Polymer‐derived ceramic adsorbent for pollutant removal from water

Polymer‐derived ceramic components (SiOC, sample W) were produced from preceramic polymer mixture and a catalyst. After curing and pyrolysis, some of the samples etched by hydrofluoric acid to obtain carbonaceous SiOC (C‐rich SiOC, sample W‐HF). W and W‐HF were tested as an adsorbent material to remove both heavy‐metal ions (Cr (III), Pb (III), and Cd (II)) and cationic dyes (Methylene Blue (MB), Rhodamine B (RB), and Crystal Violet (CV)) from aqueous solutions. HF‐treated high surface area SiOC samples had quite high adsorption affinity for cationic dyes. According the Langmuir isotherm model the maximum dye uptake values were found to be around to 50 mg/g for sample W, whereas those for sample W‐HF ranged from 104 to 186 mg/g. Regeneration studies were conducted both by heat treatment and leaching, high recovery yields (always above 97%) of MB adsorption were obtained.     

Structural Design of Polymer‐Derived SiOC Ceramic Aerogels for High‐Rate Li Ion Storage Applications

SiOC ceramic aerogels with different porosity, pore size, and specific surface area have been synthesized through the polymer‐derived ceramic route by modifying the synthesis parameters and the pyrolysis steps. Preceramic aerogels are prepared by cross‐linking a linear polysiloxane with divinylbenzene (DVB) via hydrosilylation reaction in the presence of a Pt catalyst under highly diluted conditions. Acetone and cyclohexane are used as solvent in our study. Wet gels are subsequently supercritically dried with CO₂ to get the final preceramic aerogels. The SiOC ceramic aerogels are obtained after a pyrolysis treatment at 900°C in two different atmospheres: pure Ar and H₂ (3%)/Ar mixtures. The nature of the solvent has a profound influence of the aerogel microstructure in terms of porosity, pore size, and specific surface area. Synthesized SiOC ceramic aerogels have similar chemical compositions irrespective of processing conditions with ~40 wt% of free carbon distributed within remaining mixed SiOC matrix. The BET surface areas range from 215 m²/g for acetone samples to 80 m²/g for samples derived from cyclohexane solvent. The electrochemical characterization reveals a high specific reversible capacity of more than 900 mAh/g at a charging rate of C (360 mA/g) along with a good cycling stability. Samples pyrolyzed in H₂/Ar atmosphere show a high reversible capacity of 200 mAh/g even at a high charging/discharging rate of 20 C. Initial capacities were recovered after whole cycling procedure indicating their structural stabilities resisting any kind of exfoliations.     

Flash pyrolysis of polymer-derived SiOC ceramics

For the first time, flash pyrolysis was carried out to fabricate polymer derived silicon oxycarbide (SiOC) ceramics. With the application of a DC electric field at a furnace temperature of only 780?°C, the SiOC ceramics exhibit characteristics that usually have to be pyrolyzed at ～1300?°C. Both electric field and current density accelerate the SiOC microstructure development, causing carbon and SiC phases to form at >520?°C lower pyrolysis temperatures than conventional within the SiOC matrix. With higher electric fields, the samples experience greater mass loss and linear shrinkage, while also forming more SiC and a more ordered carbon phase. The SiC formation inversely impacts the carbon content, causing a decrease in electrical conductivity. Further, reducing current density results in significant carbon precipitation without SiC formation. The fundamentals can be explained based on increased nucleation rate by the electrical field, accompanied by Joule heating and electromigration. This work is the first to demonstrate the great potential of flash pyrolysis on accelerated phase separation of polymer derived SiOC.     

High‐Temperature Creep Behavior of Dense SiOC‐Based Ceramic Nanocomposites: Microstructural and Phase Composition Effects

In this work, dense monolithic polymer‐derived ceramic nanocomposites (SiOC, SiZrOC, and SiHfOC) were synthesized via hot‐pressing techniques and were evaluated with respect to their compression creep behavior at temperatures beyond 1000°C. The creep rates, stress exponents as well as activation energies were determined. The high‐temperature creep in all materials has been shown to rely on viscous flow. In the quaternary materials (i.e., SiZrOC and SiHfOC), higher creep rates and activation energies were determined as compared to those of monolithic SiOC. The increase in the creep rates upon modification of SiOC with Zr/Hf relies on the significant decrease in the volume fraction of segregated carbon; whereas the increase of the activation energies corresponds to an increase of the size of the silica nanodomains upon Zr/Hf modification. Within this context, a model is proposed, which correlates the phase composition as well as network architecture of the investigated samples with their creep behavior and agrees well with the experimentally determined data.     

