Search Results (1,356)

Titanium oxide (TiO₂) is of great interest in solar cell manufacturing, hydrogen production, and organic compound photodegradation. The synthesis variables and methodology affect the morphology, texture, crystalline structure, and phase mixtures of TiO₂, which, in turn, affect the optical and catalytic properties of TiO₂. In this work, the effect of acetic acid as a catalyst and chelating agent on the morphology, texture, crystal structure, optical properties, and photocatalytic activity of TiO₂ samples obtained using the sol–gel method with sodium dodecyl sulfate (SDS) as a template was investigated. The results indicated that acetic acid not only catalyzes the hydrolysis of the TiO₂ precursor but also acts as a chelating agent, causing a decrease in crystallite size from 18.643 nm (T7 sample, pH = 6.8, without addition of acetic acid) to 16.536 nm (T2 sample, pH = 2). At pH 2 and 3, only the anatase phase was formed (T2 and T3 samples), whereas at pH 5 and 6.8, in addition to the anatase phase, the brookite phase (11.4% and 15.61% for samples T5 and T7, respectively) was formed. The band-gap value of TiO₂ decreased with decreasing pH during synthesis. Although the T2 sample had the highest specific surface area and pore volume (232.02 m²g⁻¹ and 0.46 gcm⁻³, respectively), the T3 sample had better efficiency in methylene blue dye photodegradation because its bird-nest-like morphology improved photon absorption, promoting better photocatalytic performance. Full article

In this study, the advanced oxidation system of peroxymonosulfate (PMS) was activated by molybdenite supported on biochar (Molybdenite@BC), and the degradation efficiency, influencing factors and degradation mechanism of sulfamethoxazole (SMX) were explored through experiments. Molybdenite@BC, a composite material used in the study, was prepared by pyrolysis at high temperature. The optimum pyrolysis temperature was 700 °C, and the mass ratio of molybdenite to biochar (BC) was 1:3. By changing dosage of Molybdenite@BC, pH value, initial concentration of PMS, and the types and concentration of inorganic anions, the effects of various factors on SMX degradation were systematically studied. The optimum reaction conditions of the Molybdenite@BC/PMS process were as follows: Molybdenite@BC dosage was 100 mg/L, PMS concentration was 0.2 mM, pH value was 6.9 ± 0.2, and initial SMX concentration was 6 mg/L. Under these conditions, the degradation rate of SMX was 97.87% after 60 min and 99.06% after 120 min. The material characterization analysis showed that Molybdenite@BC had a porous structure and rich active sites, which was beneficial to the degradation of pollutants. After the composite material was used, the peaks of MoO₂ and MoS₂ became weaker, which indicated that there was some loss of molybdenum from the material structure. Electron paramagnetic resonance (EPR) and radical quenching experiments revealed that Molybdenite@BC effectively catalyzed PMS to generate various reactive oxygen radicals and non-free radicals, including singlet oxygen (¹O₂), hydroxyl radical (^•OH), sulfate radical (SO₄^•−) and superoxide radical (^•O₂⁻). ¹O₂ played a leading role in the degradation of SMX, while ^•OH and SO₄^•− had little influence. The intermediate products of the degradation of SMX in Molybdenite@BC/PMS system were analyzed by liquid chromatography–tandem mass spectrometry (LC–MS). The results showed that there were nine main intermediate products in the process of degradation, and the overall toxicity tended to decrease during the degradation of SMX. The degradation path analysis showed that with the gradual ring opening and bond breaking of SMX, small molecular compounds were generated, which were finally mineralized into H₂O, CO₂, CO₃²⁻, H₂SO₄ and other substances. The research results confirmed that the Molybdenite@BC/PMS process provided a feasible new method for the degradation of SMX in water. Full article

