Search Results (71)

The growing demand for sustainable and efficient synthetic methodologies has brought nanocatalysis to the forefront of modern organic chemistry, particularly in the construction of heterocyclic compounds through multicomponent reactions (MCRs). Among various nanocatalysts, calcium oxide nanoparticles (CaO NPs) have gained significant attention because of their strong basicity, thermal stability, low toxicity, and cost-effectiveness. This review provides a comprehensive account of the recent strategies using CaO NPs as heterogeneous catalysts for the green synthesis of nitrogen- and oxygen-containing heterocycles through MCRs. Key reactions such as Biginelli, Hantzsch, and pyran annulations are discussed in detail, with emphasis on atom economy, reaction conditions, product yields, and catalyst reusability. In many instances, CaO NPs have enabled solvent-free or aqueous protocols with high efficiency and reduced reaction times, often under mild conditions. Mechanistic aspects are analyzed to highlight the catalytic role of surface basic sites in facilitating condensation and cyclization steps. The performance of CaO NPs is also compared with other oxide nanocatalysts, showcasing their benefits from green metrics evaluation like E-factor and turnover frequency. Despite significant progress, challenges remain in areas such as asymmetric catalysis, industrial scalability, and catalytic stability under continuous use. To address these gaps, future directions involving doped CaO nanomaterials, hybrid composites, and mechanochemical approaches are proposed. This review aims to provide a focused and critical perspective on CaO NP-catalyzed MCRs, offering insights that may guide further innovations in sustainable heterocyclic synthesis. Full article

In this study, calcium hexaboride (CaB₆) was successfully synthesized from anhydrous colemanite (Ca₂B₆O₁₁) via a mechanochemical approach. The synthesis process was optimized in two stages: by adjusting the reaction time and varying the carbon-to-colemanite ratio. Structural and compositional analyses were performed using FT-IR, XRD, SEM, and EDX techniques. The optimal synthesis condition was found to be a carbon-to-colemanite ratio of 10:1 and a reaction time of 1020 min, yielding the highest Ca–B vibrational intensities in FT-IR spectra. The mechanochemical method enabled CaB₆ formation at ambient conditions without the need for high temperature or pressure, offering a significant advantage over traditional methods. The results suggest that this method can serve as a low-energy route for the synthesis of metal borides, which are promising candidates for applications in refractory materials, electronics, and hydrogen storage systems. Full article

The chemical and structural similarity of calcium orthophosphates to hard tissues in the human body makes them suitable as biomaterials for bone implants, cements, injection systems, etc., for bone regeneration and reconstruction. Tetracalcium phosphate (Ca₄(PO₄)₂O, TTCP) is a promising component for such biomaterials due to its high calcium content and alkaline nature. The former makes it suitable for promoting mineralization, while the latter supports neutralization of the acidic environment, helping to prevent inflammation and improve the biocompatibility of the materials. However, it is the least used calcium orthophosphate due to the difficulties in its synthesis. This study examines the effect of high-energy mechanochemical activation on the phase evolution, particle morphology, and thermal behaviour of equimolar mixtures of Ca(OH)₂ and CaHPO₄, with the aim of optimizing precursor conditions for the synthesis of (TTCP)-rich ceramic materials. The results demonstrate that mechanochemical activation effectively induces structural disorder, promotes the formation of amorphous and nanocrystalline phases, and facilitates subsequent phase transitions upon calcination. The combined use of solid-state NMR, XRD, TEM, and thermal analysis provides a comprehensive understanding of the transformation pathways. Ultimately, 24 h of activation under the experimental conditions was identified as optimal for producing a precursor with a favorable phase composition for obtaining TTCP-rich ceramic materials after calcination at 1350 °C. Full article

