical, and cosmetic applications, supporting the sustainable valorization of forestry residues and aligning with circular economy principles. Full article

This review highlights recent advances in the use of nutshell-derived materials, including peanut, walnut, and other lignocellulosic shell wastes, as reinforcers in polymer composites. The focus is placed on evaluating how the incorporation of nutshell fillers influences the mechanical and thermal properties of various polymer matrices. Key findings across multiple studies show that nutshell reinforcement can significantly enhance tensile strength, modulus, thermal stability, and biodegradability, depending on filler concentration, particle size, and surface treatment. The review also discusses the sustainability and economic benefits of using agricultural waste as a functional additive, offering insights into the design of low-cost, eco-friendly polymer composites for packaging, construction, and environmental applications. Full article

Facing energy and environmental issues is recognized globally as one of the major challenges for sustainable development, to which sustainable chemistry can make significant contributions. Strontium ferrate-based materials belong to a little-known class of perovskite-type compounds in which iron is primarily stabilized in the unusual 4+ oxidation state, although some Fe³⁺ is often present, depending on the synthesis and processing conditions and the type and amount of dopant. When doped with cerium at the Sr site, the SrFeO_3−δ cubic structure is stabilized, more oxygen vacancies form and the Fe⁴⁺/Fe³⁺ redox couple plays a key role in its functional properties. Alone or combined with other materials, Ce-doped strontium ferrates can be successfully applied to wastewater treatment. Specific doping at the Fe site enhances their electronic conductivity for use as electrodes in solid oxide fuel cells and electrolyzers. Their oxygen storage capacity and oxygen mobility are also exploited in chemical looping reactions. The main limitations of these materials are SrCO₃ formation, especially at the surface; their low surface area and porosity; and cation leaching at acidic pH values. However, these limitations can be partially addressed through careful selection of synthesis, processing and testing conditions. This review highlights the high versatility and efficiency of cerium-doped strontium ferrates for energy and environmental applications, both at low and high temperatures. The main literature on these compounds is reviewed to highlight the impact of their key properties and synthesis and processing parameters on their applicability as sustainable thermocatalysts, electrocatalysts, oxygen carriers and sensors. Full article

Natural dyes and pigments are gaining importance as a sustainable alternative to synthetic dyes. Sourced from renewable materials, they are known for their biodegradable and non-toxic properties, offering a diverse range of color profiles and applications across industries such as textiles, cosmetics, food, and pharmaceuticals. This manuscript discusses various aspects of natural dyes and pigments (derived from plants and microbes), including anthocyanins, flavonoids, carotenoids, lactones, and chlorophyll. Furthermore, it highlights the polyphenolic nature of these compounds, which is responsible for their antioxidant activity and contributes to their anticancer, antibacterial, antifungal, antiprotozoal, and immunomodulatory effects. However, natural dyes are often categorized as pigments rather than dyes due to their limited solubility, a consequence of their molecular characteristics. Consequently, this manuscript provides a detailed discussion of key structural challenges associated with natural dyes and pigments, including thermal decomposition, photodegradation, photoisomerization, cross-reactivity, and pH sensitivity. Due to these limitations, natural dyes are currently used in relatively limited applications, primarily in the food industry, and, to lesser extent, in textiles and coatings. Nevertheless, with ongoing research and technological innovations, natural dyes present a viable alternative to synthetic dyes, promoting a more sustainable and environmentally conscious future. Full article

