Search Results (37)

Controlled porosity with precise pore sizes in carbon monoliths (CMs) is crucial for optimizing performance in electrochemical energy storage and adsorption applications. This study explores the influence of porosity in CMs, developed from polymer precursors via the sol–gel route, employing soft templating, in situ graphene growth, and post-activation. The effects on CO₂ and H₂ sorption and electrochemical capacitor (EC) performance are analyzed. Graphene is successfully grown in situ from graphene oxide (GO), as confirmed by several characterization analyses. The amount of GO incorporated influences the crosslink density of the polymer gel, generating various pore structures at both micro- and mesoscales, which impacts performance. For instance, CO₂ capture peaks at 5.01 mmol g⁻¹ (0 °C, 101 kPa) with 10 wt % GO, due to the presence of wider micropores that allow access to ultramicropores. For H₂ storage, the best performance is achieved with 5 wt % GO, reaching 12.8 mmol g⁻¹ (−196 °C, 101 kPa); this is attributed to the enlarged micropore volumes between 0.75 and 2 nm that are accessible by mesopores of 2 to 3 nm. In contrast, for the ECs, lower GO loadings (0.5 to 2 wt %) improve ion accessibility via mesopores (4 to 6 nm), enhancing rate capability through better conduction. Full article

The purpose of this study was to investigate the effect of different drying methods on the structure and properties of semicrystalline polymer aerogels. Aerogels, consisting of either globular or strut-like morphologies, were prepared from poly(ether ether ketone) (PEEK) or poly(phenylene sulfide) (PPS) and dried using vacuum drying, freeze-drying, or supercritical CO₂ extraction. Vacuum drying was found to result in aerogels with a higher shrinkage, smaller mesopores (with pore widths of 2–50 nm), and smaller surface areas compared to the use of supercritical extraction as the drying method. Freeze-dried aerogels tended to have properties between those of vacuum-dried aerogels and aerogels prepared with supercritical extraction. High network connectivity was found to lead to improved gel modulus, which increased the ability of aerogels to resist network deformation due to stresses induced during drying. The PEEK and PPS aerogel networks consisting of highly connected strut-like features were considerably stiffer than those composed of globular features, and thus shrank less under the forces induced by vacuum drying or freeze-drying. The aerogels prepared from PPS were found to have larger mesopores and smaller surface areas than the aerogels prepared from PEEK. The larger mesopores of the PPS aerogels induced lower capillary stresses on the aerogel network, and thus shrank less. This work demonstrates that preparing PEEK and PPS gels with strut-like features can allow aerogel processing with simpler evaporative drying methods rather than the more complex supercritical drying method. Full article

Delayed or non-healing of bone defects in an aging, multi-morbid population is still a medical challenge. Current replacement materials, like autografts, are limited. Thus, artificial substitutes from biodegradable polymers and bioactive glasses (BGs) are promising alternatives. Here, novel cerium-doped mesoporous BG microparticles (Ce-MBGs) with different cerium content were included in photocrosslinkable, methacrylated gelatin (GelMA) for promoting cellular functions of human mesenchymal stem cells (hBMSCs). The composites were studied for intrinsic morphology and Ce-MBGs distribution by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). They were gravimetrically analyzed for swelling and stability, compressive modulus via Microsquisher^® and bioactivity by Fluitest^® calcium assay and inductively coupled plasma-optical emission spectrometry (ICP-OES), also determining silicon and cerium ion release. Finally, seeding, proliferation, and differentiation of hBMSCs was investigated. Ce-MBGs were evenly distributed within composites. The latter displayed a concentration-dependent but cerium-independent decrease in swelling, while mechanical properties were comparable. A MBG type-dependent bioactivity was shown, while an enhanced osteogenic differentiation of hBMSCs was achieved for Ce-MBG-composites and related to different ion release profiles. These findings show their strong potential in promoting bone regeneration. Still, future work is required, e.g., analyzing the expression of osteogenic genes, providing further evidence for the composites’ osteogenic effect. Full article