Mechanochemical methods have received much attention in the synthesis and design of all-solid-state battery materials in recent years due to their advantages of being green, efficient, easy to operate, and solvent-free. In this review, common mechanochemical methods, including high-energy ball milling, twin-screw extrusion (TSE), and resonant acoustic mixing (RAM), are introduced with the aim of providing a fundamental understanding of the subsequent material design. Subsequently, the discussion focuses on the application of mechanochemical methods in the construction of solid-state electrolytes, anode materials, and cathode materials, especially the research progress of mechanical energy-induced polymerization strategies in building flexible composite electrolytes and enhancing interfacial stability. Through the analysis of representative work, it is demonstrated that mechanochemical methods are gradually evolving from traditional physical processing tools to functional synthesis platforms with chemical reaction capabilities. This review systematically organizes its development and research trends in the field of all-solid-state battery materials and explores potential future breakthrough directions. Full article

Conventional methods for the synthesis of porous carbons are typically time- and energy-consuming and often contribute to the excessive accumulation of waste solvents. An alternative approach is to employ environmentally friendly procedures, such as mechanochemical synthesis, which holds great potential for large-scale production of advanced carbon-based materials in coming years. This review covers mechanochemical syntheses of highly porous carbons, with a particular focus on new adsorbents and catalysts that can be obtained from biomass. Mechanochemically assisted methods are well suited for producing highly porous carbons (e.g., ordered mesoporous carbons, hierarchical porous carbons, porous carbon fibers, and carbon–metal composites) from tannins, lignin, cellulose, coconut shells, nutshells, bamboo waste, dried flowers, and many other low-cost biomass wastes. Most mechanochemically prepared porous carbons are proposed for applications related to adsorption, catalysis, and energy storage. This review aims to offer researchers insights into the potential utilization of biowastes, facilitating the development of cost-effective strategies for the production of porous carbons that meet industrial demands. Full article

The present study describes the mechanochemical synthesis and physicochemical characterization of a novel composite material composed of yellow clay, hydroxyapatite, and Clitoria ternatea L. The synthesis was carried out using a solvent-free, energy-efficient mechanochemical method. The composite was analyzed for its toxicity, particle size distribution, release of bioactive compounds, surface morphology, structural features, and electrokinetic properties. UV-VIS spectrophotometry revealed that the release of bioactive substances was approximately 1.5 to 3 times higher in the composite compared to control samples. Particle size analysis indicated a wide distribution ranging from 350 to 1300 nm. Nitrogen adsorption–desorption (ASAP) confirmed the porous nature of the material, while SEM and FTIR analyses verified the successful incorporation of all components. Electrokinetic studies showed zeta potential values ranging from +15 mV to –32 mV, indicating varying colloidal stability. The proposed composite demonstrates promising potential as a carrier of biologically active substances for pharmaceutical and cosmetic applications. Full article

In this investigation, a novel process for the synthesis of nano-ZrO₂ powders based on high-temperature mechanochemical technology (HTMT) in a short process is proposed and HTMT nano-ZrO₂ enhancement mechanism as an additive on the properties of B₄C ceramics was systematically investigated. ZrO(OH)₂ was used as a precursor, and ZrO₂-B₄C composites were prepared by optimizing the ball milling temperature and time in combination with the hot-press sintering technique. The results demonstrated that the high-temperature mechanical force causes the transition temperature of ZrO₂ from monoclinic to tetragonal crystal system to be decreased to 500 °C. The ZrO₂ treated by high-temperature ball milling at 600 °C/6 h exhibits lower microstress, higher crystallinity, and a particle size of only about 9.12 nm. HTMT nano-ZrO₂ effectively controls the size of in situ generated ZrB₂ particles in B₄C ceramics, reduces interfacial porosity and grain coarsening, and promotes densification of B₄C ceramics compared to commercially available nano-ZrO₂. With the addition of 4 wt% HTMT nano-ZrO₂, the composite showed optimal comprehensive properties: relative density of 99.75% (2.57 g/cm³), fracture toughness of 4.74 MPa/m^1/2, flexural strength of 266.61 MPa, Vickers hardness of 31.14 GPa, and fracture mode with mixed mechanism of through-crystallization and along-crystallization. Full article