BO₃³⁻, PO₄³⁻, and SO₄²⁻ anionic groups were used to study their effects on the structure and luminescence of Sm³⁺-doped ZnO. ZnO, ZnO:Sm³⁺, ZnO, Zn₄B₆O₁₃:Sm³⁺, and Zn₂P₂O₇:Sm³⁺ phosphors were successfully synthesized via combustion synthesis. While BO₃³⁻ and PO₄³⁻ ions led to the formation of new crystalline phases, the sulfate precursor decomposed during synthesis, yielding ZnO with only minor surface sulfur traces. The XRD results revealed the formation of wurtzite crystal structures in the ZnO, ZnO:Sm³⁺, and ZnO-SO₄:Sm³⁺ samples, while a complete change of structure was observed after the incorporation of borate (BO₃³⁻) and phosphate (PO₄³⁻) ions into ZnO:Sm³⁺ to Zn₄B₆O₁₃:Sm³⁺ and Zn₂P₂O₇:Sm³⁺, respectively. The structures for borate and phosphate ions were confirmed as cubic (Zn₄B₆O₁₃) and monoclinic (Zn₂P₂O₇) crystal structures, respectively. The morphological studies of ZnO:Sm³⁺ and ZnO-SO₄:Sm³⁺ were characterized by aggregated particles with different shapes and sizes. Zn₄B₆O₁₃ and Zn₂P₂O₇ samples were characterized by having cubic and rough surfaces, respectively. The oxidation state of the Sm ions was confirmed by XPS analysis. The photoluminescence studies revealed a broad-band emission for the ZnO:Sm³⁺ and ZnO-SO₄:Sm³⁺ materials and characteristic Sm³⁺ emissions (from the ⁴G_5/2 level to lower states ⁶H_J (J = 5/2, 7/2, 9/2, and 11/2)) for the Zn₄B₆O₁₃ and Zn₂P₂O₇ samples. Enhanced emissions were observed after the incorporation of anionic group systems. The most intense PL emission was observed from the Zn₄B₆O₁₃ phosphor material. The CIE calculations revealed that the best color purity results were from Zn₄B₆O₁₃, which lay in the orange region with 98% color purity. Full article

Titanium compounds are an integral component for paint pigments, food additives (E171), catalysts, precursors for resistant structural materials, medicine, and water, and air purification and disinfection processes. A new and rather promising trend for titanium dioxide production is obtaining it from minerals with magnesium titanium structure. Magnesium titanates obtained by pyrometallurgical processing of quartz–leucoxene concentrate (oil sandstones). It was found that the optimal pyrometallurgical processing conditions were 4 h and a temperature of 1425–1450 °C, with TiO₂ → Mg_XTi_YO_Z conversion exceeding 95%, and that sulfation of the magnesium titanate mixture with 60–70% H₂SO₄ for 150–210 min allows a 95% extraction of titanium compounds into solution. Investigation of the mechanism of titanium compound precipitation from Mg-Ti-containing sulfuric acid solutions revealed that in the pH range from 3 to 6, only titanium compounds were extracted from solution, while coprecipitation of magnesium compounds begins only at pH above 6.5. The product obtained by precipitation is titanium dioxide with an anatase structure, with particle distribution ranging from 0.8 to 5.0 µm and a developed surface area over 250 m²/g with mesopores characteristic of sorption materials. Full article

Methoxy radicals (CH₃O•), formed as intermediates during methane oxidation, may play an underexplored but locally significant role in the atmospheric oxidation of dimethyl sulfide (DMS), a key sulfur-containing compound emitted primarily by marine phytoplankton. This study presents a comprehensive computational investigation of the reaction mechanisms and kinetics of DMS oxidation initiated by CH₃O•, using density functional theory B3LYP-D3(BJ)/6-311++G(3df,3pd), CCSD(T)/6-311++G(3df,3pd), and UCBS-QB3 methods. Our calculations show that DMS reacts with CH₃O• via hydrogen atom abstraction to form the methyl-thiomethylene radical (CH₃SCH₂•), with a rate constant of 3.05 × 10⁻¹⁶ cm³/molecule/s and a Gibbs free energy barrier of 14.2 kcal/mol, which is higher than the corresponding barrier for reaction with hydroxyl radicals (9.1 kcal/mol). Although less favorable kinetically, the presence of CH₃O• in localized, methane-rich environments may still allow it to contribute meaningfully to DMS oxidation under specific atmospheric conditions. While the short atmospheric lifetime of CH₃O• limits its global impact on large-scale atmospheric sulfur cycling, in marine layers where methane and DMS emissions overlap, CH₃O• may play a meaningful role in forming sulfur dioxide and downstream sulfate aerosols. These secondary organic aerosols lead to cloud condensation nuclei (CCN) formation, subsequent changes in cloud properties, and can thereby influence local radiative forcing. The study’s findings underscore the importance of incorporating CH₃O• driven oxidation pathways into atmospheric models to enhance our understanding of regional sulfur cycling and its impacts on local air quality, cloud properties and radiative forcing. These findings provide mechanistic insights that improve data interpretation for atmospheric models and extend predictions of localized variations in sulfur oxidation, aerosol formation, and radiative forcing in methane-rich environments. Full article

