Novel granular bentonite-carbon sorbents: textural characterization, adsorption-desorption isotherm, kinetics, and cost estimation.

This research focuses on the synthesis of novel low-cost granular sorbents based on bentonite clay of the Navbahor deposit, dust fraction of Angren brown coal, and agricultural wastes such as straw and sawdust to meet the internal needs of the Republic of Uzbekistan. The impact of the initial mixture ingredients on the structural and textural properties of bentonite-coal sorbents (BCSs) has been studied using X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectroscopy, optical microscopy, and nitrogen adsorption-desorption analysis. For determining the sorption capacity of BCSs, a standard model substance methylene blue (MB), was applied. It was revealed that the maximum adsorption amount of MB was 5.3 mg∙g-1 during 2 h of contact. Prolonging the contact time to 24 h allowed for more extensive diffusion of dye molecules into the sorbent's pores, increasing the adsorption capacity to 13 mg∙g-1. It was demonstrated that BCSs could be regenerated by strong oxidizing agents such as sulfuric acid and hydrogen peroxide, with sulfuric acid proving more effective. Regeneration fully restores sorption properties, particularly at low dye concentrations (up to 0.2 mg∙ml-1). Despite slight reductions in adsorption capacity over multiple regeneration cycles, the sorbents maintain their structural integrity and durability. It is shown that compared to imported expensive activated carbon, the gross profitability of the in-house production of such granular BCSs within the territory of Uzbekistan increases from 48 to 78%, while the net income increases almost three times.

Construction of mechanically robust and recyclable catalytic hydrogel based on hydroxypropyl cellulose-supported by montmorillonite/ionic liquid with different anions for pollutants(4-NP, MB, CR, Rhb) degradation.

Dye wastewater poses a serious threat to the environment and human health, necessitating sustainable degradation methods. In this study, Na-based Montmorillonite (MMT) was exfoliated using different ionic liquids ([C16MIM][Cl], [C16MIM][BF4], [C16MIM][PF6]), and silver nanoparticles (Ag NPs) were green-synthesized using hydroxypropyl cellulose (HPC). The HPC significantly enhanced the dispersion of MMT in the hydrogel. By introducing lauryl methacrylate (LMA), a hydrophobic associative network was constructed in PAM/LMA/HPC/MMT@ILs&Ag NPs hydrogel. This hydrogel demonstrated outstanding mechanical properties, with a stress of 833.21 kPa, strain of 3300 %, and toughness of 14.36 MJ/m3. It also exhibited excellent catalytic activity, with a rate constant of 0.83 min-1 for 4-nitrophenol degradation at 28 °C. The effects of temperature and catalyst concentration on the catalytic reaction were systematically investigated. This study presents a simple green synthesis approach for Ag NPs using HPC, achieving superior mechanical performance and stable MMT dispersion in aqueous solutions.

Recent advances of application of bentonite-based composites in the environmental remediation.

Bentonite-based composites have been widely utilized in the removal of various pollutants due to low cost, environmentally friendly, ease-to-operate, whereas the recent advances concerning the application of bentonite-based composites in environmental remediation were not available. Herein, the modification (i.e., acid/alkaline washing, thermal treatment and hybrids) of bentonite was firstly reviewed; Then the recent advances of adsorption of environmental concomitants (e.g., organic (dyes, microplastics, phenolic and other organics) and inorganic pollutants (heavy metals, radionuclides and other inorganic pollutants)) on various bentonite-based composites were summarized in details. Meanwhile, the effect of environmental factors and interaction mechanism between bentonite-based composites and contaminants were also investigated. Finally, the conclusions and prospective of bentonite-based composites in the environmental remediation were proposed. It is demonstrated that various bentonite-based composites exhibited the high adsorption/degradation capacity towards environmental pollutants under the specific conditions. The interaction mechanism involved the mineralization, physical/chemical adsorption, co-precipitation and complexation. This review highlights the effect of different functionalization of bentonite-based composites on their adsorption capacity and interaction mechanism, which is expected to be helpful to environmental scientists for applying bentonite-based composites into practical environmental remediation.

