Search Results (49)

Natural bentonite, dominated by montmorillonite-type layered aluminosilicates, is increasingly considered as an inexpensive and environmentally acceptable support or catalyst for the thermochemical conversion of waste carbon streams. Its relevance to catalysis arises from a combination of cation-exchange capacity, swelling behavior, hierarchical porosity after modification, and the possibility of generating Brønsted, Lewis, redox and metallic active sites. This review critically evaluates bentonite modification strategies—acid activation, alkaline and sodium exchange, inorganic oxide pillaring, transition- and noble-metal impregnation, organosilane or surfactant functionalization, and carbon-based hybridization—with emphasis on their consequences for texture, acidity, thermal stability, metal dispersion and catalytic behavior. The review then connects these structure–property relationships with the emerging application of modified bentonites in plastic-waste thermocatalysis and hydrogen-rich product formation. The recent literature indicates that acid-modified bentonite can substantially improve liquid hydrocarbon formation from polyethylene, binder-free bentonite pellets can operate at kilogram-batch scale for drop-in fuels, and Ni-, Fe- or Ni–Fe-modified bentonite-type catalysts can promote tar cracking, reforming and gas upgrading. However, direct evidence for high hydrogen yields from plastic waste over bentonite remains narrower than the evidence for liquid-fuel production, biomass pyrolysis or model-compound reforming. Therefore, this article distinguishes between direct plastic-waste evidence and transferable evidence from biomass, acetic acid, tar and hydrocarbon reforming studies. The analysis identifies Ni-impregnated acid-activated or pillared bentonite, Ni–Fe/bentonite, and La/Ca-promoted Ni/bentonite as the most promising routes for plastic-derived hydrogen-rich syngas, while acid activation alone is best regarded as a pretreatment rather than a complete catalyst design. Key limitations include catalyst deactivation by coke, metal sintering, chloride poisoning from PVC, inconsistent reporting of gas yields, and insufficient life-cycle and techno-economic analysis. A roadmap is proposed for designing reproducible, scalable bentonite catalysts for circular plastic-waste valorization. Full article

SiO₂ aerogels are promising candidates for energy-efficient glazing because of their low thermal conductivity and optical transparency; however, conventional formulations often fail to reconcile optical, thermal, and mechanical performance. This work aimed to resolve this bottleneck via controllable sol–gel synthesis and ambient pressure drying. Using methyltrimethoxysilane (MTMS) as the single silicon source, this study systematically explored the effects of alkaline catalyst type, water-to-MTMS ratio, and surfactant selection, and further developed an MTMS–dimethyl dimethoxy silicane (DMDMS) composite silicon source. Tetramethylammonium hydroxide (TMAOH) catalysis, a water-to-MTMS molar ratio of 7:1, and Pluronic F-127 (F127) surfactant yielded a uniform, hydrophobic aerogel with 93.50% porosity and 89.74% transmittance at 800 nm. The optimized composite system (MTMS:DMDMS = 9:1, 6 mL water, 2.0 g F127) enhanced compressive strength by 22.4% relative to pure MTMS aerogel, with 70.15% visible transmittance and thermal conductivity of 0.027 W/(m·K). These results demonstrate that multi-parameter formulation control can achieve a practical balance among mechanical robustness, optical transparency, and thermal insulation. This study provides a theoretical and process foundation for the engineering application of high-performance transparent thermal insulation materials. Full article

Considering the expanded interest in reducing organic solvents in synthesis, surfactants and surfactant-based catalysis have been used to carry out various organic transformations in water. In recent years, the integration of Lewis and Brønsted acid catalysis with micellar systems has gained considerable attention as a powerful approach to enhance reaction efficiency while minimizing the environmental impact of synthetic processes. In this article, we depict the most recent advances in the water-interceded synthesis of different organic systems by utilizing different surfactant-type catalysts, which are important structural motifs in pharmaceuticals, agrochemicals and functional materials. Further, these methods incorporate green reaction media, mild reaction conditions, and a great yield of product with high purity in a shorter interval of time. Understanding the scope and impact of this area, authors have made efforts to collect and compile the data that indicates many named reactions, such as Friedlander annulation, aldol condensation, the Biginelli reaction, the Mannich reaction, Suzuki–Miyaura cross-coupling, etc., now take place using surfactant-based catalysts. Full article