Synthesis and characterization of monolithic carbon/silicon carbide composite aerogels

Resorcinol–formaldehyde/silica composite (RF/SiO₂) aerogels were synthesized using sol–gel process followed by supercritical CO₂ drying. Monolithic carbon/silicon carbide composite (C/SiC) aerogels were formed from RF/SiO₂ aerogels after carbothermal reduction. X-ray diffraction and transmission electron microscopy demonstrate that β-SiC was obtained after carbothermal reduction. Scanning electron microscopy and nitrogen adsorption/desorption reveal that the as-prepared C/SiC aerogels are typical mesoporous materials. The pore structural properties were measured by nitrogen adsorption/desorption analysis. The resulting C/SiC aerogels possess a BET surface area of 564 m²/g, a porosity of 95.1 % and a pore volume of 2.59 cm³/g. The mass fraction of SiC in C/SiC aerogels is 31 %.     

Synthesis of resorcinol-formaldehyde/silica composite aerogels and their low-temperature conversion to mesoporous silicon carbide

Resorcinol-formaldehyde/silica composite (RF/SiO₂) gels were acid-catalyzed formed in one pot at 27 °C within 60 min, and then dried to aerogels with supercritical fluid CO₂. After carbonization in nitrogen atmosphere and a magnesiothermic reaction at 700 °C, RF/SiO₂ aerogels were successfully converted to monolithic mesoporous silicon carbide (SiC aerogels). The starting RF/SiO₂ aerogels had an interpenetrating organic/inorganic network and the resulting SiC products preserved monolithic mesoporous morphology similar to the original templates. The as-synthesized SiC aerogels consisted of nanocrystalline β-SiC, possessed a BET surface area of 232 m²/g and showed sufficient mesoporosity. They had a direct band gap of about 3.2 eV (less than that of bulk β-SiC) and showed photoluminescence at room temperature. The mechanisms about the formation of RF/SiO₂ gels and the conversion to SiC aerogels were discussed. Potentially, the reported method can be used to convert many metal or semimetal oxide/carbon composite aerogels to carbide aerogels at relatively low temperature for many catalytic, electronic, photonic and thermal applications.     

Synthesis of monolithic SiC aerogels with high mechanical strength and low thermal conductivity

The monolithic silicon carbide (SiC) aerogels were converted from catechol-formaldehyde/silicon composite (CF/SiO₂) aerogels through carbothermal reduction and calcination. In the process of preparing the CF/SiO₂ aerogel, a new method was proposed to produce more silicon carbide and enhanced the mechanical properties of the SiC aerogel. This method was realized by adding an alkaline silica sol as supplemental silicon source. The principle process of CF/SiO₂ aerogels converting to SiC aerogels was discussed based on experiment and results analysis, while the microstructure, mechanical properties, and thermal properties of the prepared SiC aerogels were investigated. The results show that the as-synthesized SiC aerogels consist of β-SiC and a small amount of α-SiC nanocrystalline. It possessed a mesoporous structure and a low thermal conductivity 0.049 W/(m∙K), a relatively high compressive strength 1.32 MPa, and a relatively high specific surface area 162 m²/g. Due to their outstanding thermal and mechanical properties, the prepared SiC aerogels present potential applications in thermal insulation field, such as space shuttles and aerospace carrier thermal protection materials.     

Morphological features of porous silicon carbide obtained via a carbothermal method

Samples of porous silicon carbide were obtained using sucrose or carbon and aerosil or silica mesoporous molecular sieves (SBA‐3, SBA‐15, KIT‐6 and MCF). Fibers content in silicon carbide samples is higher when the mesopore surface area of carbon materials derived from carbon‐silica composites is lower. Based on the found correlation between the morphology and porosity of SiC and mesopore surface area of the carbon component in the composites, a templating action of carbon in carbothermal reduction was suggested.     

