Search Results (23)

Rapid industrialization has escalated environmental pollution caused by organic compounds, posing critical challenges for wastewater treatment. Advanced oxidation processes based on peroxymonosulfate (PMS) suffer from metal leaching and catalyst recycling challenges. To address these limitations, this study developed a nitrogen-doped biochar aerogel (NBA) derived from poplar wood powder as an eco-friendly and easily recoverable PMS activator. The NBA catalyst, optimized by tuning the calcination temperature to achieve a specific surface area of 297.5 m² g⁻¹, achieved 97% bisphenol A (BPA) removal within 60 min with a catalyst dosage of 0.3 g/L and 1.0 mM PMS under mild conditions. The material exhibited broad pH adaptability (pH 3.5–9), recyclability (>94% efficiency after thermal treatment), and versatility in degrading seven pollutants (BPA, phenol, 4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, rhodamine 6G, and levofloxacin) through synergistic radical (•OH, SO₄^•−, O₂^•−) and non-radical (¹O₂) pathways. X-ray photoelectron spectroscopy (XPS) analyses revealed that nitrogen doping enhanced PMS activation by optimizing electronic structures. This study highlights the potential of waste biomass-derived carbon aerogels as eco-friendly, efficient, and reusable catalysts for advanced oxidation processes in wastewater treatment. Full article

Phenolic aerogel is one of the most widely used lightweight thermal protective materials at present. With changes in the application environments, higher requirements are put forward for the heat resistance and mechanical properties of phenolic aerogel. In this paper, boric acid was used to modify phenolic resin, and then boron-modified phenolic aerogel was prepared. The chemical structure of modified phenolic resin was studied by infrared spectroscopy (FTIR). The microstructure, thermal stability, heat resistance in air, and compression resistance of phenolic aerogel were studied by volume shrinkage, scanning electron microscope, thermogravimetric analysis, high-temperature combustion test, and mechanical test. The results showed that the modification introduced boron oxygen bonds on the phenolic main chain. The compatibility difference between boron and phenolic resin with different content has a significant impact on the performance of phenolic aerogel. When boron content is 5–10% of phenolic resin, the network structure and thermal stability of phenolic aerogel can be significantly improved, and the maximum compressive strength of phenolic aerogel can also be improved. Boron-modified phenolic aerogel is expected to play an important role in the field of thermal insulation. Full article

Previous reviews by authors indicate the continuing development and improvement of thermal protective systems through the introduction of polymer nanocomposites into polymer matrix composites. These materials perform as thermal protective systems for a variety of aerospace applications, such as thermal protection systems (TPSs), solid rocket motor (SRM) nozzles, internal insulation of SRMs, leading edges of hypersonic vehicles, and missile launch structures. A summary of the most recent global technical research is presented. Polymeric resin systems continue to emphasize phenolic resins and other materials. New high-temperature organic resins based on phthalonitrile and polysiloxane are described and extend the increased temperature range of resin matrix systems. An important technical development relates to the transformation of the resin matrix, primarily phenolic resin, into an aerogel or a nanoporous material that penetrates uniformly within the reinforcing fiber configuration with a corresponding particle size of <100 nm. Furthermore, many of the current papers consider the use of low-density carbon fiber or quartz fiber in the use of low-density felts with high porosity to mimic NASA’s successful use of rigid low-density carbon/phenolic known as phenolic impregnated carbon ablator (PICA). The resulting aerogel composition with low-density non-wovens or felts possesses durability and low density and is extremely effective in providing insulation and preventing heat transfer with low thermal conductivity within the aerogel-modified thermal protective system, resulting in multiple features, such as low-density TPSs, increased thermal stability, improved mechanical properties, especially compressive strength, lower thermal conductivity, improved thermal insulation, reduced ablation recession rate and mass loss, and lower backside temperature. The utility of these TPS materials is being expanded by considering them for infrastructures and ballistics besides aerospace applications. Full article