The decomposition of silicates in sulfuric acid to extract rare earth elements (REE) is typically characterized by the formation of an amorphous silica layer surrounding the receding crystal that may act as a passivation barrier limiting the rate of mineral dissolution. In this context, sulfuric acid treatment experiments coupled with detailed characterization of the evolution of the decomposition reaction were performed on natural allanite (CaREEAl₂Fe²⁺Si₃O₁₁O[OH]), as well as synthetic neodymium disilicate (Nd₂Si₂O₇), orthosilicate (Ca₂Nd₈(SiO₄)₆O₂), and orthophosphate (NdPO₄) phases in order to investigate if there are key factors, operating on a wide range of silicates, that negatively impact REE recovery. While, as expected, the acid strength is the driver in promoting the decomposition of the orthophosphate, for the silicates investigated, no matter their crystalline structure and chemical resistance, there is a severe passivation mechanism at play in concentrated H₂SO₄. However, in all cases, this effect can be minimized by water dilution, which strongly enhances sulfate-forming cation transfer across the produced amorphous silica layer. Taking into consideration this distinct characteristic of the mode of decomposition of silicates in sulfuric acid should help in defining optimal extraction strategies. Full article

This article presents a comprehensive study of the nitrogen-radon thermal mineral waters of the Jety-Oguz area, located in the southeastern part of the Issyk-Kul intermountain artesian basin (Northern Tien Shan). Based on new data from chemical and isotopic (δ¹⁸O, δD) analyses of natural waters (lake, river, and mineral) and the chemical composition of the water-bearing rocks, we identify the formation mechanisms of mineral waters with diverse composition, total dissolved solids (TDS), and temperature. Three main genetic types have been identified: (1) saline, high-TDS (up to 12.8 g/L) chloride sodium-calcium thermal waters (up to 32 °C). These waters are of meteoric origin and circulate within Middle Carboniferous carbonate rocks, acquiring their unique composition at depths of up to 3.0 km, where reservoir temperatures reach ~105 °C; (2) chloride-sulfate sodium-calcium waters (0.5 g/L, fresh, 22 °C), formed in alluvial deposits within the zone of active water exchange; and (3) low-TDS (1.8 g/L, brackish) waters of mixed composition, resulting from the mixing of a deep fluid with infiltrating meteoric waters. Isotopic data confirm a meteoric origin for all studied waters, including the high-TDS thermal types. The chemical composition diversity is attributed to several processes: mixing between the deep, high-TDS fluid and low-TDS infiltration waters, intense dissolution of evaporite rocks, and water–rock interaction. These findings are crucial for understanding the genesis of mineral waters in the Tien Shan intermountain basins and provide a scientific basis for their sustainable balneological exploitation. Full article

This study explores the application of a cobalt–manganese oxide catalyst supported on coal gangue (CoMnOx@CG) for peroxymonosulfate (PMS) activation to degrade phenol in coal chemical wastewater (CCW). The synthesized CoMnOx@CG catalyst demonstrated remarkable catalytic activity, achieving above 90% phenol removal within 10 min at pH 9 and 11. More importantly, the catalyst exhibited excellent stability and reusability, maintaining over 85% phenol removal efficiency after four consecutive cycles and cobalt leaching below 100 μg/L. Quenching experiments and electron paramagnetic resonance (EPR) analyses revealed that singlet oxygen (¹O₂), sulfate radicals (SO₄·⁻), and hydroxyl radicals (·OH) contributed to the degradation process. When treating actual CCW, the system significantly reduced both phenol and fluorescent dissolved organic matter, demonstrating its effectiveness for complex wastewater matrices. CoMnOx@CG provides a sustainable and practical solution for alkaline refractory wastewater remediation. Full article

