Search Results (22)

In this work, we report a green synthesis of zinc oxide (ZnO) nanoparticles using aqueous and ethanolic extracts of Tradescantia spathacea (purple maguey) as bioreducing and stabilizing agents, which are plant extracts not previously employed for metal oxide nanoparticle synthesis. This method provides an efficient, eco-friendly, and reproducible route to obtain ZnO nanoparticles, while minimizing environmental impact compared to conventional chemical approaches. The extracts were prepared following a standardized protocol, and their phytochemical profiles, including total phenolics, flavonoids, and antioxidant capacity, were quantified via UV-Vis spectroscopy to confirm their reducing potential. ZnO nanoparticles were synthesized using zinc acetate dihydrate as a precursor, with variations in pH and precursor concentration in both aqueous and ethanolic media. UV-Vis spectroscopy confirmed nanoparticle formation, while X-ray diffraction (XRD) revealed a hexagonal wurtzite structure with preferential (101) orientation and lattice parameters a = b = 3.244 Å, c = 5.197 Å. Scanning electron microscopy (SEM) showed agglomerated morphologies, and Fourier transform infrared spectroscopy (FTIR) confirmed the presence of phytochemicals such as quercetin, kaempferol, saponins, and terpenes, along with Zn–O bonding, indicating surface functionalization. Zeta potential measurements showed improved dispersion under alkaline conditions, particularly with ethanolic extracts. This study presents a sustainable synthesis strategy with tunable parameters, highlighting the critical influence of precursor concentration and solvent environment on ZnO nanoparticle formation. Notably, aqueous extracts promote ZnO synthesis at low precursor concentrations, while alkaline conditions are essential when using ethanolic extracts. Compared to other green synthesis methods, this strategy offers control and reproducibility and employs a non-toxic, underexplored plant source rich in phytochemicals, potentially enhancing the crystallinity, surface functionality, and application potential of the resulting ZnO nanoparticles. These materials show promise for applications in photocatalysis, in antimicrobial coatings, in UV-blocking formulations, and as functional additives in optoelectronic and environmental remediation technologies. Full article

Volatile fatty acids (VFA) are valuable intermediates with growing demand in chemical, pharmaceutical, and environmental applications. Their sustainable production from organic waste is increasingly explored in the context of circular economy and biorefinery models. This study investigates the co-fermentation of waste-activated sludge (WAS) and the organic fraction of municipal solid waste (OFMSW) as a strategy for integrated VFA and biogas production. Semi-continuous experiments were carried out to assess the effect of the substrates ratio (WAS:OFMSW = 90:10 and 30:70), hydraulic retention time (HRT), and pH control (5, 9, no control) on VFA yield and composition. Results showed that higher OFMSW content and alkaline conditions favoured VFA production, with a maximum yield of 144.9 mgHAc·gVS⁻¹ at pH 9 and 70:30 ratio. Acetate dominated, while butyrate production peaked at 114.1 mgHBu·gVS⁻¹ under high sludge conditions. However, the addition of alkali required for pH control may lead to excessive accumulation of alkaline-earth metal ions, which can disrupt biological processes due to their potential toxicity. Anaerobic digestion of fermentation residues enhanced biomethane yields significantly (0.27 NL·gVS⁻¹ vs. 0.05 NL·gVS⁻¹ from raw sludge). The proposed process demonstrates potential for converting wastewater treatment plants into biorefineries, maximising resource recovery while reducing environmental impact. Full article

This study explores the use of alkaline earth metal carboxylates as sustainable alternatives to conventional ammonium-based lixiviants for the eco-friendly extraction of weathered crust elution-deposited rare earth ores. We investigated the impact of lixiviant concentration, pH, and leaching temperature on the extraction efficiency of rare earths and aluminum, utilizing magnesium acetate and calcium acetate alongside traditional ammonium salts. The results showed that a leaching rate exceeding 91% for rare earths was achieved, while aluminum leaching remained under 30% at 298 K, pH 6.5–7.0, and 0.20 mol/L concentration of carboxylates. Notably, magnesium acetate was particularly effective in extracting medium and heavy rare earths at lower concentrations. A double electric layer model was used to clarify the leaching mechanism, indicating that zeta potential and double electric layer thickness were significantly affected by the concentration and pH of the leaching agents. Overall, this method presents an efficient approach for low-impurity extraction, offering valuable insights for sustainable mineral resource development. Full article

