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Soil minerals influence the biogeochemical cycles of fluoride (F) and phosphorus (P), impacting soil quality and bioavailability to plants. However, the cooperative mechanisms of soil minerals in governing F and P in the soil environment remain a grand challenge. Here, we reveal the essential role of a typical soil mineral, montmorillonite (Mt), in the cycling and fate of F and P. The results show that the enrichment of metal sites on the Mt surface promotes the mineralization of F to the fluorapatite (FAP) phase, thereby remaining stable in the environment, simultaneously promoting P release. This differential behavior leads to a reduction in the level of F pollution and an enhancement of P availability. Moreover, solid-state NMR and HRTEM observations confirm the existence of metastable F-Ca-F intermediates, emphasizing the pivotal role of Mt surface sites in regulating crystallization pathways and crystal growth of FAP. Furthermore, the in situ atomic force microscopy and theoretical calculations reveal molecular fractionation mechanisms and adsorption processes. It is observed that a competitive relationship exists between F and P at the Mt interface, highlighting the thermodynamically advantageous pathway of forming metastable intermediates, thereby governing the activity of F and P in the soil environment at a molecular level. This work paves the way to reveal the important role of clay minerals as a mineralization matrix for soil quality management and offers new strategies for modulating F and P dynamics in soil ecosystems.
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Fluoretos , Fósforo , Fluoretos/química , Fósforo/química , Solo/química , Argila/química , Apatitas/química , Bentonita/química , Adsorção , Minerais/química , Silicatos de Alumínio/químicaRESUMO
Lake sediments connection to the biogeochemical cycling of phosphorus (P) and carbon (C) influences streamwater quality. However, it is unclear whether and how the type of sediment controls P and C cycling in water. Here, the adsorption behavior of montmorillonite (Mt) with different interlayer cations (Na+, Ca2+, or Fe3+) on dissolved organic matter (DOM) and P was investigated to understand the role of Mt in regulating the organic carbon-to-phosphate (OC/P) ratio within freshwater systems. The adsorption capacity of Fe-Mt for P was 3.2-fold higher than that of Ca-Mt, while it was 1/3 lower for DOM. This dissimilarity in adsorption led to an increased OC/P in Fe-Mt-dominated water and a decreased OC/P in Ca-Mt-dominated water. Moreover, an in situ atomic force microscope and high-resolution mass spectrometry revealed molecular fractionation mechanisms and adsorptive processes. It was observed that DOM inhibited the nucleation and crystallization processes of P on the Mt surface, and P affected the binding energy of DOM on Mt through competitive adsorption, thereby governing the interfacial P/DOM dynamics on Mt substrates at a molecular level. These findings have important implications for water quality management, by highlighting the role of clay minerals as nutrient sinks and providing new strategies for controlling P and C dynamics in freshwater systems.
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Matéria Orgânica Dissolvida , Fósforo , Argila , Adsorção , Minerais/química , Lagos/química , CarbonoRESUMO
To achieve a high separation efficiency of photogenerated carriers in semiconductors, constructing high-quality heterogeneous interfaces as charge flow highways is critical and challenging. This study successfully demonstrates an interfacial chemical bond and internal electric field (IEF) simultaneously modulated 0D/0D/1D-Co3 O4 /TiO2 /sepiolite composite catalyst by exploiting sepiolite surface-interfacial interactions to adjust the Co2+ /Co3+ ratio at the Co3 O4 /TiO2 heterointerface. In situ irradiation X-ray photoelectron spectroscopy and density functional theory (DFT) calculations reveal that the interfacial Co2+ OTi bond (compared to the Co3+ OTi bond) plays a major role as an atomic-level charge transport channel at the p-n junction. Co2+ /Co3+ ratio increase also enhances the IEF intensity. Therefore, the enhanced IEF cooperates with the interfacial Co2+ OTi bond to enhance the photoelectron separation and migration efficiency. A coupled photocatalysis-peroxymonosulfate activation system is used to evaluate the catalytic activity of Co3 O4 /TiO2 /sepiolite. Furthermore, this work demonstrates how efficiently separated photoelectrons facilitate the synergy between photocatalysis and peroxymonosulfate activation to achieve deep pollutant degradation and reduce its ecotoxicity. This study presents a new strategy for constructing high-quality heterogeneous interfaces by consciously modulating interfacial chemical bonds and IEF, and the strategy is expected to extend to this class of spinel-structured semiconductors.