A huge challenge is how to prepare flexible silicone aerogel materials with good flame retardancy, thermal stability, and hydrophobic properties. In this paper, resorcinol–formaldehyde was introduced into the silicone network composed of methyltrimethoxysilane (MTMS), phenyltriethoxysilane (PTES), and dimethyldimethoxysilane (DMDMS). Flexible hybrid aerogels with excellent thermal insulation, flame retardant, and hydrophobic properties were prepared by the sol–gel method and ambient pressure drying (APD), and the preparation process does not require long-term solvent exchange, only about 3 h of soaking and washing of the wet gel. The results show that the prepared phenolic-silicone aerogel has low density (0.093 g/cm³), low thermal conductivity (0.041 W/m·K), high flexibility, and compression fatigue resistance. The phenolic microspheres are bonded to the silicone skeleton to maintain the original flexibility. After 50% compression deformation, it returns to the original size normally, and there is no significant change in the stress of the sample after 50 compression cycles. Compared with pure silicone aerogels, the hybrid aerogels doped with phenolic have better char yield (65.28%) and higher decomposition temperature (609 °C). The hybrid aerogel sample has good flame-retardant properties, which can withstand alcohol lamp burning without being ignited. The micron-sized phenolic beads give the hybrid aerogels better hydrophobic properties, showing a higher static water contact angle (152°). The excellent thermal and mechanical properties mean that the hybrid aerogels prepared in this paper have good application prospects for aerospace, outdoor equipment, and other fields. Full article

In order to prepare flexible thermal protection aerogel materials, using dimethyldimethoxysilane (DMDMS) and methyltrimethoxysilane (MTMS) as co-precursors, isocyanate-propyltrimethoxysilane (CFS-006) was added to the co-precursor as a coupling agent, and resorcinol and formaldehyde were added to the sol solution to prepare a phenolic silicone hybrid aerogel (FAS) by the sol–gel method. The prepared FAS aerogel had no phase separation problem, the density was only 0.118 g/cm³, the hydrophobic angle reached 155.3°, and it had certain flexibility. It could be compressed to 70% and still be restored to its original state. The FAS aerogel also had a low thermal conductivity of 0.0318 W/(m·K) and good high temperature insulation. The introduction of phenolic groups improved thermal stability; Tmax increased to 643.7 °C, and the residual carbon rate was 24.5%. This work has positive significance for the future combination of aerogels and textiles in the preparation of firefighting protective clothing. Full article

Thermally stable high-performance phenolic resin aerogels (PRAs) are of great interest for thermal insulation because of their light weight, fire retardancy and low thermal conductivity. However, the drawbacks of PRA synthesis, such as long processing time, inherent brittleness and significant shrinkage during drying, greatly restrict their wide applications. In this work, PRAs were synthesized at ambient pressure through a near-net shape manufacturing technique, where boron-containing thermosetting phenolic resin (BPR) was introduced into the conventional linear phenolic resin (LPR) to improve the pore characteristics, mechanical properties and thermal performances. Compared with the traditional LPR-synthesized aerogel, the processing time and the linear shrinkage rate during the drying of the PRAs could be significantly reduced, which was attributed to the enhanced rigidity and the unique bimodal pore size distribution. Furthermore, no catastrophic failure and almost no mechanical degradation were observed on the PRAs, even with a compressive strain of up to 60% at temperatures ranging from 25 to 200 °C, indicating low brittleness and excellent thermo-mechanical stability. The PRAs also showed outstanding fire retardancy. On the other hand, the PRAs with a density of 0.194 g/cm³ possessed a high Young’s modulus of 12.85 MPa and a low thermal conductivity of 0.038 W/(m·K). Full article