Heteroaggregation and deposition behaviors of carboxylated nanoplastics with different types of clay minerals in aquatic environments: Important role of calcium(II) ion-assisted bridging.

The widespread utilization of plastic products ineluctably leads to the ubiquity of nanoplastics (NPs), causing potential risks for aquatic environments. Interactions of NPs with mineral surfaces may affect NPs transport, fate and ecotoxicity. This study aims to investigate systematically the deposition and aggregation behaviors of carboxylated polystyrene nanoplastics (COOH-PSNPs) by four types of clay minerals (illite, kaolinite, Na-montmorillonite, and Ca-montmorillonite) under various solution chemistry conditions (pH, temperature, ionic strength and type). Results demonstrate that the deposition process was dominated by electrostatic interactions. Divalent cations (i.e., Ca2+, Mg2+, Cd2+, or Pb2+) were more efficient for screening surface negative charges and compressing the electrical double layer (EDL). Hence, there were significant increases in deposition rates of COOH-PSNPs with clay minerals in suspension containing divalent cations, whereas only slight increases in deposition rates of COOH-PSNPs were observed in monovalent cations (Na+, K+). Negligible deposition occurred in the presence of anions (F-, Cl-, NO3-, CO32-, SO42-, or PO43-). Divalent Ca2+ could incrementally facilitate the deposition of COOH-PSNPs through Ca2+-assisted bridging with increasing CaCl2 concentrations (0-100 mM). The weakened deposition of COOH-PSNPs with increasing pH (2.0-10.0) was primarily attributed to the reduce in positive charge density at the edges of clay minerals. In suspensions containing 2 mM CaCl2, increased Na+ ionic strength (0-100 mM) and temperature (15-55 ◦C) also favored the deposition of COOH-PSNPs. The ability of COOH-PSNPs deposited by four types of clay minerals followed the sequence of kaolinite > Na-montmorillonite > Ca-montmorillonite > illite, which was related to their structural and surface charge properties. This study revealed the deposition behaviors and mechanisms between NPs and clay minerals under environmentally representative conditions, which provided novel insights into the transport and fate of NPs in natural aquatic environments.

Mechanism of self-supporting montmorillonite composite material for bio-enhanced degradation of chlorotetracycline: Electron transfer and microbial response.

The efficient degradation of antibiotics holds significant implications for mitigating environmental pollution. This study synthesized a montmorillonite chitosan composite material (MMT-CS) using the gel template method. Subsequently, a bio-enhanced reactor was constructed to facilitate the degradation of chlorotetracycline (CTC). The addition of MMT-CS composite material enables the degradation of different concentrations of CTC. MMT-CS, a conductive carrier, effectively promotes microbial adhesion and boosts the metabolic activity of functional microorganisms. Additionally, it facilitates the maintenance of microbial activity under CTC pressure by promoting the secretion of extracellular polymeric substances, increasing critical enzyme activity, and enhancing the electron transfer capacity within the system. In this MMT-CS bio-enhanced process, Paracoccus (11.4%) and Bacillus (3.9%) are utilized as essential bacteria genes. The results of metabolic pathways prediction indicated significant enhancements in membrane-transport, nucleotide-metabolism, replication-repair, and lipid-metabolism. Thus, the developed self-supporting MMT-CS bio-enhanced process ensured the stability of the system during the removal of antibiotics.

Preparation of iota-carrageenan@bentonite@4-phenyl-3-thiosemicarbazide ternary hydrogel for adsorption of Losartan potassium and sulfamethoxazole.