Low-temperature thermal energy storage with polymer-derived ceramic aerogels

Thermal energy storage (TES) with phase change materials (PCMs) presents some advantages when shape-stabilization is performed with ceramic aerogels. These low-density and ultra-porous materials guarantee high energy density and can be easily regenerated through simple pyrolysis while accounting for moderate mechanical properties. However, the small pore size that typically characterizes these sorbents can hinder the crystallization of PCMs, slightly reducing the energy density of the stabilized compound. In this work, we present the use of polymer-derived mesoporous SiC and SiOC aerogels for the stabilization of polyethylene glycol and a fatty alcohol (PureTemp 23), having a melting temperature of 17 and 23°C, respectively. Their TES performances point out maximum thermal efficiency values of around 80%. These performances are discussed accounting for the results of thermogravimetric analysis, differential scanning calorimetry, and leaking tests.     

Growth of SiOC/SiC nanostructures from cured polysiloxane-silica composite

SiOC/SiC nanostructures were produced by the pyrolysis of silica reinforced silicone polymer cured through platinum catalyzed hydrosilylation route. The base polymers used were vinyl terminated poly(dimethyl-co-diphenyl) siloxane (V-PMPS) and trimethylsilyl terminated poly(dimethyl-co-diphenyl-co-methyl hydrogen) siloxane (TMS-PMPHS). While TMS-PMPHS was synthesised from non-halogenated precursors by acid catalyzed ring opening/co-condensation approach, V-PMPS was used as received. The cured polymers were characterised for their spectral and thermal properties. Incorporation of silica filler to V-PDMS resulted in composite with higher onset of decomposition temperature compared to the unfilled counterpart. Pyrolysis of the filled polymer was carried out at different temperatures and the products were analysed by FTIR, Raman spectroscopy, XRD, FESEM and EDAX. It was found that one dimensional ceramic nanostructures are produced from the silica filled composite at lower temperature of 900 °C compared to the unfilled system. The size of the nanostructures increased with increase in the pyrolysis temperature.     

Fabrication and properties of lightweight SiOC fiber-based assembly aerogels with hierarchical pore structure

Here we report a novel aerogel material assembled by the electrospun SiOC fibers with a hierarchical pore structure. The fibrous aerogels were successfully fabricated by the gel-casting and freeze-drying method using the SiOC fibers as the matrix and the silica sols as the binders. The effect of the SiOC fiber content and the silica sol content on the properties of the samples were investigated. The SiOC fibrous aerogels after calcined at 1000?°C exhibited low densities of 46.87–128.48?mg/cm³, low thermal conductivities of 0.0302–0.0440?W/m?K, high compressive strengths of 18–167?kPa and relatively high specific surface areas of 12.48–34.87?m²/g. Such unique fibrous aerogel materials are foreseen as the promising high-temperature insulators, absorbents and supports.     

Photocatalytic degradation of methanol on titania and titania–silica aerogels prepared by non-alkoxide sol–gel route

Titania and titania–silica aerogels were prepared by alkoxide or non-alkoxide sol–gel route and subsequent supercritical drying with carbon dioxide at low temperature. The resulting aerogels having high surface area and mesoporosity were used as photocatalysts for gas phase methanol degradation reaction. Photocatalytic degradation reactions were carried out on titania and titania–silica aerogels, and commercial Degussa P-25 titania. The photocatalytic activities of titania and titania–silica aerogels were higher than that of the P-25. While the conversion of methanol degradation over the P-25 catalyst was only 50–60%, that for the titania aerogel was observed to be above 98% due to the higher specific surface area and the well developed mesoporous structure. In spite of lower titania contents, much higher surface area and high dispersion of titania of titania–silica aerogel gave rise to the high photocatalytic activity in comparison to those of titania aerogels. Moreover, titania–silica aerogel was also used for the photodegradation and adsorption hybrid system. It was observed that the high removal efficiency for methanol was caused by the combination of higher catalytic activity and adsorption capacity.     