The review critically discusses the methodological approach used to characterize the mechanism and to assess kinetic parameters in catalytic processes promoted by surfactant-based nanozymes. Using the hydrolysis of carboxylic and phosphoric esters as model reactions, it quantitatively analyzes several examples in which the catalytic system consists either of aggregates formed by non-functional surfactants or of surfactants bearing one or more reactive functions, ranging from classical nucleophiles to transition metal ions. This analysis highlights both the importance of the design of the kinetic experiments and of the selection of the appropriate experimental conditions, and the need to apply the correct model and set of kinetic equations in the interpretation of the data, in order to obtain kinetic parameters with true chemical significance. Improper kinetic modeling may lead to misleading rate enhancements and false claims of very high activity of the system studied. The aim of the review is not to provide a general overview of micelle and liposome-promoted catalysis, but rather to offer methodological tools to correctly assess rate accelerations with these systems. Full article

The global change toward sustainable manufacturing has intensified the development of alternatives to petrochemical-based surfactants, which are environmentally recalcitrant and fossil dependent. Biosurfactants have emerged as the most promising petrochemical-based surfactant substitutes, due to their biodegradability, low toxicity, and robust performance under extreme conditions; however, their industrial use is hindered by high production costs, limited productivity, and complex downstream processing, for instance high protein content can make the ultrafiltration (downstream strategy) unfeasible. This review critically examines recent advances in integrated bioprocess design to overcoming these constraints, with particular emphasis on the convergence of enzymatic catalysis and microbial fermentation. Comparative assessment across key biosurfactant classes demonstrates that tailored enzymatic transformations, enabled by lipases, glycosyltransferases, acyltransferases, and oxidoreductases, offer precision in structural modification unattainable through fermentation alone, enabling programmable amphiphilicity and improved functional performance. Thus, the translation of enzymatic and hybrid routes to industry remains restricted by enzyme stability, cofactor regeneration, and process engineering challenges. Emerging strategies such as continuous fermentation, in situ product recovery, and machine learning-based process control show strong potential to enhance productivity and reduce energy demands. By integrating molecular design, metabolic engineering, and intensified bioprocessing, this review delineates a strategic framework for advancing next-generation biosurfactants toward commercial viability within circular and sustainable value chains. Full article

CeO₂ is a crucial functional material in catalysis and energy applications, whose performance is highly morphology-dependent. Traditional synthesis methods often rely on organic templates or surfactants, which complicate the processes and pose environmental concerns. This study introduces an eco-friendly approach utilizing a methanol–water (MeOH-H₂O) mixed solvent system combined with NH₄HCO₃ to achieve controllable synthesis of multi-morphology CeO₂ without surfactants or templates. The effects of different solvent systems (pure H₂O, pure MeOH, and their mixtures) and NH₄HCO₃ as an inexpensive regulator on precursor phase behavior and crystallization were systematically investigated. By optimizing the Ce:N molar ratios (1:1 to 1:7) as well as reaction times (0.5 to 36 h), our findings indicate that H₂O significantly enhances crystallinity (from 40.9% to 61.4% for precursors, reaching 70.3% after calcination) and promotes octahedra formation in the MeOH-H₂O mixed system, while NH₄HCO₃ acts as a structure-directing agent to control size (e.g., ~240 nm octahedra at Ce:N = 1:1, up to 375 nm at Ce:N = 1:2) and partially substitutes for high-temperature calcination in improving crystallinity. Variety morphologies, including plates, dendrites, octahedra, and hollow structures, were successfully synthesized. This work elucidates the synergistic mechanism by which solvents and NH₄HCO₃ influence CeO₂ nucleation and growth, thereby providing an environmentally friendly synthesis route with significant potential applications in catalysis and energy storage. Full article