2,5-bis(hydroxymethy)lfuran (BHMF), a renewable compound with extensive industrial applications, can be obtained by selective hydrogenation of the C=O group of 5-hydroxymethylfurfural (HMF), a platform molecule derived from lignocellulosic biomass. In this work, we perform kinetic modeling of the selective liquid-phase hydrogenation of HMF to BHMF over a Cu/SiO₂ catalyst prepared by precipitation–deposition (PD) at a constant pH. Physicochemical characterization, using different techniques, confirms that the Cu/SiO₂–PD catalyst is formed by copper metallic nanoparticles of 3–5 nm in size highly dispersed on the SiO₂ surface. Before the kinetic study, the Cu/SiO₂-PD catalyst was evaluated in three solvents: tetrahydrofuran (THF), 2-propanol (2-POH), and water. The pattern of catalytic activity and BHMF yield for the different solvents was THF > 2-POH > H₂O. In addition, selectivity to BHF was the highest in THF. Thus, THF was chosen for further kinetic study. Several experiments were carried out by varying the initial HMF concentration (C⁰_HMF) between 0.02 and 0.26 M and the hydrogen pressure (P_H2) between 200 and 1500 kPa. In all experiments, BHMF selectivity was 97–99%. By pseudo-homogeneous modeling, an apparent reaction order with respect to HFM close to 1 was estimated for a C⁰_HMF between 0.02 M and 0.065 M, while when higher than 0.065 M, the apparent reaction order changed to 0. The apparent reaction order with respect to H₂ was nearly 0 when C⁰_HMF = 0.13 M, while for C⁰_HMF = 0.04 M, it was close to 1. The reaction orders estimated suggest that HMF is strongly absorbed on the catalyst surface, and thus total active site coverage is reached when the C⁰_HMF is higher than 0.065 M. Several Langmuir–Hinshelwood–Hougen–Watson (LHHW) kinetic models were proposed, tested against experimental data, and statistically compared. The best fitting of the experimental data was obtained with an LHHW model that considered non-competitive H₂ and HMF chemisorption and strong chemisorption of reactant and product molecules on copper metallic active sites. This model predicts both the catalytic performance of Cu/SiO₂-PD and its deactivation during liquid-phase HMF hydrogenation. Full article

Dry Turkish oak (Quercus cerris) sawdust, untreated and treated with three activators, (H₃PO₄, NaOH and H₂O₂) was pyrolyzed under limited-oxygen conditions to obtain biochar samples. The electrochemical properties of these samples were tested and compared to the properties of several commercial carbon blacks. The electrochemical characterization was performed via cyclic voltammetry, analyzing the response toward two commonly used redox probes, [Fe(CN)₆]^3−/−4− and [Ru(NH₃)₆]^2+/3+. The influence of the scan rate on this response was investigated, and the resulting data were used to obtain the values of the heterogenous charge transfer constant, k₀. Higher k₀ values were observed for carbon blacks than for investigated biochar samples. The detection of 4-nitrophenol and heavy metal ions was used to assess the applicability of biochars for electroanalytical purposes. The response of untreated biochar was comparable with the response of Vulcan carbon black, which showed the best response of all analyzed carbon blacks. Full article

Biomorphic mineralization was employed to synthesize novel Mn–Ce and Mn–Co–Ce oxide fibers using commercial cotton as a biotemplate, aiming to assess their catalytic performance in diesel soot combustion and CO oxidation. Two synthesis protocols—one with and one without citric acid—were investigated. The inclusion of citric acid led to fibers with more uniform morphology, attributed to improved precursor distribution, although synthesis yields decreased for Co-containing systems. In soot combustion tests, Mn–Ce catalysts synthesized with citric acid outperformed their monometallic counterparts. While cobalt incorporation enhanced the mechanical robustness of the fibers, it did not significantly boost catalytic activity. Selected formulations were also evaluated for CO oxidation, with Mn–Co–Ce fibers achieving T₅₀ values in the 240–290 °C range, comparable to Co–Ce nanofibers reported in the literature. These results demonstrate that biomorphic fibers produced through a simple and sustainable route can offer competitive performance in soot and CO oxidation applications. Full article

The thermal modification of wood has emerged as a sustainable and effective method for enhancing the physical, chemical, and mechanical properties of wood without the use of harmful chemicals. This review summarizes the current state-of-the-art in thermal wood modification, focusing on the mechanisms of wood degradation during treatment and the resulting changes in the properties of the material. The benefits of thermal modification of wood include improved dimensional stability, increased resistance to biological decay, and improved durability, while potential risks such as reduced mechanical strength, color change, and higher costs of wood under certain conditions are also discussed. The review highlights recent advances in process optimization and evaluates the trade-offs between improved performance and possible structural drawbacks. Finally, future perspectives are outlined for sustainable applications of thermally modified wood in various industries. Emerging trends and future research directions in the field are identified, aiming to improve the performance and sustainability of thermally modified wood products in construction, furniture, and other industries. Full article