A rising quantity of drugs has been discharged into the aquatic environment, posing a substantial hazard to public health. In the current work, a novel hydrogel (i.Carr@Bent@PTC), comprised of iota-carrageenan, bentonite, and 4-phenyl-3-thiosemicarbazide, was successfully prepared. The introduction of 4-phenyl-3-thiosemicarbazide and bentonite in iota-carrageenan significantly increased the mechanical strength of iota-carrageenan hydrogel and improved its degree of swelling, which can be attributed to the hydrophilic properties of PTC and Bent. The recorded contact angle was 70.8°, 59.1°, 53.9°, and 34.6° for pristine i.Carr, i.Carr@Bent, and i.Carr@Bent@PTC, respectively. The low contact angle measurement of the Bent and PTC loaded-i.Carr hydrogel was attributed to the hydrophilic Bent and PTC. The ternary i.Carr@Bent@PTC hydrogel demonstrated broad pH adaptability and excellent adsorption capacities for sulfamethoxazole (SMX) and losartan potassium (LP), i.e., 467.61 mg. g-1 and 274.43 mg. g-1 at 298.15 K, respectively. The pseudo-first-order (PSO) model provided a better fit for the adsorption kinetics. The adsorption of SMX and LP can be better explained by employing the Sips and Langmuir isotherm models. As revealed by XPS and FTIR investigations, π-π stacking, complexation, electrostatic interaction, and hydrogen bonding were primarily involved in the adsorption mechanisms.

Immobilization of Horseradish Peroxidase onto Montmorillonite/Glucosamine-Chitosan Composite for Electrochemical Biosensing of Polyphenols.

Glucosamine-chitosan synthesized by the Maillard reaction was combined with montmorillonite to obtain a nanohybrid composite to immobilize horseradish peroxidase. The material combines the advantageous properties of clay with those of the chitosan derivative; has improved water solubility and reduced molecular weight and viscosity; involves an eco-friendly synthesis; and exhibits ion exchange capacity, good adhesiveness, and a large specific surface area for enzyme adsorption. The physicochemical characteristics of the composite were analyzed by infrared spectroscopy and X-ray diffraction to determine clay-polycation interactions. The electrochemical response of the different polyphenols to glassy carbon electrodes modified with the composite was evaluated by cyclic voltammetry. The sensitivity and detection limit values obtained with the biosensor toward hydroquinone, chlorogenic acid, catechol, and resorcinol are (1.6 ± 0.2) × 102 µA mM-1 and (74 ± 8) nM; (1.2 ± 0.1) × 102 µA mM-1 and (26 ± 3) nM; (16 ± 2) µA mM-1 and (0.74 ± 0.09) µM; and (3.7± 0.3) µA mM-1 and (3.3 ± 0.2) µM, respectively. The biosensor was applied to quantify polyphenols in pennyroyal and lemon verbena extracts.

Novel chitosan-based barrier materials for environmental containment: Synthesis, characterization, and contaminant removal capacities and mechanisms.

This study critically appraises employing chitosan as a composite with bentonite, biochar, or both materials as an alternative to conventional barrier materials. A comprehensive literature review was conducted to identify the studies reporting chitosan-bentonite composite (CBC), chitosan amended biochar (CAB), and chitosan-bentonite-biochar composite (CBBC) for effective removal of various contaminants. The study aims to review the synthesis of these composites, identify fundamental properties affecting their adsorption capacities, and examine how these properties affect or enhance the removal abilities of other materials within the composite. Notably, CBC composites have the advantage of adsorbing both cationic and anionic species, such as heavy metals and dyes, due to the cationic nature of chitosan and the anionic nature of montmorillonite, along with the increased accessible surface area due to the clay. CAB composites have the unique advantage of being low-cost sorbents with high specific surface area, affinity for a wide range of contaminants owing to the high surface area and microporosity of biochar, and abundant available functional groups from the chitosan. Limited studies have reported the utilization of CBBC composites to remove various contaminants. These composites can be prepared by combining the steps employed in preparing CBC and CAB composites. They can benefit from the favorable adsorption properties of all three materials while also satisfying the mechanical requirements of a barrier material. This study serves as a knowledge base for future research to develop novel composite barrier materials by incorporating chitosan and biochar as amendments to bentonite.