This study presents a novel approach for synthesizing porous silica materials using various biomass-derived carboxylic acids as non-surfactant, eco-friendly porogens. Different carboxylic acids were selected, and their influence on the properties of the final materials was systematically investigated. The silica synthesis was performed using only the intrinsic acidity of carboxylic acids without pre-hydrolysis of the silica precursor - tetraethyl orthosilicate (TEOS). Citric and tartaric acids had a favorable effect on the formation of mesoporous silica, whereas the oxalic, ascorbic, maleic, and mandelic acids led to the formation of microporous silica. The optimal synthesis compositions and parameters were thoroughly investigated. A mesoporous silica with a uniform pore size was prepared using tartaric acid, and the pore size was controlled by the drying temperature. Template removal via water extraction yielded silica materials with superior textural properties compared to conventional high-temperature calcination, while allowing the recovery and reuse of organic acids. Our results confirm that using carboxylic acids can be efficiently and economically applied for the controlled synthesis of mesoporous silica suitable for different applications, such as adsorption, drug delivery, and catalysis. Full article

The design of sustainable nanomaterials for catalysis is a key challenge in green chemistry. Herein, we report the synthesis of halloysite nanotube (Hal)-based nanomaterials selectively functionalized with a bio-inspired polydopamine (PDA) coating, which enables the controlled anchoring of palladium and copper nanoparticles (PdNPs and CuNPs). This mild and ecofriendly strategy yields highly dispersed and ultrasmall (<5 nm) metal nanoparticles without the need for surfactants or harsh reagents. The resulting materials, Hal@PDA/PdNPs and Hal@PDA/CuNPs, were evaluated in two well-established model reactions commonly employed to probe catalytic performance: cinnamaldehyde hydrogenation and 4-nitrophenol reduction. Hal@PDA/PdNPs displayed complete conversion and >90% selectivity toward hydrocinnamaldehyde at low Pd loading (0.8 wt%) and maintained its efficiency over six catalytic cycles (TOF up to 0.1 s⁻¹), while Hal@PDA/CuNPs retained high activity through eight consecutive runs in the reduction of 4-nitrophenol. Hal@PDA/CuNPs proved to be an excellent recyclable catalyst for the reduction of 4-nitrophenol, retaining high activity through eight consecutive runs. Overall, this study introduces a robust and modular approach to fabricating halloysite-based nanocatalysts, demonstrating their potential as green platforms for metal nanoparticle-mediated transformation. Full article

Bio-based surfactants have demonstrated significant potential as economically viable and environmentally sustainable alternatives to petroleum-derived surfactants, with the global biosurfactant market expanding from USD 4.41 billion in 2023 to a projected USD 6.71 billion by 2032, representing a compound annual growth rate of 5.4%. While conventional surfactants such as alkyl aryl sulfates and alkyl benzene sulfonates exhibit extremely high aquatic toxicity and impose substantial ecological costs, biosurfactants including lipopeptides (surfactin, iturin, fengycin, lichenysin) produced by Bacillus species and glycolipids (rhamnolipids, sophorolipids, trehalose lipids, mannosylerythritol lipids) from Pseudomonas demonstrate superior biodegradability. However, current biosurfactant production costs, ranging from 5 to20 USD/kg, cannot compete effectively with synthetic surfactants, averaging approximately 2 USD/kg, necessitating comprehensive process improvements to achieve commercial viability. The utilization of renewable agricultural feedstocks containing 65–70% carbohydrates, including corn stover, sugarcane bagasse, rice bran, and palm oil mill effluent, has achieved production costs as low as 3.8 USD/kg through advanced optimized pretreatment technologies, enzyme catalysis, simultaneous saccharification and fermentation (SSF), and downstream processes, resulting in cost reductions compared to conventional methods. The implementation of artificial intelligence and machine learning algorithms for bioprocess optimization enables simultaneous optimization of genetic engineering, metabolic pathways, and fermentation parameters, achieving yield improvements and cost reductions, with projections indicating production costs below 2.50 USD/kg being needed in the next decade to achieve cost parity with synthetic surfactants, maintaining economic viability. Full article