The closed mesoporous polymer gels have garnered significant attention as advanced thermal insulation materials due to their superior lightweight characteristics and excellent thermal management capabilities. To accurately predict their thermal performance, this study develops a novel mathematical model that integrates fractal geometry theory, Kirchhoff’s thermal conduction principles, comprehensive Rosseland diffusion approximation, and Mie scattering theory. The conductive thermal conductivity component was formulated based on a diagonal cross fractal structure, while the radiative component was derived considering microscale radiative effects. Model predictions exhibit strong agreement with experimental results from various mesoporous polymer gels, achieving a prediction error of less than 11.2%. Furthermore, a detailed parametric analysis was conducted, elucidating the influences of porosity, cell size, temperature, refractive index, and extinction coefficient. The findings identify a critical cell size range (1–100 µm) and porosity range (0.74–0.97) where minimum thermal conductivity occurs. This proposed modeling approach offers a robust and efficient theoretical tool for designing and optimizing the thermal insulation characteristics of closed mesoporous polymer gels, thereby advancing their application in diverse energy conversion and management systems. Full article

The uranium tailings mineral body is large and loose, and this could lead to radioactive contamination. Nuclides and heavy metals released from uranium tailings can be reduced through reinforcement treatment. The current study investigated the effect of CaCl₂ solutions with the same volume and different mass fractions on uranium tailing reinforcement under the premise of fixing the dosage of metakaolin, sodium hydroxide, sodium silicate, and the water reducer. It was found that, when 20.0% CaCl₂ was injected, the hydration reaction occurred more efficiently, and a more uniform gel polymer was produced. The degree of polymerization was higher, as well as the degree of aggregation near macropores. A large number of closed mesopores formed on the solidified surface. The pore structure of the solidified body was significantly improved; uranium ore particles had smaller gaps between them; the solidified body was better compacted; the leaching rates of uranium and its heavy metal ions were significantly reduced; and the compressive strength of the solidified body improved. In the triaxial test, the solidified body had a strength increase of 4.7 times. In addition to SEM, XPS, and XRD, the solidified samples were analyzed. In uranium slag solidified bodies, C-S-H and C-A-H gels and C-A-S-H and N-A-S-H polymers were formed. The gel polymers were wrapped around the uranium tailing particles, resulting in an 82.6% reduction in uranium leaching and a 57.2% reduction in radon exhalation. Full article

Polymers with micro- and mesoporous structure are promising as materials for gas storage and separation, encapsulating agents for controlled drug release, carriers for catalysts and sensors, precursors of nanostructured carbon materials, carriers for biomolecular immobilization and cellular scaffolds, as materials with a low dielectric constant, filtering/separating membranes, proton exchange membranes, templates for replicating structures, and as electrode materials for energy storage. Sol–gel technologies, track etching, and template synthesis are used for their production, including in micelles of surfactants and microemulsions and sublimation drying. The listed methods make it possible to obtain pores with variable shapes and sizes of 5–50 nm and achieve a narrow pore size distribution. However, all these methods are technologically multi-stage and require the use of consumables. This paper presents a review of the use of macromolecular architecture in the synthesis of micro- and mesoporous polymers with extremely high surface area and hierarchical porous polymers. The synthesis of porous polymer frameworks with individual functional capabilities, the required chemical structure, and pore surface sizes is based on the unique possibilities of developing the architecture of the polymer matrix. Full article