Despite being the most abundant renewable resource in Estonia, wood has not been fully utilized for its potential value. To fully harness its potential, wood needs to be processed to its core components, such as fibers, wood sugars, and lignin, using chemical, thermochemical, or enzymatic methods. Researchers at TalTech are working on developing a comprehensive value chain for wood valorization, encompassing the production of food additives, thermoplastics, coating materials, and fine chemicals. Traditionally, lignin, a byproduct of the wood fractionation, was burned for energy. However, TalTech researchers are now using lignin to create novel thermoplastics, catalytic materials, and fine chemicals via fermentation processes. Here we show that the conversion of lignin into novel functional materials can be tailored by selecting appropriate extraction methods and source biomass. For instance, organosolv lignin extracted from barley straw exhibits the largest BET active surface area for lignin-based aerogels compared to those produced from softwood or hardwood organosolv lignins. Additionally, we showcase the potential of actinobacterial enzymes to detoxify phenol-containing wood sugar solutions, enabling their utilization in fermentation processes involving a wider array of microbial species. Full article

Rapid extraction and concentration systems based on green materials such as cellulose or lignin are promising. However, there is still a need to optimize the material properties and production processes. Unlike conventional cellulose or lignin sorbent materials, aquatic reed root cells can concentrate external organic pollutants in the water and accumulate them in the plant. Inspired by this, a new nanocellulose–lignin aerogel (NLAG) was designed, in which nanocellulose was used as a substrate and lignin and polyamide epoxy chloropropane were used to crosslink cellulose in order to enhance the strength of the NLGA, resulting in good mechanical stability and water–oil amphiphilic properties. In practical applications, the organic membrane on the NLAG can transport organic pollutants from water to the NLAG, where they are immobilized. This is evidenced by the fact that the aerogel can remove more than 93% of exogenous phenol within a few minutes, highly enriching it inside. In addition, the aerogel facilitates filtration and shape recovery for reuse. This work establishes a novel biopolymer–aerogel-based extraction system with the advantages of sustainability, high efficiency, stability, and easy detachability, which are hard for the traditional adsorbent materials to attain. Full article

Carbon xerogels (CXs) are materials obtained via the pyrolysis of resins prepared via the sol–gel polycondensation of resorcinol and formaldehyde. These materials attract great attention as adsorbents, catalyst supports, and energy storage materials. One of the most interesting features of CXs is the possibility of fine-tuning their structures and textures by changing the synthesis conditions in the sol–gel stage. Thus, the first part of this review is devoted to the processes taking place in the polycondensation stage of organic precursors. The formation of hydroxymethyl derivatives of resorcinol and their polycondensation take place at this stage. Both of these processes are catalyzed by acids or bases. It is revealed that the sol–gel synthesis conditions, such as pH, the formaldehyde/resorcinol ratio, concentration, and the type of basic modifier, all affect the texture of the materials being prepared. The variation in these parameters allows one to obtain CXs with pore sizes ranging from 2–3 nm to 100–200 nm. The possibility of using other precursors for the preparation of organic aerogels is examined as well. For instance, if phenol is used instead of resorcinol, the capabilities of the sol–gel method become rather limited. At the same time, other phenolic compounds can be applied with great efficiency. The methods of gel drying and the pyrolysis conditions are also reviewed. Another important aspect analyzed within this review is the surface modification of CXs by introducing various functional groups and heteroatoms. It is shown that compounds containing nitrogen, sulfur, boron, or phosphorus can be introduced at the polycondensation stage to incorporate these elements into the gel structure. Thus, the highest surface amount of nitrogen (6–11 at%) was achieved in the case of the polycondensation of formaldehyde with melamine and hydroxyaniline. Finally, the methods of preparing metal-doped CXs are overviewed. Special attention is paid to the introduction of a metal precursor in the gelation step. The elements of the iron subgroup (Fe, Ni, Co) were found to catalyze carbon graphitization. Therefore, their introduction can be useful for enhancing the electrochemical properties of CXs. However, since the metal surface is often covered by carbon, such materials are poorly applicable to conventional catalytic processes. In summary, the applications of CXs and metal-doped CXs are briefly mentioned. Among the promising application areas, Li-ion batteries, supercapacitors, fuel cells, and adsorbents are of special interest. Full article