This study investigated the antioxidant and antiadipogenic activities of sulfated polysaccharide (SPs) from the red seaweed Gracilaria caudata. First, sulfated polysaccharide-rich extracts (SPREs) from fifteen tropical seaweeds were screened to evaluate both their chemical composition and antioxidant potential. Among all samples, G. caudata exhibited the highest total antioxidant capacity, which justified its selection for detailed characterization. Sequential acetone precipitation produced three SPs (F1.5, F2.0, and F3.0), differing in sulfate content, monosaccharide composition, and molecular weight. In vitro assays revealed that F1.5 had the highest total antioxidant capacity and strong iron-chelating activity, while F2.0 exhibited the most effective hydroxyl radical scavenger. Importantly, F1.5 was the only SP that was non-cytotoxic to non-tumor cell lines. In 3T3-L1 preadipocytes, F1.5 attenuated H₂O₂-induced oxidative stress by reducing ROS and MDA levels and restoring GSH and SOD activity, achieving effects comparable to those of quercetin. Moreover, F1.5 inhibited adipogenic differentiation in a dose-dependent manner, as evidenced by decreased Oil Red O staining and reduced glycerol release. Collectively, these findings indicate that F1.5 exerts both antioxidant and antiadipogenic activities, highlighting G. caudata as a promising natural source of bioactive polysaccharides with potential nutraceutical applications. Nonetheless, further studies are required to elucidate the molecular mechanisms underlying these effects, validate the efficacy in vivo, and assess bioavailability and safety before clinical translation can be considered. Full article

The oxygen evolution reaction (OER) in water splitting involves complex multi-electron–proton transfer processes and represents the rate-determining step limiting overall electrolysis efficiency. Developing non-noble-metal catalysts with high activity and stability is therefore essential. Herein, a heterogeneous synthesis strategy was employed to in situ construct an iron-rich layered sulfate precursor (Fe_0.42Co_0.58-SO₄/NF) on nickel foam, which underwent deep self-reconstruction in alkaline electrolyte to form nanoflower-like Fe_0.42Co_0.58OOH/NF. The optimized catalyst maintained its iron-rich composition and hierarchical structure, delivering outstanding OER performance with an overpotential of 220 mV at 10 mA·cm⁻², a Tafel slope of 31.9 mV·dec⁻¹, and stability exceeding 12 h at 600 mA·cm⁻². Synchrotron analyses revealed dynamic transitions between mono-μ-O and di-μ-O Fe–M (M = Fe, Co) oxygen bridges during reconstruction, which enhanced both structural robustness and active-site density. The Fe-rich environment promoted the formation of Fe³⁺–O–Fe³⁺ units that synergized with Co⁴⁺ species to activate the lattice oxygen mechanism (LOM), thereby accelerating OER kinetics. This work elucidates the key role of oxygen-bridge geometry in optimizing catalytic activity and durability, providing valuable insights into the rational design of Fe–Co-based non-noble-metal catalysts with high iron content for efficient water oxidation. Full article