New ways of ensuring sustainable development in various areas of life are being intensively researched. One of the key priorities is to maximize the use of invaluable natural ingredients in cosmetic products while minimizing the negative impact on the environment. In this study, a three-component natural composite based on amber, diatomite, and Phytokeratin^TM (hydrolyzed plant protein) was developed using mechanochemical synthesis. The goal was to maximize the release of biologically active substances, such as succinic acid and Phytokeratin^TM, in aqueous solution. The physicochemical properties of the materials were characterized using Scanning Electron Microscopy (SEM), thermogravimetric (TG) and differential thermogravimetric (DTG) analysis, Fourier Transform Infrared (FTIR) spectroscopy, and Ultraviolet–Visible (UV-Vis) spectrophotometry. Additionally, Density Functional Theory (DFT) was used to perform quantum chemical calculations and characterize molecular interactions in the composite. The optimized composite demonstrated favorable release characteristics and structural properties, confirming its suitability for cosmetic applications. DFT calculations revealed the potential molecular-level interactions between the organic components, indicating the stability and functional integration of the composite. The resulting innovative composite was successfully incorporated into eco-friendly cosmetic formulations, including a solid shampoo bar and a nail conditioner. Full article

The synthesis of CaKFe₄As₄ superconducting compounds either requires the adoption of high-temperature synthesis or implies the intimate mixing of the precursors via mechanochemical routes before the thermal step in order to avoid chemical inhomogeneities that lead to thermodynamically stable unwanted phases. High Energy Ball Milling (HEBM) represents a useful tool to ensure the comminution of the elements and their dispersion to obtain the target phase. The adoption of mechanochemical treatments is, however, known to lead to the formation of aggregates of small crystals, leading to a powder morphology not optimal for practical applications. In this work, we report our findings in the synthesis of CaKFe₄As₄ polycrystalline compounds showing the effect of milling energy on the morphology and phase composition of the powders. To overcome the limits of conventional synthesis, we report the results of a novel synthesis approach for CaKFe₄As₄ materials, highlighting how the choice of the proper precursors and the adoption of milder treatments can represent the key to optimizing the powder morphology. Full article

The ZnO/hydroxyapatite nanocomposite was prepared by attrition in a planetary mill from hydroxyapatite (HA) and ZnO nanopowders. The photocatalytic degradation of synthetic dye, methyl orange (MO), was evaluated under stirring and UV irradiations by measuring the spectroscopically UV-VIS absorbance of the solution in order to determine the remanent dye concentration. The samples CZH3 (75% ZnO) and CZH4 (25% ZnO) highlighted the best MO retention from aqueous solution by adsorption and photodegradation effects. The high absorbance of the proposed nanocomposites showed their potential to be used as photocatalysts for wastewater treatment to enable the retention of organic pollutants. Full article

This study investigates the thermoelectric properties of Se-rich β-Ag₂Se synthesized via a mechanochemical method followed by spark plasma sintering (SPS) in less than 30 min of the total reaction time. Importantly, only a short 10 min milling process followed by appropriate SPS was enough to produce single-phase Ag₂Se_1+x samples with varying selenium content (where x = 0, 0.01, 0.02, 0.04). The introduction of excess selenium significantly influenced the thermoelectric performance, optimizing the carrier concentration during synthesis and resulting in substantial thermoelectric improvements. The sample with nominal composition Ag₂Se_1.01 exhibited a high dimensionless figure-of-merit (ZT) >0.9 at 385 K, which is nearly six times higher than the reference sample (β-Ag₂Se). Our findings bring valuable insight into the technology of optimization of thermoelectric characteristics of Se-rich β-Ag₂Se, highlighting its potential for applications in thermoelectric devices. The study demonstrates the energetically efficient and environmental advantage of our mechanochemical route to produce Se-rich β-Ag₂Se, providing a solvent-free and commercially viable alternative synthesis for energy (thermoelectric and solar energy). Full article