A nano-structured conjugated polymer with multiple micro-/meso-pores was synthesized by post-crosslinking of an end-functionalized hyperbranched conjugated prepolymer. Firstly, an AB₂ monomer 3-((3,5-dibromo-4-(octyloxy)phenyl)ethynyl)-6-ethynyl-9-octyl-9H-carbazole (PECz) was synthesized and polymerized by Sonogashira reaction to give the -Br end-functionalized hyperbranched conjugated prepolymer hb-PPECz. The photophysical and electrochemical properties of hb-PPECz were investigated. The λ_max of absorption and emission of hb-PPECz in tetrahydrofuran (THF) solution was 313 and 483 nm, respectively. The optical energy bandgap, highest occupied molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) energy levels of hb-PPECz were 2.98, −5.81, and −2.83 eV, respectively. Then, the prepolymer hb-PPECz was post-crosslinked by Heck reaction with divinylbenzene to give the porous conjugated polymer c-PPECz. The effects of hb-PPECz concentration and added dispersant polyvinylpyrrolidone (PVP K-30) on the morphology and porosity of c-PPECz were investigated. The resulting c-PPECzs showed multiple porous structures mainly constructed by micropores and mesopores. Under a higher hb-PPECz concentration (4 wt/v%), a bulky gel product was obtained. Under lower hb-PPECz concentrations (0.6 wt/v%~2 wt/v%), the resulting c-PPECzs were mainly composed of nano-sized particles. Nearly spheric nanoparticles (200~300 nm) (c-PPECz-5) were obtained under the concentration of 1 wt/v% in the presence of PVP (10 wt% of hb-PPECz). The Brunauer–Emmett–Teller (BET) surface area, pore volume, average pore size, and percentage of pore size below 10 nm of c-PPECz-5 were 10.7781 m²·g⁻¹, 0.0108 cm³·g⁻¹, 4.0081 nm, and 94.47%, respectively. Full article

Poly(ether ether ketone) (PEEK) was found to form gels in the benign solvent 1,3-diphenylacetone (DPA). Gelation of PEEK in DPA was found to form an interconnected, strut-like morphology composed of polymer axialites. To our knowledge, this is the first report of a strut-like morphology for PEEK aerogels. PEEK/DPA gels were prepared by first dissolving PEEK in DPA at 320 °C. Upon cooling to 50 °C, PEEK crystallizes and forms a gel in DPA. The PEEK/DPA phase diagram indicated that phase separation occurs by solid–liquid phase separation, implying that DPA is a good solvent for PEEK. The Flory–Huggins interaction parameter, calculated as χ₁₂ = 0.093 for the PEEK/DPA system, confirmed that DPA is a good solvent for PEEK. PEEK aerogels were prepared by solvent exchanging DPA to water then freeze-drying. PEEK aerogels were found to have densities between 0.09 and 0.25 g/cm³, porosities between 80 and 93%, and surface areas between 200 and 225 m²/g, depending on the initial gel concentration. Using nitrogen adsorption analyses, PEEK aerogels were found to be mesoporous adsorbents, with mesopore sizes of about 8 nm, which formed between stacks of platelike crystalline lamellae. Scanning electron microscopy and X-ray scattering were utilized to elucidate the hierarchical structure of the PEEK aerogels. Morphological analysis found that the PEEK/DPA gels were composed of a highly nucleated network of PEEK axialites (i.e., aggregates of stacked crystalline lamellae). The highly connected axialite network imparted robust mechanical properties on PEEK aerogels, which were found to densify less upon freeze-drying than globular PEEK aerogel counterparts gelled from dichloroacetic acid (DCA) or 4-chlorphenol (4CP). PEEK aerogels formed from DPA were also found to have a modulus–density scaling that was far more efficient in supporting loads than the poorly connected aerogels formed from PEEK/DCA or PEEK/4CP solutions. The strut-like morphology in these new PEEK aerogels also significantly improved the modulus to a degree that is comparable to high-performance crosslinked aerogels based on polyimide and polyurea of comparable densities. Full article

A mesoporous silica support was synthesized using the sol–gel method from trichlorosilane. There is a tendency for the specific surface area and the proportion of silica particles mesopores to increase during all stages of sol–gel synthesis. It has been shown that the insertion of hexane and toluene, as additional solvents, into the structure-forming polyethylene glycol, makes it possible to regulate the pore size and specific surface area of silica. Silica functionalization was carried out using SILP technology. The activities of the catalytic systems based on polymer and inorganic supports immobilized by imidazole-based ionic liquids during the trichlorosilane disproportionation reaction were compared. There is a tendency for the monosilane yield for catalytic systems based on an inorganic support to increase. We identified the most promising catalyst in terms of monosilane yield and proposed a bifunctional catalyst that exhibited activity in two parallel reactions: trichlorosilane disproportionation and silicon tetrachloride hydrogenation. Full article