This study investigates the effect of added sodium sulfate on the performance of high-volume slag-cement mortar (HVSCM). Herein, Na₂SO₄ (0, 1, 2, and 4 wt.% Na₂O) was used to modify HVSCM. The compressive strength, fracture properties, microstructure, and environmental impact of the synthesized samples were analyzed. The results showed that the 1 day compressive strength of HVSCM can be improved by 345.5% with the addition of 4% Na₂O (as Na₂SO₄), compared to samples without Na₂SO₄. However, the 28 day compressive strength of Na₂SO₄-activated HVSCM was 14.3–26.4% lower than that of the non-activated HVSCM, though still comparable to OPC. Regarding fracture properties, the initial fracture toughness of non-activated HVSCM was 45.6% higher than that of Ordinary Portland cement (OPC) mortar. Furthermore, Na₂SO₄ activation further increased initial fracture toughness, with the sample containing 4% Na₂O showing a 101.1% improvement over OPC. In contrast, fracture energy was not significantly influenced by Na₂SO₄ addition. Microstructurally, the enhanced fracture properties of non-activated HVSCM were attributed to a higher degree of C-(A)-S-H polymerization and a denser binder phase. Sodium sulfate introduced sodium ions to strengthen electrostatic attraction and cohesion between C-(A)-S-H globules, offsetting reduced polymerization. Environmental assessment confirms that both activated and non-activated HVSCM substantially reduce embodied energy and CO₂ relative to OPC, while the additional embodied energy associated with Na₂SO₄ activation remains limited (<12%). Overall, this work provides a comprehensive understanding of the fracture behavior of Na₂SO₄-activated HVSCM, elucidating its capacity to enhance early-age strength and fracture toughness while highlighting its limited effect on long-term strength and fracture energy. These findings support the tailored use of Na₂SO₄ activation for sustainable construction applications. Full article

This study conducted an intensive air quality model evaluation as a response to the urgent need to understand the reliability, consistency, and uncertainty of air quality models supporting the implementation of the PM_2.5 Air Pollution Control Action Plan in China. Five regional air quality models of CMAQ version 5.02, CMAQ version 5.3.2, CAMx version 6.2, CAMx version 7.1, and NAQPMS have been evaluated for the CO, SO₂, NO₂, O₃, PM₁₀, and PM_2.5 concentration and components. A unified statistical method and the same observational data set of 2017, comprising 17 air pollution episodes collected from four super monitoring stations in the regions of Beijing–Tianjin–Hebei, Yangtze River Delta, Pearl River Delta, and Chengdu–Chongqing in China, have been used for the evaluation. All the participating models performed well in simulating the mean PM_2.5 concentrations, with an NMB ranging from −0.29 to −0.04, showing that the participating models are basically suitable for simulation and as evaluation tools for PM_2.5 in regulatory applications. However, the participating models showed a great variability for PM_2.5 components, with the NME ranging from 0.48 to 0.53. The models performed reasonably well in simulating the mean sulfate, nitrate, BC, and NH₄⁺ concentration in PM_2.5, while they were diversified in simulating the mean OC concentrations. The participating models also consistently performed well in simulating the concentration of NO₂, CO, and O₃. However, the models generally overestimated SO₂ concentrations, and to some extent underestimated PM₁₀ concentrations, which is likely attributable to uncertainties in emission sources and the rapid implementation of strict control policies for SO₂. The evaluation work of this study shows that there remains significant potential for further enhancement. Updating and improving the emission inventory should be prioritized to achieve better results, and further investigations into the uncertainties associated with the meteorological simulations, chemical mechanisms, and physical parameterization options of air quality models should also be conducted in future work. Full article

Vertical shafts are the lifelines of coal mines, serving as critical conduits for resources and personnel. However, the long-term exposure of shaft walls to groundwater erosion significantly reduces their service life and increases the risk of structural failures. This issue is particularly pressing in Inner Mongolia and Henan Provinces, two of China’s major coal-producing regions, where the challenge of sulfate attack on shafts in deep stratigraphic environments has become a growing concern. This study focused on the corrosion damage observed in these two typical auxiliary shafts: the net diameters and depths of the auxiliary shafts in Shunhe Coal Mine and Mataihao Coal Mine are 6 m and 768.5 m and 9.2 m and 457 m, respectively. The rock section shaft walls in the study range from 5 to 10 m in thickness and are constructed using C40 to C60 grade concrete. To assess the extent of this damage, we conducted a comprehensive analysis of shaft wall samples using water analysis, XRD (X-ray diffraction) analysis, FT-IR (Fourier transform infrared) spectroscopy, and XRF (X-ray fluorescence) analysis. The findings reveal that the identified secondary sulfate reaction products within the shaft wall concrete include calcium sulfate, gypsum, ettringite, and thaumasite. The CaO loss rates in the auxiliary shaft walls of Shunhe Coal Mine and Mataihao Coal Mine are as high as 66% and 47%, respectively. Additionally, the concentrations of SO₃ and MgO in both mines exceed normal levels by up to 5 and 11 times, and 13 and 3 times, respectively. Despite this, severe corrosion is primarily confined to the inner surface of the auxiliary shaft walls, without significant penetration into the deeper shaft structure. The corrosion damage is predominantly concentrated in the shaft sections where the geological environment is characterized by bedrock. This study provides field evidence and laboratory analyses to inform the mitigation of sulfate attack in auxiliary shafts. Full article