Geopolymers can be used as a thermally insulated material because of their considerable porosity, whereas the combined effect of various modifying agents on their heat-insulating properties remains unexplored. Here, orthogonal experiments were carried out to evaluate the thermal insulation performance of fly ash geopolymer modified by phenolic resin, silica aerogel, and hydrogen peroxide. Moreover, variance analysis and range analysis were applied to estimate the influence of modifying agents on the thermal insulation performance of the geopolymer. The results demonstrate that the thermal conductivity of fly ash geopolymer significantly reduces (from 0.48 W/m·K to 0.12 W/m·K) due to the combined effect of the three modifying agents. Based on the variance analysis and range analysis, the optimum thermal conductivity ultimately reaches 0.08 W/m·K via a best composition scheme of the three modifying agents. Moreover, phenolic resin can facilitate the formation of a network structure and increase the porosity of micron pores (>1 μm). Hydrogen peroxide can be decomposed into O₂ in an alkaline environment and leave large-diameter pores (>1 μm) during curing. Some silica aerogel is embedded in the geopolymer matrix as microspheres with extremely low thermal conductivity, whereas the rest of the silica aerogel may react with the alkali activator to form water, and subsequently leaves pores (>1 μm) after evaporation of water during the curing. In addition, a newly modified Maxwell–Euchen model using iterative calculation and considering the Knudsen effect (pores of micron or even nanometer scale) is proposed and validated by the experimental data. The foamed geopolymer in this research can be used as a reference for building insulation layer design. This research unravels phenolic resin-, silica aerogel-, and hydrogen peroxide-influenced thermal insulation mechanisms of geopolymer that may have impacts on deployment of a thermally insulating material in the construction field. Full article

This paper considers the synthesis of a novel nanocomposite based on reduced graphene oxide and oxidized carbon nanotubes modified with polyaniline and phenol-formaldehyde resin and developed through the carbonization of a pristine aerogel. It was tested as an efficient adsorbent to purify aquatic media from toxic Pb(II). Diagnostic assessment of the samples was carried out through X-ray diffractometry, Raman spectroscopy, thermogravimetry, scanning and transmission electron microscopy, and infrared spectroscopy. The carbonized aerogel was found to preserve the carbon framework structure. The sample porosity was estimated through nitrogen adsorption at 77 K. It was found that the carbonized aerogel predominantly represented a mesoporous material having a specific surface area of 315 m²/g. After carbonization, an increase in smaller micropores occurred. According to the electron images, the highly porous structure of the carbonized composite was preserved. The adsorption capacity of the carbonized material was studied for liquid-phase Pb(II) extraction in static mode. The experiment results showed that the maximum Pb(II) adsorption capacity of the carbonized aerogel was 185 mg/g (at pH 6.0). The results of the desorption studies showed a very low desorption rate (0.3%) at pH 6.5 and a rate of about 40% in a strongly acidic medium. Full article

The weak inherent non-covalent interactions between carbon aerogel backbone nanoparticles obtained by the pyrolysis of conventional organic aerogel can lead to poor mechanical properties. When applied in the thermal protection system of a high-speed spacecraft, the preparation of carbon aerogel insulation materials with excellent formability and high mechanical strength still remains a huge challenge. This work reports an efficient approach for fabricating carbon foam-reinforced carbon aerogel composites by compounding the nanoporous polyimide aerogel into the microporous pre-carbonized phenolic resin-based carbon foam via vacuum impregnation, gelatinizing and co-carbonization. Benefiting from the co-shrinkage caused by co−carbonization, the thermal insulation capacity of the carbon aerogel and the formability of the pre−carbonized foam are efficiently utilized. The shrinkage, density and carbon yield of aerogels, pre-carbonized foams and the composites at different temperatures were measured to analyze the formation of the interfacial gap within the composite. The co-carbonization mechanism of the polyimide aerogels and phenolic resin-based pre-carbonized foams was analyzed through XPS, TG-MS, and FT-IR. Among the prepared samples, CF30-CPI-1000 °C with small interfacial gaps showed the lowest thermal conductivity, which was as low as 0.56 W/(m·K) at 1900 °C, and the corresponding compressive strength and elastic modulus were as high as 0.532 MPa and 9.091 MPa, respectively. Full article