Sodium carboxymethyl cellulose hydrogels containing montmorillonite-NaClO2 for postharvest preservation of Chinese bayberries.

Owing to their lack of outer skin, Chinese bayberries are highly susceptible to mechanical damage during picking, which accelerates bacterial invasion and rotting, shortening their shelf life. In this study, montmorillonite (MMT) was used to absorb an aqueous sodium chlorite solution embedded in a carboxymethyl cellulose sodium hydrogel after freeze drying, and the hydrogel was crosslinked by Al3+ ions. Al3+ hydrolyzed to produce H+, creating an acidic environment within the hydrogel and reacting with NaClO2 to slowly release ClO2. We prepared a ClO2 slow-release hydrogel gasket with 0.5 wt% MMT-NaClO2 and investigated its storage effect on postharvest Chinese bayberries. Its inhibition rates against Escherichia coli and Listeria monocytogenes were 98.84% and 98.96%, respectively. The results showed that the gasket preserved the appearance and nutritional properties of the berries. The antibacterial hydrogel reduced hardness loss by 26.57% and ascorbic acid loss by 46.36%. This new storage method could also be applicable to other fruits and vegetables.

Aldehyde-containing clays: a sustainable approach against the olive tree pest, Bactrocera oleae.

A set of organic/inorganic layered materials was obtained by functionalizing a montmorillonite-containing bentonite natural clay with linear aliphatic C6 or C7 aldehydes through a cost-effective and technologically simple incipient-wetness deposition method. The solids were investigated by means of a multi-technique approach (X-ray powder diffraction, XRPD, scanning electron microscopy, SEM, Fourier-transform infrared spectroscopy, FT-IR, thermogravimetric analysis, TGA, elemental analysis and solid-state nuclear magnetic resonance, ssNMR) to clarify the nature of the deposited organic species and the mode of interaction between the aldehyde and the clay. Since both natural clays and short-chain linear aldehydes find application as alternative strategies in the control of the olive fruit fly, Bactrocera oleae, the hybrid layered materials were tested under real-life conditions and their insect-inhibiting capability was evaluated in open-field trials on olive tree orchards in Tuscany, Central Italy. Specific tests were conducted to evaluate the resistance of the solids to weathering and their capability to provide a constant and long-lasting release of the bioactive ingredient. Aldehyde-containing bentonite clays have shown promising performance in controlling B. oleae infestation (with up to 86-95% reduction of affected olive fruits) in open-field trials across two years in two locations with different pedological and meteo-climatic characteristics.

Electrochemical and quantum chemical approaches to the study of dopamine sensing using bentonite and l-cysteine modified carbon paste electrode.

This work presents a significant investigation involving both electrochemical experiment and quantum chemical simulation approaches. The objective was to characterize the electrochemical detection of dopamine (DA). The detection was carried out using a modified carbon paste electrode (CPE) incorporating bentonite (Bent) and l-cysteine (CySH) (named as CySH/Bent/CPE). To understand and explain the oxidation mechanism of DA on the CySH/Bent modified electrode surface, the coupling of the two approaches were exploited. The CySH/Bent/CPE showed excellent electroactivity toward DA such as good sensibility, selectivity, stability, and regenerative ability. The developed sensor shows a dynamic linear range from 0.8 to 80 µM with a limit of detection and quantification of 0.5 µM and 1.5 µM, respectively. During the quantitative analysis of DA in presence of ascorbic acid (AA) and uric acid (UA) the electrochemical oxidation signals of AA, DA, and UA distinctly appear as three separate peaks. The potential differences between the peaks are 190 mv, 150 mv, and 340 mV for the AA-DA, DA-UA, and AA-UA oxidation pairs, respectively. These observations stem from square wave voltammetry (SWV) studies, along with the corresponding redox peak potential separations. The developed sensor is simple and accurate to monitor DA in human serum samples. On the other hand, CySH acts as an electrocatalyst on the CySH/Bent/CPE surface by increasing its active electron transfer sites, as suggested by the quantum chemical modeling with analytical results of Fukui. Furthermore, the voltammetric results obtained agree well with the theoretical calculations.