Sludge alkaline fermentation liquid (AFL) is a potential carbon source for biological denitrification. However, its effectiveness is limited due to the presence of nutrients and heavy metals. In this study, acid-modified sepiolite (MSEP) was used to extract short-chain fatty acids (SCFAs) from AFL under optimized conditions and then with the prepared MSEP-AFL as a carbon source for denitrification. The optimal condition with an MSEP dosage of 1.96 g/L and pH 7.93 at 30 °C was obtained based on single-factor experiments and response surface methodology (RSM). Carbon balance revealed that 96.2% of the SCFAs, including 43.7% acetate and 23.5% propionic acid, was retained in the MSEP, demonstrating its high selectivity. The adsorption process followed the pseudo-second-order kinetic and Langmuir isothermal model, indicating dominant physical adsorption on the surface or in the fiber pores. This was further supported by the changes in the morphological features and surface properties of the MSEP. In the batch nitrate utilization experiments, the prepared MSEP-AFL was proven to be efficient as a carbon source, with a nitrate removal efficiency of 88.7% and a specific denitrification rate of 8.2 mg NOx-N/g VSS·h, which was 22% higher than that of the AFL. This was due to the establishment of a delicate “release–utilization” balance. These findings contribute to our understanding of the use of AFL for denitrification. Full article

Bimetallic Pt₃Eu/C, Pt₃La/C, and Pt₃Ce/C electrocatalysts have been prepared, characterized, and tested for ethanol electro-oxidation (EEO). The materials were synthesized by chemical reduction with NaBH₄, rendering nanosized particles with actual compositions close to the nominals and no alloy formation. X-ray photoelectron spectroscopy (XPS) confirmed that the auxiliary rare-earth metals were present on the surface in oxide form. The electrochemical analyses in acid and alkaline EEO evidenced that, compared to Pt/C, the addition of rare earth metals in the form of oxides reduced the onset potential, increased the current density, and enhanced the stability. The results were fully confirmed in the DEFC single-cell measurements. Finally, the presence of rare earth metals in the oxidized form increased the percentage of acetic acid as the final product, making the electrocatalysts more selective and efficient than Pt/C, where acetaldehyde was the main product. Full article

Levoglucosan is an anhydrosugar from biomass that has important applications as a platform for obtaining many value-added derivatives with high demand in the chemical industry and bioproducts by fermentation, including biofuels, among others. Thus, the experimental strategy was to intensify the levoglucosan production in the condensable fraction (bio-oil) from pyrolysis gases using different biomass pretreatments before fast pyrolysis according to the following conditions: (a) biomass washing with 10% acetic acid; (b) biomass washing with 0.1% HNO₃, followed by impregnation with 0.1% H₂SO₄; and (c) biomass impregnation with 0.1% H₂SO₄. The pyrolysis was carried out in a pyroprobe reactor, coupled to GC/MS to verify the progress of the chemicals formed at 400, 500, and 600 °C. Although levoglucosan was the main target, the programs showed more than 200 pyrolytic compounds of which more than 40 were identified, including organic acids, ketones, aldehydes, furans, and phenols. Then, principal component analysis (PCA) allowed for the discrimination of the simultaneous effect of biomass acid treatment and pyrolysis temperature on the formation of the pyrolytic products. All treated biomasses with acids resulted in a levoglucosan yield increase, but the best result was achieved with acetic acid at 500 °C which resulted from 7-fold higher levoglucosan production with changes in the profiles by-products formed concerning untreated biomass. This result was attributed to the alkali and alkaline earth metals reduction and partial removal of lignin content and extractives by acid washing, increasing the cellulose and hemicellulose relative content in the treated biomass. This hypothesis was also confirmed by scanning electron microscope (SEM) and Fourier transform infrared (FTIR) qualitative analysis. Thus, the results achieved in this work show the potential of this biomass for levoglucosan production and other pyrolytic products, thereby being able to mitigate the environmental impact of this agricultural residue and contribute to the development of the coffee agro-industrial chain and the production of bioenergy from lignocellulosic biomass. Full article