The increasing interest in innovative solutions for addressing bone defects has driven research into the use of Bioactive Mesoporous Glasses (MBGs). These materials, distinguished by their well-ordered mesoporous structure, possess the capability to accommodate plant extracts with well-established osteogenic properties, including bovine lactoferrin (bLF), as part of their 3D scaffold composition. This harmonizes seamlessly with the ongoing advancements in the field of biomedicine. In this study, we fabricated 3D scaffolds utilizing MBGs loaded with extracts from parsley leaves (PL) and embryogenic cultures (EC), rich in bioactive compounds such as apigenin and kaempferol, which hold potential benefits for bone metabolism. Gelatin Methacryloyl (GelMa) served as the polymer, and bLF was included in the formulation. Cytocompatibility, Runx2 gene expression, ALP enzyme activity, and biomineralization were assessed in preosteoblastic MC3T3-E1 cell cultures. MBGs effectively integrated PL and EC extracts with loadings between 22.6 ± 0.1 and 43.6 ± 0.3 µM for PL and 26.3 ± 0.3 and 46.8 ± 0.4 µM for EC, ensuring cell viability through a release percentage between 28.3% and 59.9%. The incorporation of bLF in the 3D scaffold formulation showed significant differences compared to the control in all assays, even at concentrations below 0.2 µM. Combinations, especially PL + bLF at 0.19 µM, demonstrated additive potential, with superior biomineralization compared to EC. In summary, this study highlights the effectiveness of MBGs in incorporating PL and EC extracts, along with bLF, into 3D scaffolds. The results underscore cytocompatibility, osteogenic activity, and biomineralization, offering exciting potential for future in vivo applications. Full article

In this study, a starch cryoaerogel formulation was developed as a carrier for poorly water-soluble drugs, like atorvastatin. Cryoaerogels were generated through a sol–gel method combined with a freeze-drying technique, and atorvastatin was incorporated into the obtained mesoporous systems during the solvent exchange stage. The formulated drug-loaded polymer structures were characterized in terms of their physicochemical properties, solid-state behavior, and cytotoxicity. They had a pore size of 27.56 nm and a drug loading size of 38.60%. Fourier transform infrared (FTIR) and scanning electron microscopy (SEM) analyses indicated that atorvastatin was successfully incorporated into the cryoaerogel pores. The amorphous nature of the loaded drug was confirmed via X-ray diffraction (XRD). Furthermore, after the atorvastatin incorporation into the cryogel, the volume of nitrogen adsorbed on one gram of cryoaerogel (Vm), as well as the specific surface area (aBET) were reduced. The comparison between the drug release profiles of crystalline atorvastatin and the loaded formulation of atorvastatin showed that by including the drug into the pores of the developed cryoaerogel matrix its solubility was significantly improved—the time for the dissolution of 30% pure atorvastatin (t_30%) was approximately 4 h, whereas the determined t_30% for the formulated cryoaerogels was only 1 h. Moreover, the data from the MTT assay illustrated that the designed cryoaerogel could be used as a safe oral atorvastatin delivery system. According to obtained results, it could be concluded that the starch cryoaerogel formulation is a promising candidate for oral delivery of poorly water-soluble therapeutic agents. Full article

The aim of this work is to effectively combine the advantages of polymer and ceramic nanoparticles and improve the comprehensive performance of lithium-ion batteries (LIBs) diaphragm. A flexible film composed of electro-spun P(VDF-HFP) nanofibers covered by a layer of mesoporous silica (P(VDF-HFP)@SiO₂) was synthesized via a sol–gel transcription method, then used as a scaffold to absorb organic electrolyte to make gel a electrolyte membrane (P(VDF-HFP)@SiO₂-GE) for LIBs. The P(VDF-HFP)@SiO₂-GE presents high electrolyte uptake (~1000 wt%), thermal stability (up to ~350 °C), ionic conductivity (~2.6 mS cm⁻¹ at room temperature), and excellent compatibility with an active Li metal anode. Meanwhile, F-doping carbon/silica composite nanofibers (F-C@SiO₂) were also produced by carbonizing the P(VDF-HFP)@SiO₂ film under Ar and used to make an electrode. The assembled F-C@SiO₂|P(VDF-HFP)@SiO₂-GE|Li half-cell showed long-cycle stability and a higher discharge specific capacity (340 mAh g⁻¹) than F-C@SiO₂|Celgard 2325|Li half-cell (175 mAh g⁻¹) at a current density of 0.2 A g⁻¹ after 300 cycles, indicating a new way for designing and fabricating safer high-performance LIBs. Full article