There are 880 studies focused on trivalent chrome baths, and several studies suggest the formation of ${\left[Cr\left(III\right)L(H_{2}O{)}_5\right]}^{2+}$, where $L$ is an additive such as oxalate. The literature suggests that this compound decreases the energy needed in the electrodeposition process. We call this approach the inner-sphere complex hypothesis because these complexes are suggested, such as principal intermediate compounds. There are several disadvantages of this postulate, which are numbered in our study. This hypothesis was tested via Fourier transform infrared spectroscopy performed in attenuated total reflectance (ATR) mode. In addition, the potassium bis(oxalato) diaqua chromate (III) dihydrate ($K\left[Cr{\left(C_2{O}_4\right)}_2{\left(O{H}_2\right)}_2\right]·2H_{2}O$) compound was selected as a probe molecule because it contains bridging $C-O-Cr$ bonds, which are supposedly the largest number of bonds in the inner-sphere complexes in bath solutions. There is strong evidence of numerous bridging $C-O-Cr$ bonds in the solid sample; conversely, in solution, $Cr\left(III\right)$ prefers to form terminal bonds ($Cr-O$). These results suggest that the concentration of the inner-sphere complex is lower in solution. In solutions containing chromium (III) sulfate and oxalate anions, the concentrations of these complexes are much lower. Although some inner-sphere complexes are formed, their concentration does not seem to be relevant to the electrodeposition process. Otherwise, at high ionic strengths, the formation of ion pairs and hydrogen bonds between $Cr\left(III\right)$ and additives is probable. Our research highlights the importance of vibrational spectroscopy in resolving the mechanics of the trivalent chrome electrodeposition process. This is the first study reporting a band of $Cr-O$ bonds in trivalent chrome baths. Full article

Samples of flotation tailings generated during the exploitation and processing of Zn–Pb–Cu–Ag ore from the Rudnik mine (Serbia) were investigated for their mineralogical, geochemical, and magnetic susceptibility properties. The flotation tailings consist of a complex mineral assemblage, including silicates, carbonates, sulfides, phosphates, sulfates, oxides, hydroxides, and native elements. Quartz, calcite, and orthoclase dominate the coarse fraction (>400 µm), accompanied by epidote, Ca-garnet, and Ca-clinopyroxene. Sulfide minerals are concentrated in finer fractions (<400 µm), with pyrite and arsenopyrite being the most abundant, followed by pyrrhotite, sphalerite, galena, and chalcopyrite. These sulfides occur as dispersed grains within a silicate–carbonate matrix. Post-depositional oxidative alteration is moderately developed, with pyrite replaced by hematite, galena by cerussite, and chalcopyrite by malachite. Geochemical analyses reveal that SiO₂ (avg. 38.98 wt%), Fe₂O₃ (avg. 23.68 wt%), Al₂O₃ (avg. 8.95 wt%), CaO (avg. 9.03 wt%) and MgO (avg. 1.50 wt%) dominate the composition. Economically significant metals include Zn (avg. 0.47 wt%), Pb (avg. 0.20 wt%), Cu (avg. 0.11 wt%), Ag (max. 19 µg/g), and Bi (max. 130 µg/g). Mass magnetic susceptibility shows a strong correlation with S (r = 0.92), Co (r = 0.90), and Bi (r = 0.87); moderate correlation with Fe₂O₃, Al₂O₃, and As; and negative correlation with Mn, TiO₂, Zn, and Pb. The ferromagnetic phase most likely originates from pyrrhotite, as well as hematite formed during pyrite alteration and goethite. Full article