The advancing effects of various alkali and alkaline earth metals (inclusive of K, Ca, and Sr) modified Cu/SiO₂ catalysts, prepared with a modified precipitation-gel method, were investigated for the production of ethanol via hydrogenation of methyl acetate. Our results showed that Sr-doped catalysts exhibited the best and most consistent results during catalytic tests. A series of techniques, including X-ray diffraction technique, Raman spectroscopy, N₂ adsorption/desorption, N₂O titration method, FTIR spectroscopy, and H₂ temperature, programmed desorption and reduction (TPD and TPR), and X-ray Photoelectron Spectroscopy, which was used to check the detailed characterization of Sr modification in the catalyst and its structural impacts on the properties of the catalyst. These results demonstrated that the addition of 5%Sr could strengthen the intrinsic stability of the catalyst by formulating the appropriate ratio of Cu⁺/(Cu⁰ + Cu⁺) to facilitate catalytic outcome improvement. The addition of 5%Sr-30%Cu/SiO₂ under the most favorable conditions, resulting in the peak conversion of MA (95%) and ethanol selectivity (96%), indicates its magnificent catalytic stabilizing effects. Furthermore, the best performing catalyst was compared and tested under various conditions (LHSV and temperatures) and a 300 h long life run. Full article

The information taken from David A. Scott’s book “Copper and Bronze in Art” was crucial for this research on copper corrosion products in Stuttgart. The examples discussed are: (1) the nature and variability of ‘Black Spots’ (or ‘Brown Fuzzies’), mainly copper sulfides, resulting from the action of sulfurous gases on copper containing materials at different relative humidities; (2) cupric hydroxide occurring during maritime corrosion or by cleaning, patination, and pigment synthesis (Bremen blue) when alkaline solutions are used; (3) the wondrous phenomenon of curly malachite, which does not imply any human involvement; (4) chalconatronite formed by the contact of metal to alkaline surface films on soda glass, providing sodium and carbonate ions; (5) the formation of copper formates in contact with glass by the action of electrolytes from the glass hydrolysis and the pollutant formaldehyde reacting to the formate; (6) syntheses and crystal structure determination by powder X-ray diffraction (no single crystals needed) of various basic copper acetates (‘verdigris’) with the aim to better differentiate between historic production methods. Full article

This paper investigated the effect of mineral surface oxidation on the floatability of Kevitsa low-grade Ni-Cu ore. Physicochemical measurements, ethylene diamine tetra acetic acid (EDTA) extraction, and oxygen uptake experiments were carried out with slurry and recycled process water samples obtained from the Kevitsa Cu-Ni sequential concentrator plant. The pH of recycled process water, copper flotation feed, and nickel flotation feed dropped by 0.7, 0.4, and 0.7 points, respectively, from May to July. The oxygen demand increased from recycled process water to the copper flotation feed, then dropped for the nickel flotation feed. The nickel flotation feed Redox potential (ORP) was lowest for July, while EDTA extractable metals increased from May to July. There was a 20% drop in nickel recoveries from May to July. Based on ORP measurements of the nickel flotation feed, good nickel flotation takes place in a moderately oxidizing (75–170 mV) and alkaline (9.2–9.7 pH) environment. Therefore, the ORP/pH of the nickel flotation feed is important to the nickel flotation. The results showed that at the Kevitsa plant, the grinding process is an electrochemically active environment, which, together with the incoming recycled process water quality, defines the degree of mineral surface oxidation for flotation. The increasing corrosiveness of the recycled process water increased mineral surface oxidation and depressed pentlandite flotation. Laboratory flotation experiments confirmed the observed poor plant flotation response when the corrosiveness of recycled process water increased. Total dissolved solids (TDS) was proven to be a reliable online parameter for the corrosiveness of the recycled process water and was inversely proportional to the pentlandite recovery. The findings of this study may help the plant develop ways to enable a timely response to changes in recycled process water quality to prevent harmful impacts on pentlandite flotation. Full article