Ag-based electrical contact materials are essential in low-voltage devices such as relays, switches, circuit breakers, and contactors. Historically, Ag-CdO composites have been preferred due to their superior electrical and thermal conductivities, resistance to arcing, and mechanical strength. However, the toxicity of Cd has led to increased restrictions on its use. With the aim of contributing to the development of a new environment-friendly, Ag-Zn₂SnO₄-based electrical contact material, the kinetics of the hot mechanochemical oxidation of a Ag-Sn-Zn solid solution obtained by mechanical alloying were investigated. The results indicated that the proposed synthesis route produces Ag-based composites with a homogeneous distribution of nanoscale Zn₂SnO₄ precipitates, which is unattainable through conventional material processing methods. This kinetic study established that the mechanochemical oxidation of the Ag-Sn-Zn solid solution follows the Johnson–Mehl–Avrami–Kolmogorov model. An analysis of the microstructure and the relationship between the activation energy “Ea” and the Avrami exponent “n” from experimental data fitting suggests that the primary mechanism for the oxidation of the Ag-Sn-Zn solid solution during the hot mechanochemical process is related to the three-dimensional oxide growth being limited by oxygen diffusion after its immediate initial nucleation. Full article

In this paper, the results of the technological combustion of SHS heat insulators based on mineral origins are presented. It is shown that after mechanochemical treatment of minerals—diatomite—the kinetic characteristics of the combustion process change, providing targeted formation of the phase composition, structure, and properties of the SHS composite. A positive effect of using various modifiers during the MCT of diatomite—the activation of the combustion process—was established. The selection of modifiers provides an increase in the strength of the synthesized SHS composites as a result of the formation of aluminate compounds in the synthesis products, and a decrease in thermal conductivity to 0.157 W/m*K due to the formation of the ultraporous structure of the samples. Full article

CaWO₄ nanoparticles were obtained by facile mechanochemical synthesis at room temperature, applying two different milling speeds. Additionally, a solid-state reaction was employed to assess the phase composition, structural, and optical characteristics of CaWO₄. The samples were analyzed by X-ray diffraction (XRD), transition electron microscopy (TEM), and Raman, infrared (IR), ultraviolet–visible (UV–Vis) reflectance, and photoluminescence (PL) spectroscopies. The phase formation of CaWO₄ was achieved after 1 and 5 h of applied milling speeds of 850 and 500 rpm, respectively. CaWO₄ was also obtained after heat treatment at 900 °C for 12 h. TEM and X-ray analyses were used to calculate the average crystallite and grain size. The Raman and infrared spectroscopies revealed the main vibrations of the WO₄ groups and indicated that more distorted structural units were formed when the compound was synthesized by the solid-state method. The calculated value of the optical band gap of CaWO₄ significantly increased from 2.67 eV to 4.53 eV at lower and higher milling speeds, respectively. The determined optical band gap of CaWO₄, prepared by a solid-state reaction, was 5.36 eV. Blue emission at 425 (422) nm was observed for all samples under an excitation wavelength of 230 nm. CaWO₄ synthesized by the solid-state method had the highest emission intensity. It was established that the intensity of the PL peak depended on two factors: the morphology of the particles and the crystallite sizes. The calculated color coordinates of the CaWO₄ samples were located in the blue region of the CIE diagram. This work demonstrates that materials with optical properties can be obtained simply and affordably using the mechanochemical method. Full article

Recent environmental concerns have increased demand for renewable polymers and sustainable green resource usage, such as biomass-derived components and carbon dioxide (CO₂). Herein, we present crosslinked polyurethanes (CPUs) fabricated from CO₂- and biomass-derived monomers via a facile solvent-free ball milling process. Furan-containing bis(cyclic carbonate)s were synthesized through CO₂ fixation and further transformed to tetraols, denoted FCTs, by aminolysis and utilized in CPU synthesis. Highly dispersed polyurethane-based hybrid composites (CPU–Ag) were also manufactured using a similar ball milling process. Due to the malleability of the CPU matrix, enabled by transcarbamoylation (dynamic covalent chemistry), CPU-based composites are expected to present very low interfacial thermal resistance between the heat sink and heat source. The characteristics of the dynamic covalent bond (i.e., urethane exchange reaction) were confirmed by the results of dynamic mechanical thermal analysis and stress relaxation analysis. Importantly, the high thermal conductivity of the CPU-based hybrid material was confirmed using laser flash analysis (up to 51.1 W/m·K). Our mechanochemical approach enables the facile preparation of sustainable polymers and hybrid composites for functional application. Full article