Drilling fluid systems for deep and ultra-deep wells are hampered by both high-temperature downhole environments and lengthy cycle periods. Suppose that the gel particle-plugging agent, the primary treatment agent in the system, fails to offer durable and stable plugging performance. In such a scenario, the borehole wall is susceptible to instability and landslide after prolonged immersion, leading to downhole accidents. In this study, novel core-shell gel particles (modified ZIF) with ZIF particles employed as the core material and organosilicon-modified polyethylene polyamine (PEPA) as the polymer shell were fabricated using PEPA, in-house synthesized (3-aminopropyl) triethoxysilane (APTS), and the ZIF-8 metal-organic framework (MOF) as the raw materials to enhance the long-term plugging performance of gel plugging agents. The modified ZIF particles are nanoscale polygonal crystals and differ from conventional core-shell gel particles in that they feature high molecular sieve catalytic activity due to the presence of numerous interior micropores and mesopores. As a result, modified ZIF exhibits the performance characteristics of both rigid and flexible plugging agents and has an excellent catalytic cross-linking effect on the sulfonated phenolic resin (SMP-3) and sulfonated lignite resin (SPNH) in drilling fluids. Consequently, a cross-linking reaction occurs when SMP-3 and SPNH flow through the spacings in the plugging layer formed by the modified ZIF particles. This increases the viscosity of the liquid phase and simultaneously generates an insoluble gel, forming a particle-gel composite plugging structure with the modified ZIF and significantly enhancing the long-term plugging performance of the drilling fluid. Full article

Silicon-based ceramic aerogels obtained by the polymer pyrolysis route possess excellent thermophysical properties, but their poor mechanical properties limit their broader applicability in thermal insulation materials. Herein, SiCN(O) ceramic aerogels were prepared under the toughening effect of a crosslinker (hexamethylene diisocyanate, HDI), which maintains the structural integrity of the aerogel during the wet gel-to-aerogel conversion. The aerogel maintained a high surface area (88.6 m² g⁻¹) and large pore volume (0.21 cm³ g⁻¹) after pyrolysis. Based on this, mullite-fiber-reinforced SiCN(O) aerogels composites with outstanding thermal insulation properties and better mechanical performance were synthesized via ambient pressure impregnation. Furthermore, the effect of the impregnation concentration on the mechanical and insulation properties of the composites was investigated. The results revealed that the composite prepared with a solution ratio of 95 wt.% exhibited a low density (0.11 g cm⁻³) and a low thermal conductivity (0.035 W m⁻¹ K⁻¹), indicating an ~30% enhancement in its thermal insulation performance compared to the mullite fiber; the mesoporous aerogel structures wrapped on the mullite fibers inhibited the gas thermal conduction inside the composites. Full article

Considering the safety problem that is caused by liquid electrolytes and Li dendrites for lithium batteries, a new quasi-solid-state polymer electrolyte technology is presented in this work. A layer of 1,4-phenylene bridged polysilsesquioxane (PSiO) is synthesized by a sol-gel way and coated on the electrospun polyacrylonitrile (PAN) nanofiber to prepare a PAN@PSiO nanofiber composite membrane, which is then used as a quasi-solid-state electrolyte scaffold as well as separator for lithium batteries (LBs). This composite membrane, consisting of the three-dimensional network architecture of the PAN nanofiber matrix and a mesoporous PSiO coating layer, exhibited a high electrolyte intake level (297 wt%) and excellent mechanical properties. The electrochemical analysis results indicate that the ionic conductivity of the PAN@PSiO-based quasi-solid-state electrolyte membrane is 1.58 × 10⁻³ S cm⁻¹ at room temperature and the electrochemical stability window reaches 4.8 V. The optimization of the electrode and the composite membrane interface leads the LiFePO₄|PAN@PSiO|Li full cell to show superior cycling (capacity of 137.6 mAh g⁻¹ at 0.2 C after 160 cycles) and excellent rate performances. Full article