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Phosphogypsum (PG) presents considerable potential for agricultural applications as a secondary primary resource. However, it currently lacks environmentally friendly, economically viable, efficient, and sustainable reuse protocols. This study firstly developed a PG-based mineral slow-release fertilizer (MSRFs) by internalization and fixation of urea within the PG lattice via facet-engineering strategy. The molecular dynamics simulations demonstrated that the binding energy of urea to the (041) facet of PG surpassed that of the (021) and (020) facets, with urea's desorption energy on the (041) facet notably higher than on the (021) and (020) facets. Guided by these calculations, we selectively exposed the (041) dominant facet of PG, and then achieving complete urea fixation within the PG lattice to form urea-PG (UPG). UPG exhibited a remarkable 48-fold extension in N release longevity in solution and a 45.77% increase in N use efficiency by plants compared to conventional urea. The facet-engineering of PG enhances the internalization and fixation efficiency of urea for slow N delivery, thereby promoting nutrient uptake for plant growth. Furthermore, we elucidated the intricate interplay between urea and PG at the molecular level, revealing the involvement of hydrogen and ionic bonding. This specific bonding structure imparts exceptional thermal stability and water resistance to the urea within UPG under environmental conditions. This study has the potential to provide insights into the high-value utilization of PG and present innovative ideas for designing efficient MSRFs.
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Sulfato de Cálcio , Fertilizantes , Fósforo , Sulfato de Cálcio/química , Fósforo/química , Ureia/química , Minerais/química , Nitrogênio/química , Simulação de Dinâmica Molecular , Agricultura/métodos , NutrientesRESUMO
The microstructure of Au metal cocatalyst has been shown to significantly influence its optical and electronic properties. However, the impact of Au defect engineering on photocatalytic activity remains underexplored. In this study, we synthesize different Au-TiO2 composites by in-situ hybridizing face-centered cubic (F-Au) and twin boundary defect Au (T-Au) nanoparticles (NPs) onto the surface of TiO2. We find that T-Au NPs with twin defects serve as highly efficient cocatalysts for converting alcohols into their corresponding aldehydes while also generating H2. The optimized T-Au/TiO2 composite yields an H2 evolution rate of 6850 µmol h-1 g-1 and a BAD formation rate of 6830 µmol h-1 g-1, about 38 times higher than that of blank TiO2. Compared to F-Au/TiO2, the T-Au/TiO2 composite enhances charge separation, extends the lifetime of electrons, and provides more active sites for H2 reduction. The twin defect also improves alcohol reactant adsorption, boosting overall photocatalytic performance. This research paves the way for more studies on defect engineering in metal cocatalysts for enhanced catalytic activities in organic synthesis and H2 evolution.
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This study evaluated the adsorption of five volatile organic compounds (VOCs) on Opoka, precipitated silica, and palygorskite, to elucidate the effect of their pore size on VOCs adsorption. The adsorption capacity of these adsorbents is not only highly correlated with their surface area and pore volume, but also notably improved by the presence of micropores. The variation in adsorption capacity for different VOCs was primarily influenced by their boiling point and polarity. Palygorskite, which had the smallest total pore volume (0.357 cm3/g) but the largest micropore volume (0.043 cm3/g) among the three adsorbents, exhibited the highest adsorption capacity for all tested VOCs. Additionally, the study constructed slit pore models of palygorskite with micropores (0.5 and 1.5 nm) and mesopores (3.0 and 6.0 nm), calculated and discussed the heat of adsorption, concentration distribution, and interaction energy of VOCs adsorbed on different pore models. The results revealed that the adsorption heat, concentration distribution, total interaction energy, and van der Waals energy decrease with increasing pore size. The concentration of VOCs in 0.5 nm pore was nearly three times that in 6.0 nm pore. This work can also provide guidance for further research on using adsorbents with mixed microporous and mesoporous structures to control VOCs.