We systematically investigated the morphology-controlled synthesis of Cu₂O micro-nano crystals, especially under surfactant-free conditions, targeting a simple, rapid, and morphologically controllable preparation strategy for polyhedral Cu₂O micro-nano crystals. By systematically investigating the effects of NaOH concentration, types of reducing agents, and copper salt precursors on crystal growth, precise control over the morphology of Cu₂O crystals under surfactant-free conditions was achieved. This method can rapidly prepare variously faceted Cu₂O crystals under mild conditions (70 °C, 7 min), including regular polyhedra with low-index facets exposure including cubes, octahedra and rhombic dodecahedra, as well as more complex polyhedra with high-index facets exposure such as 18-faceted, 26-faceted, 50-faceted and 74-faceted crystals. NaOH concentration is found to be the key factor in controlling Cu₂O crystal morphology: as the concentration of NaOH increases, the morphology of Cu₂O crystals gradually transforms from cubes that fully expose the {100} faces to regular polyhedra that expose the {110}, {111} faces, and even other high-index faces, ultimately presenting octahedra that fully expose the {111} faces. Additionally, Cu₂O crystals with unique morphologies such as hollow cubes and 18-faceted with {110} face etched can be obtained by introducing surfactants or prolonging reaction durations. This work provides new insights into the morphology control of Cu₂O crystals and establishes foundation in acquiring distinct Cu₂O polyhedra in a facile manner for their application in catalysis, optoelectronics, sensing, and energy conversion fields. Full article

Anisotropic particles have a wide range of applications in materials science such as emulsion stabilization, oil–water separation, and catalysis due to their asymmetric structure and properties. Nevertheless, designing and synthesizing large quantities of anisotropic particles with controlled morphologies continue to present considerable challenges. In this study, we successfully synthesized anisotropic microspheres using a soap-free seed emulsion polymerization method. This approach combines the benefits of seed emulsion polymerization with emulsion interfacial polymerization. By varying the concentrations of dissolved polymeric monomers, 3-methacryloyloxypropyltrimethoxysilane (MPS), and the initiator of potassium persulfate (KPS), different shapes of bowl, cap, and three-sided concave particles were obtained in surfactant-free aqueous solutions, simplifying the post-treatment process. The cap particles are Janus particles with good emulsion stability to toluene/water emulsions over 30 days. The catalytic degradation of 4-nitrophenol (4-NP) was investigated after loading silver nanoparticles on the surface of the particles by in situ deposition. The anisotropic particles obtained in this work have potential applications in emulsion stabilization and catalysis. Full article

Environmentally persistent free radicals (EPFRs) generated on particles under irradiation in water have attracted particular attention, and their formation mechanisms are not well understood. This study investigated the photoformation of EPFRs on both actual samples collected from an oil production plant in Panjin, Liaoning, China, and simulated Fe(III)-montmorillonite samples in water. The EPFRs detected on actual samples were not easily generated compared with those in the soil or in the air, based on the concentrations of identified PAHs. EPR signals in the range of 10¹⁷ to 10¹⁸ spin/g were detected on the simulated Fe(III)-montmorillonite samples. Their g factors were smaller than 2.0030, which indicated the generation of carbon-centered EPFRs. The primary byproducts were identified by chromatography–mass spectrometry (GC-MS), and a possible EPFR formation pathway during PAH degradation was proposed. Hydrogenation of PAHs during the photoformation of EPFRs was observed and might be due to the catalysis of the simulated particles and the interaction of the intermediates. Meanwhile, the effects of the typical anions (NO₂⁻ and Cl⁻) and the surfactant (TWEEN^® 80 and sodium dodecyl sulfate) were investigated and indicated that the phototransformation process and adsorption process would affect the formation of EPFRs. Overall, our study provided useful information to understand the photoformation of EPFRs in aqueous environments. Full article