In materials research, the control of wettability is important for many applications. Since they are typically based on phenolics, organic aerogels, and xerogels are intrinsically hydrophilic in nature, and examples of the chemical functionalization of such gels are scarce and often limited to powders. This study reports on the silylation of monolithic resorcinol-formaldehyde (RF) xerogels using solutions of silyl chlorides and triflates, respectively, in combination with an amine base. The resulting gels are structurally characterized by means of elemental analysis, X-ray photoelectron spectroscopy, pycnometry, sorption analysis, and scanning electron microscopy with electron-dispersive X-ray spectroscopy. The wetting behavior of the silylated gels was studied by the determination of the contact angle to water after exposure of the gels to ambient air. Additionally, the uptake of liquid water and aqueous acids and bases was investigated. As a result, processes for the functionalization of RF xerogels with sterically demanding silyl moieties have been established. Although the analyses indicate that silylation occurred to a rather small extent, highly hydrophobic gels resulted which retained the wetting behavior over the course of several months with contact angles of >130°. Monoliths bearing sterically demanding silyl groups showed higher stability towards aqueous acid than trimethylsilylated RF gels. Full article

The production of novel materials and value-added chemicals from lignin has received considerable attention in recent years. Due to its abundant occurrence in nature, there is a growing interest in utilizing lignin as a feedstock for functional materials production, for example aerogels. Much like in the synthesis of phenol-based resins, the vacant ortho positions of the aromatic rings in lignin can crosslink with formaldehyde and form polymeric gels. After drying the hydrogels with supercritical CO₂, highly porous aerogels are obtained. Current study focuses on the preparation and thorough parametrization of organosolv lignins from different types of lignocellulosic biomass (aspen, pine, and barley straw) as well as their utilization for the preparation of lignin-5-methylresorcinol-formaldehyde aerogels. The thorough structural characterization of the obtained aerogels was carried out by gas adsorption, IR spectroscopy, and scanning electron microscopy. The obtained lignin-based monolithic mesoporous aerogels had specific surface areas and total pore volumes in the upward ranges of 450 m²/g and 1.4 cm³/g, respectively. Full article

Fenton reactions with metal complexes of substituted porphyrins and hydrogen peroxide are useful tools for the mineralization of environmentally dangerous substances. In the homogeneous phase, autooxidation of the prophyrin ring may also occur. Covalent binding of porphyrins to a solid support may increase the lifetime of the catalysts and might change its activity. In this study, highly water-insoluble copper and iron complexes of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin were synthesized and bonded covalently to a very hydrophilic silica aerogel matrix prepared by co-gelation of the propyl triethoxysilyl-functionalized porphyrin complex precursors with tetramethoxysilane, followed by a supercritical carbon dioxide drying. In contrast to the insoluble nature of the porphyrin complexes, the as-prepared aerogel catalysts were highly compatible with the aqueous phase. Their catalytic activities were tested in the mineralization reaction of phenol, 3-chlorophenol, and 2,4-dichlorophenol with hydrogen peroxide. The results show that both aerogels catalyzed the oxidation of phenol and chlorophenols to harmless short-chained carboxylic acids under neutral conditions. In batch experiments, and also in a miniature continuous-flow tubular reactor, the aerogel catalysts gradually reduced their activity, due to the slow oxidation of the porphyrin ring. However, the rate and extent of the degradation was moderate and did not exclude the possibility that the as-prepared catalysts, as well as their more stable derivatives, might find practical applications in environment protection. Full article