Many heritage objects consist of glass in contact with metals. By ion exchange with absorbed water, alkaline aqueous films are formed on the glass surface. They contain sodium and/or potassium, hydroxide, and carbonate (uptake of carbon dioxide) ions. These electrolytes induce corrosion while in contact with metal. Surprisingly, this phenomenon has only been realised by research in Stuttgart in the last two decades. About 350 affected objects were detected in the meantime in a number of heritage collections. Because of the special electrolytes, unusual corrosion products are often formed. The unknown structure and formula of three of them could be determined by modern X-ray powder diffraction data evaluation. One example is the basic potassium lead carbonate, KOH‧2PbCO₃, detected on a pewter lid of a glass jug. The sodium analogon of already known structure was found in hollow glass balls mirrored on the inside with molten lead. Chalconatronite, Na₂[Cu(CO₃)₂]‧3H₂O, is known as a corrosion product of copper alloys in contact with soda solutions (here: from glass degradation). Exposed to acetic acid emissions (e.g., from wood), it transforms to a sodium copper acetate carbonate of hitherto undetermined structure. The ubiquitous pollutant formaldehyde reacts directly to formate in the alkaline medium provided by glass degradation. On copper alloys in contact with glass, formates are, therefore, frequent: Na₄Cu₄O(HCOO)₈(OH)₂‧4H₂O in 50% of all cases and in 33% Cu₂(HCOO)(OH)₃. Zinc (from brass) forms Zn(HCOO)₂‧2H₂O and Zn₄Cu₃(Zn_1−xCu_x)₆(HCOO)₈ (OH)₁₈·6H₂O. There are a number of other corrosion products, e.g., containing zinc and carboxylates awaiting further characterisation. Preventive conservation needs to slow down corrosion by dry storage (not lower than 35% rH). Pollutants need to be avoided by careful selection of materials for storage, display, and conservation. Full article

Chemical solution deposition (CSD) of BaTiO₃ (BT) or BT-based thin films relies on using a carboxylic acid and alcohol as the solvents for alkaline-earth carboxylate and transition-metal alkoxide, respectively; however, the esterification reaction of the solvents may lead to in-situ water formation and precipitation. To avoid such an uncontrolled reaction, we developed a route in which ethylene glycol (EG) is used as the solvent for Ba-acetate. The EG-based BT coating solutions are stable for at least a few months. The thermal decomposition of the BT xerogel obtained by drying the EG-based solutions depends on the choice of the solvent for the Ti-alkoxide as well: in the case of EG and 2-methoxyethanol solvents carbon residues are removed at only about 1100 °C, while in the case of ethanol it is concluded at about 700 °C. About 100 nm thick BT films derived from the EG-ethanol solution deposited on platinized silicon reveal dense, crack-free columnar microstructure. They exhibit local ferro- and piezoelectric properties. The macroscopic polarization-electric field loops were obtained up to a quite high electric field of about 2.4 MV/cm. The EG-ethanol based CSD route is a viable alternative to the established acetic acid–alcohol route for BT and BT-based films. Full article