Eco-friendly electronic food labels: Development and application of Ion-SSPB double network hydrogel.

Although various conductive hydrogels have been developed for sensing, ideal materials for meeting the safety and toughness requirements of food detection are still lacking. This study introduces Ion-SSPB, a conductive hydrogel fabricated from eco-friendly, food-grade materials such as corn starch (CS), sodium alginate (SA), polyvinyl alcohol (PVA) and bentonite (BT). It leverages a green manufacturing approach designed for application in electronic food sensors. The hydrogel is achieved through a double network strategy and salt immersion method, which endows it with tunable mechanical and rheological properties. A key innovation of Ion-SSPB is the incorporation of bentonite, which enhances its performance, including low swelling, freezing resistance, and minimal residual adhesion. The hydrogel with 4% (w/v) BT concentration (Ion-SSPB4%) is an effective medium for detecting impedance changes in mangoes, correlating with their ripening stages. The Ion-SSPB hydrogel represents a significant advancement in the field of electronic food labels, combining environmental sustainability with technical efficacy.

Programable sewage-cleaning technology: Regenerating chitosan biofilms with anti-bacterial capacity via self-purification of water pollutants.

In this paper, a novel programable sewage-cleaning technology for the regeneration of antibacterial nanocomposites via the removal of wastewater pollutants is presented. Montmorillonite (MMT) was encapsulated in poly(vinyl alcohol) (PVA)-enhanced chitosan (CTS) hydrogels to form MMT-loaded nanocomposite biofilms (PCM). The PCM nanocomposite biofilms exhibited increased breaking strength and elongation at break, by factors of approximately 1.38 and 1.40, respectively, compared with those of the pure PVA/CTS biofilms. The maximum adsorption capacity of the PCM nanocomposite biofilms toward tetracycline and Ag(I) is 275.0 and 567.0 mg/g, respectively. The adsorbed nanocomposite biofilms exhibited excellent antibacterial properties against Staphylococcus aureus and Escherichia coli. Meanwhile, the nanocomposite also showed an effective adsorption capacity toward other toxic components, where the highest adsorption capacity is 2748.0 mg/g (for methyl blue). The simulation results indicated that the adsorption behaviors of the malachite green, neutral red, methyl blue, tetracycline, Cu(II), Zn(II), and Ag(I) by the PCM nanocomposite biofilms followed pseudo-second-order kinetic and Freundlich isotherm models. Furthermore, the PCM nanocomposite biofilms are stable in PBS solution but degradable in lysozyme-containing PBS solution, suggesting their potential application in the wastewater treatment as well as antibacterial fields.

Zeolites synthesis from phyllosilicates and their performance for CO2 adsorption.

Five phyllosilicates (kaolinite, montmorillonite, saponite, sepiolite and palygorskite) have been selected as starting materials for the synthesis of zeolites. Among them, kaolinite and montmorillonite display the lowest Si/Al molar ratio leading to aluminosilicates with high crystallinity. Thus, the hydrothermal treatment under basic conditions forms 4A zeolite when kaolinite is used as starting material while 13X zeolite is obtained when montmorillonite is used as starting material. The microporosity and CO2-adsorption capacity of the prepared zeolites are directly related to its crystallinity. Thus, in order to improve it, raw phyllosilicates were subjected to a microwave-assisted treatment to remove undesired Mg or Fe-species, which have a negative effect in the assembling of the zeolites by hydrothermal basic conditions in a second step. The highest adsorption value was 3.85 mmol/g at 25 °C and 760 mm of Hg for Mont-A-B sample after the consecutive treatments.

Effects of montmorillonite on the loading and release of Piper betle L. extract applied for wound dressing based on chitosan/polyvinyl alcohol.