Organosilicon materials have shown potential as dehydration agents for waterlogged wooden artifacts. These materials can polymerize under normal conditions to form polymers with favorable mechanical strength, antibacterial properties, and aging resistance. However, the insolubility of most organosilicon hindered their penetration into waterlogged wood, which may lead to an unwanted cracking. This study aimed to evaluate the effectiveness of polydimethylsiloxane (PDMS) and hydroxy-terminated polydimethylsiloxane (PDMS-OH) with low viscosity and moderate reactivity for dehydrating waterlogged wooden artifacts from the Nanhai No.1 shipwreck. Four surfactants ((3–aminopropyl) triethoxysilane (APTES), alkyl polyoxyethylene ether (APEO), tri-methylstearylammonium chloride (STAC), and fatty alcohol polyoxyethylene ether (AEO)) and cosurfactant were employed to transform the two kinds of water-repellent silicone oils into eight groups of highly permeable oil-in-water (O/W) emulsions. Under the catalysis of a neutral catalyst, in situ polymerization occurred within the wood cells. Group P2-2 formulated with PDMS-OH and APEO showed the best efficiency in maintaining the dimensions of the wood during dehydration. The dehydrated wood exhibited a natural color and texture with a minimal volume shrinkage rate of 1.89%. The resulting polymer adhered uniformly to the cell walls, effectively reinforcing the wood cell structure. The weight percent gain of the wood was only 218%, and the pores of the cell lumen were well maintained for future retreatment. This method effectively controlled the sol–gel reaction process of the organosilicon and prevented damage to the wooden artifact during the dehydration process. Moreover, the dehydrated wood samples only experienced a low weight gain of 17% at 95% relative humidity (RH), indicating their great environmental stability. Full article

The unique structural properties of porous ceramics, such as low thermal conductivity, high surface area, controlled permeability, and low density, make this material valuable for a wide range of applications. Its uses include insulation, catalyst carriers, filters, bio-scaffolds for tissue engineering, and composite manufacturing. However, existing processing methods for porous ceramics, namely replica techniques and sacrificial templates, are complex, release harmful gases, have limited microstructure control, and are expensive. In contrast, the direct foaming method offers a simple and cost-effective approach. By modifying the surface chemistry of ceramic particles in a colloidal suspension, the hydrophilic particles are transformed into hydrophobic ones using surfactants. This method produces porous ceramics with interconnected pores, creating a hierarchical structure that is suitable for applications like nano-filters. This review emphasizes the importance of interconnected porosity in developing advanced ceramic materials with tailored properties for various applications. Interconnected pores play a vital role in facilitating mass transport, improving mechanical properties, and enabling fluid or gas infiltration. This level of porosity control allows for the customization of ceramic materials for specific purposes, including filtration, catalysis, energy storage, and biomaterials. Full article

Semiconductor hollow spheres have garnered significant attention in recent years due to their unique structural properties and enhanced surface area, which are advantageous for various applications in catalysis, energy storage, and sensing. The present study explores the surfactant-assisted synthesis of bismuth ferrite (BiFeO₃) hollow spheres, emphasizing their enhanced visible-light photocatalytic activity. Utilizing a novel, facile, two-step evaporation-induced self-assembly (EISA) approach, monodisperse BiFeO₃ hollow spheres were synthesized with a narrow particle size distribution. The synthesis involved Bi/Fe citrate complexes as precursors and the triblock copolymer Pluronic P123 as a soft template. The BiFeO₃ hollow spheres demonstrated outstanding photocatalytic performance in degrading the emerging pollutants Rhodamine B and metronidazole under visible-light irradiation (100% degradation of Rhodamine B in <140 min and of metronidazole in 240 min). The active species in the photocatalytic process were identified through trapping experiments, providing crucial insights into the mechanisms and efficiency of semiconductor hollow spheres. The findings suggest that the unique structural features of BiFeO₃ hollow spheres, combined with their excellent optical properties, make them promising candidates for photocatalytic applications. Full article