In addition to C, H and O, some biomass is also rich in mineral elements. The recovery and utilization of special mineral elements is of great significance to prepare functional materials and alleviate the current energy shortage. Herein, we describe a facile strategy for making full use of the chemical composition (C, Fe) and special structure of red blood cells (RBCs) from waste pig blood to fabricate a dual metal (Fe, Co)-nitrogen (N)-doped porous carbon catalyst by pyrolysis of a mixture of RBCs biomass, cobaltous acetate, and melamine. The porous catalyst displays a comparable activity for oxygen reduction reaction (ORR) to that of commercial Pt/C catalyst, with a half-wave potential of 0.821 V_vsRHE in alkaline media and 0.672 V_vsRHE in acid electrolyte. Especially, the as-prepared catalyst shows excellent methanol tolerance and stability in both acidic and alkaline electrolytes, which is superior to commercial Pt/C catalysts. The excellent ORR activity of FeCo-N/C_(RBC) can be ascribed to the porous morphology and the cooperation between metal and nitrogen species. This work provides a novel idea of exploiting the composition of renewable biomass to modulate the activity and stability of carbon-based ORR catalysts. Full article

The development of electrocatalysts for energy conversion and storage devices is of paramount importance to promote sustainable development. Among the different families of materials, catalysts based on transition metals supported on a nitrogen-containing carbon matrix have been found to be effective catalysts toward oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) with high potential to replace conventional precious metal-based catalysts. In this work, we developed a facile synthesis strategy to obtain a Fe-N-C bifunctional ORR/HER catalysts, involving wet impregnation and pyrolysis steps. Iron (II) acetate and imidazole were used as iron and nitrogen sources, respectively, and functionalized carbon black pearls were used as conductive support. The bifunctional performance of the Fe-N-C catalyst toward ORR and HER was investigated by cyclic voltammetry, rotating ring disk electrode experiments, and electrochemical impedance spectroscopy in alkaline environment. ORR onset potential and half-wave potential were 0.95 V and 0.86 V, respectively, indicating a competitive performance in comparison with the commercial platinum-based catalyst. In addition, Fe-N-C had also a good HER activity, with an overpotential of 478 mV @10 mAcm⁻² and Tafel slope of 133 mVdec⁻¹, demonstrating its activity as bifunctional catalyst in energy conversion and storage devices, such as alkaline microbial fuel cell and microbial electrolysis cells. Full article

The disposal of voluminous, highly alkaline, bauxite residue (BR), the industrial by-product of alumina production by the Bayer process, constitutes an intricate global environmental problem. BR, containing valuable metals such as rare-earth elements (REEs)—in particular, scandium (Sc)—can be used as a secondary source for REE extraction. The scope of this study was the investigation of bioleaching as an innovative and environmentally friendly approach for the extraction of Sc from BR. The bioleaching parameters were studied on Greek BR and experiments were performed using different microbial cultures and solid to liquid ratios (S/L). The maximum extraction of Sc was 42% using Acetobacter tropicalis in a one-step bioleaching process at 1% S/L. The main organic acids produced were acetic, oxalic, and citric. The bioleaching data indicated a probable synergistic effect of the different organic acids produced by microorganisms along with a more targeted leaching mechanism. Full article

Heavy metals in soil pose a constant risk for animals and humans when entering their food chains, and limited means are available to reduce plant accumulation from more or less polluted soils. Biochar, which is made by pyrolysis of organic residues and sees increasing use as a soil amendment to mitigate anthropogenic C emissions and improve agronomic soil properties, has also been shown to reduce plant availability of heavy metals in soils. The cause for the reduction of metal uptake in plants when grown in soils enriched with biochar has generally been researched in terms of increased pH and alkalinity, while other potential mechanisms have been less studied. We conducted a pot experiment with barley using three soils differing in metal content and amended or not with 2% biochar made from Miscanthus x giganteus, and assessed plant contents and changes in bioavailability in bulk and rhizosphere soil by measuring extractability in acetic acid or ammonium nitrate. In spite of negligible pH changes upon biochar amendment, the results showed that biochar reduced extractability of Cu, Pb and Zn, but not of Cd. Rhizosphere soil contained more easily extractable Cu, Pb and Zn than bulk soil, while for Cd it did not. Generally, reduced plant uptake due to biochar was reflected in the amounts of metals extractable with ammonium nitrate, but not acetic acid. Full article