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Inspired by the features of both transition metal oxide and natural clinoptilolite (flaky structure with suitable pore diameter and open skeleton structure), we adopted a robust strategy by immobilization of nickel ferrite nanoparticles (NiFe2O4) on the clinoptilolite surface via typical citric acid combustion method. The hybrid catalyst exhibited enhanced peroxymonosulfate (PMS) activation efficiency and bisphenol A (BPA) degradation performance. Calculated by effective equivalent of NiFe2O4, it is found that the reaction rate constant (k) of NiFe2O4/clinoptilolite/PMS system (0.1859 min-1) was 11.9 times higher than that of bare NiFe2O4/PMS system (0.0156 min-1), which demonstrated that catalyst would be conjugated to PMS or contaminant efficiently and renders the rapid degradation and mineralization in the presence of clinoptilolite. After comprehensive characterization analysis and DFT simulations, natural mineral carrier effect (i.e. decreased crystalline size, increased oxygen vacancy content, etc.), abundant surface-bonded and structural hydroxyl groups as well as effective bonding with iron or nickel ions charged for the potential activation mechanism of PMS by NiFe2O4/clinoptilolite composite. And it is indicated that not only â¢OH and SO4â¢-, but also 1O2 was involved into series reactions. Overall, this study put forward a green and promising technology for high-toxic wastewater treatment.
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Developing low-cost, high-efficiency catalysts for advanced oxidation processes remain a key issue for the degradation of organic pollutants. In this study, a novel FeCo2O4/rectorite composite was synthesized via a facile combustion process and employed to activate peroxymonosulfate (PMS) for dealing with atrazine (ATZ). The addition of rectorite could result in higher specific surface area, smaller pore size and more hydroxyl groups, which were beneficial to enrich pollutants to the adsorption sites and provide sufficient reactive sites. After meticulous evaluation, the degradation efficiency of FeCo2O4/rectorite composite towards ATZ exhibited improved PMS activation efficiency which was about 2.6 times than that of pure FeCo2O4. Based on the characterization results, the sulfate radicals and hydroxyl radicals were considered to be the main free radicals which were involved into the circulation of Co(II)-Co(III)-Co(II) as well as the oxidation of ≡Fe(II), which was responsible for the remarkable catalytic efficiency. In addition, the chemical stability and superior catalytic performance of FeCo2O4/rectorite should also be attributed to the chemical combination between metal ions and the surface hydroxyl groups of rectorite. Overall, these findings are beneficial for understanding the mechanism of PMS activation by natural mineral-based catalysts and contributing to the practical application of sulfate-based technology for organic wastewater treatment.
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Metais/química , Peróxidos/química , Poluentes Químicos da Água/química , Silicatos de Alumínio , Atrazina/química , Catálise , Radical Hidroxila/química , Minerais , Modelos Químicos , Nanopartículas , Oxirredução , Papel (figurativo) , SulfatosRESUMO
A novel kind of g-C3N4/rectorite composite with high visible-light photoactivity was developed via a mild and cost effective two-step process. Ciprofloxacin (CIP), a typical antibiotic, was applied to evaluate the photoactivity of the received catalysts. Furthermore, the by-products of CIP photodegradation were analyzed and the possible degradation pathways were also discussed. Compared with bare photocatalysts, the received composite possessed well reusability and higher photoactivity towards CIP. According to the characterization analysis results, layered g-C3N4 was successfully immobilized on layered rectorite, which could not only promote its adsorption capacity but also provide more reactive sites for CIP adsorption and photodegradation. Compared with bare g-C3N4, the photoactivity of the prepared composite was significantly enhanced. The enhancement should be mainly due to the lower recombination rate of photogenerated carriers and the improved adsorption capacity toward CIP. This study demonstrated that the obtained g-C3N4/rectorite composite should be a promising alternative material in wastewater treatment.