In this study, we investigate the influence of montmorillonite (MMT) on the loading and release of Piper betle L. extract (PLE)-a medicinal herb containing active secondary metabolites with antibacterial, antioxidant, and anti-inflammatory effects. MMT (1 %, 3 %, 5 %) was blended into the chitosan/polyvinyl alcohol (CS/PVA) biocomposite film by the solution evaporation method, and then PLE was loaded onto this biocomposite using the immersion method. The tensile strength and the ability to absorb exudates of the CS/PVA film improved with the increase in MMT content. The MMT 3 % film was considered to have the best properties: good mechanical properties with a tensile strength of 27.44 ± 0.27 MPa and elongation at break of 14.57 ± 0.30 %, potential for wound dressing due to its ability to absorb wound exudate (swelling degree 61.70 ± 0.30 %) and a suitable water vapor transmission rate (1999 ± 47 g/m2·d). The presence of MMT (1 %, 3 %, 5 %) in the CS/PVA film led to an increase in the PLE loading efficiency of the films compared to the film without MMT, up to 1.65, 1.73, and 1.87 times, respectively. The MMT 3 % and 5 % films also exhibited a sustained PLE release effect for up to 24 h. MMT increased PLE bioavailability through bioactivity tests: antibacterial activity against both E. coli and S. aureus, antioxidant activity, effective healing of 2nd-degree burn wounds, and biocompatibility with the L929 fibroblasts cell line. The combination of physicochemical properties and biological activities proved that the MMT/PLE drug delivery system based on the CS/PVA biocomposite is promising for wound dressing.

Water-triggered shape memory cellulose / sodium alginate / montmorillonite composite sponges for rapid hemostasis.

Uncontrollable bleeding caused by severe trauma is life-threatening. Therefore, it is of great significance to develop hemostatic materials that meet the rapid hemostasis of wounds. In this study, a water-triggered shape memory carboxylated cellulose nanofiber/sodium alginate/montmorillonite (CNSAMMTCa) composite hemostatic sponge was prepared, which can promote coagulation by concentrating the blood and activating intrinsic pathway. The anisotropic three-dimensional porous structure formed by directional freeze-drying technology improved the performance of composite sponges which showed good prospects in rapid hemostasis. The results showed that CNSAMMTCa composite sponge had good porous structure, water absorption ability, cytocompatibility and blood cell aggregation capacity. Simultaneously, we confirmed that CNSA3MMT2Ca has best coagulation performance in the mouse censored bleeding model and liver rupture bleeding model. Therefore, CNSAMMTCa composite hemostatic sponge is a safe and efficient rapid hemostatic material which is expected to become an alternative material for clinical hemostatic materials.

Effect of compaction on bisulfide diffusive transport through MX-80 bentonite.

Canada's deep geological repository (DGR) design includes an engineered barrier system where highly compacted bentonite (HCB) surrounds the copper-coated used fuel containers (UFCs). Microbial-influenced corrosion is a potential threat to long-term integrity of UFC as bisulfide (HS-) may be produced by microbial activities under anaerobic conditions and transported via diffusion through the HCB to reach the UFC surface, resulting in corrosion of copper. Therefore, understanding HS- transport mechanisms through HCB is critical for accurate prediction of copper corrosion allowance. This study investigated HS- transport behaviour through MX-80 bentonite at dry densities 1070-1615 kg m-3 by performing through-diffusion experiments. Following HS- diffusion, bromide (Br-) diffusion and Raman spectroscopy analyses were performed to explore possible physical or mineralogical alterations of bentonite caused by interacting with HS-. In addition, accessible porosity ε was estimated using extended Archie's law. Effective diffusion coefficient of HS- was found 2.5 × 10-12 m2 s-1 and 5.0× 10-12 m2 s-1 for dry densities 1330 and 1070 kg m-3, respectively. No HS- breakthrough was observed for highly compacted bentonite (1535-1615 kg m-3) over the experimental timeframe (170 days). Raman spectroscopy results revealed that HS- reacted with iron in bentonite and precipitated as mackinawite and, therefore, it was immobilized. Finally, results of this study imply that HS- transport towards UFC will be highly controlled by the available iron content and dry density of the buffer material.

Magnetized bentonite modified rice straw biochar: Qualitative and quantitative analysis of Cd(II) adsorption mechanism.

Industrialization has caused a significant global issue with cadmium (Cd) pollution. In this study, Biochar (Bc), generated through initial pyrolysis of rice straw, underwent thorough mixing with magnetized bentonite clay, followed by activation with KOH and subsequent pyrolysis. Consequently, a magnetized bentonite modified rice straw biochar (Fe3O4@B-Bc) was successfully synthesized for effective treatment and remediation of this problem. Fe3O4@B-Bc not only overcomes the challenges associated with the difficult separation of individual bentonite or biochar from water, but also exhibited a maximum adsorption capacity of Cd(II) up to 241.52 mg g-1. The characterization of Fe3O4@B-Bc revealed that its surface was rich in C, O and Fe functional groups, which enable efficient adsorption. The quantitative calculation of the contribution to the adsorption mechanism indicates that cation exchange and physical adsorption accounted for 65.87% of the total adsorption capacity. In conclusion, Fe3O4@B-Bc can be considered a low-cost and recyclable green adsorbent, with broad potential for treating cadmium-polluted water.

Critical Role of Mineral Fe(IV) Formation in Low Hydroxyl Radical Yields during Fe(II)-Bearing Clay Mineral Oxygenation.

In subsurface environments, Fe(II)-bearing clay minerals can serve as crucial electron sources for O2 activation, leading to the sequential production of O2•-, H2O2, and •OH. However, the observed •OH yields are notably low, and the underlying mechanism remains unclear. In this study, we investigated the production of oxidants from oxygenation of reduced Fe-rich nontronite NAu-2 and Fe-poor montmorillonite SWy-3. Our results indicated that the •OH yields are dependent on mineral Fe(II) species, with edge-surface Fe(II) exhibiting significantly lower •OH yields compared to those of interior Fe(II). Evidence from in situ Raman and Mössbauer spectra and chemical probe experiments substantiated the formation of structural Fe(IV). Modeling results elucidate that the pathways of Fe(IV) and •OH formation respectively consume 85.9-97.0 and 14.1-3.0% of electrons for H2O2 decomposition during oxygenation, with the Fe(II)edge/Fe(II)total ratio varying from 10 to 90%. Consequently, these findings provide novel insights into the low •OH yields of different Fe(II)-bearing clay minerals. Since Fe(IV) can selectively degrade contaminants (e.g., phenol), the generation of mineral Fe(IV) and •OH should be taken into consideration carefully when assessing the natural attenuation of contaminants in redox-fluctuating environments.

Interface Binding Mechanism of Nanoclay Hybridized Coacervate Microdroplets for the Controllable Construction of Protocells.

Coacervate microdroplets, a protocell model in exploring the origin of life, have gained significant attention. Clay minerals, catalysts during the origin of life, are crucial in the chemical evolution of small molecules into biopolymers. However, our understanding of the relationship between clay minerals and the formation and evolution of protocells on early Earth remains limited. In this work, the nanoclay montmorillonite nanosheet (MMT-Na) was employed to investigate its interaction with coacervate microdroplets formed by oligolysine (K10) and adenine nucleoside triphosphate (ATP). As an anionic component, MMT-Na was noted to promote the formation of coacervate microdroplets. Furthermore, the efficiency of ssDNA enrichment and the degree of ssDNA hybridization within these microdroplets were significantly improved. By combining inorganic nanoclay with organic biopolymers, our work provides an efficient way to enrich genetic biomolecules in the primitive Earth environment and builds a nanoclay-based coacervate microdroplets, shedding new light on life's origin and protocell evolution.