Macroporous polymer-derived SiO2/SiOC monoliths freeze-cast from polysiloxane and amorphous silica derived from rice husk

A freeze-casting route towards macroporous SiOC/SiO₂ ceramic nanocomposites from preceramic polymers was developed. Amorphous SiOC/SiO₂ monolith with pore channels aligned along the freezing direction were obtained from commercially available methyl-phenyl-vinyl-hydrogen polysiloxane (Silres® H62C) and amorphous silica derived from rice husk ash freeze-cast with water or tert-butyl alcohol, crosslinked and pyrolyzed at 1100 °C in nitrogen. The influence of processing parameters such as solvent (tert-butyl alcohol or water), polymer to silica ratio (2:1, 1:1, 1:2), cooling rate (2, 4, 6 °C/min) and pre-crosslinking of polysiloxane on the porosity and structure of the obtained ceramic nanocomposites were assessed by X-ray tomography, XRD, solid state NMR, scanning electron microscopy and mercury porosimetry. The microstructure of SiOC ceramics derived from the Silres H62C polysiloxane was studied as well.     

热处理对粉煤灰酸渣基二氧化硅气凝胶结构和疏水性的影响

粉煤灰酸渣是粉煤灰经酸溶提铝后的副产品,主要化学成分为无定形二氧化硅,其资源化利用不仅解决了粉煤灰酸渣堆存带来的环境问题,还能获得附加值较高的二氧化硅气凝胶。以粉煤灰酸渣制备的水玻璃为原料,通过溶胶-凝胶—溶剂交换/表面改性—常压干燥工艺成功制备了低密度（0.083 g/cm³）、高比表面积（708 m²/g）、高疏水性（接触角为143°）的多孔二氧化硅气凝胶。通过热重-差热分析、红外光谱分析、接触角测试、扫描电镜分析、氮气吸附-脱附测试等手段对热处理前后二氧化硅气凝胶的结构和疏水性进行了表征。结果表明,随着热处理温度升高,二氧化硅气凝胶的比表面积增大、疏水性逐渐减弱直至消失。300 ℃热处理后,二氧化硅气凝胶仍具有较强的疏水性（接触角约为128°）,密度为0.080 g/cm³。当热处温度为400~600 ℃时,二氧化硅气凝胶仍具有中孔结构,由疏水性变为亲水性,密度从0.073 g/cm³增加到0.078 g/cm³。     

The influence of preparation method on the physicochemical properties of titania–silica aerogels: Part two

Titania–silica aerogels with different titania content were prepared. Four preparation methods differing mainly in approach to precursors hydrolysis were applied, while only three of them allowed total hydrolysis of silica precursor before titania precursor was added. The preparation of mixed products of titania and silica hydrolysis precursors containing gels was followed by high temperature supercritical drying (HTSCD) and thermal treatment at 500 °C. Obtained mixed oxides in form of aerogels were characterized by BET surface areas up to 1000 m²/g, mesopore volumes up to 1.6 cm³/g and bulk densities as low as 0.04 g/cm³. Even 18 h lasting aging did not allow to produce narrow diameter range mesoporous materials, their broad pore diameter distributions resulted in average pore sizes varying from 10 to nearly 30 nm. XRD measurements proved the presence of anatase crystalline form of titania, while silica was present in amorphous form. SEM studies indicated presence of isolated titania particles on titania–silica surface while joint hydrolysis method was applied. Titania–silica aerogels obtained by the simultaneous hydrolysis of precursors and the impregnation method showed high photocatalytic activity in degradation of salicylic acid in water. Activities of these mesoporous photocatalysts were higher than commercial P25 Degussa TiO₂. Comparison of activity of pure TiO₂ (P25 Degussa) and aerogels indicates higher utilization of titania present in mesoporous mixed oxides.     

Synthesis of an ordered mesoporous carbon with graphitic characteristics and its application for dye adsorption

An ordered mesoporous carbon (OMC) was prepared by a chemical vapor deposition technique using liquid petroleum gas (LPG) as the carbon source. During synthesis, LPG was effectively adsorbed in the ordered mesopores of SBA-15 silica and converted to a graphitic carbon at 800 °C. X-ray diffraction and nitrogen adsorption/desorption data and high-resolution transmission electron microscopy (HRTEM) of the OMC confirmed its ordered mesoporous structure. The OMC was utilized as an adsorbent in the removal of dyes from aqueous solution. A commercial powder activated carbon (AC) was also investigated to obtain comparative data. The efficiency of the OMC for dye adsorption was tested using acidic dye acid orange 8 (AO8) and basic dyes methylene blue (MB) and rhodamine B (RB). The results show that adsorption was affected by the molecular size of the dye, the textural properties of carbon adsorbent and surface-dye interactions. The adsorption capacities of the OMC for acid orange 8 (AO8), methylene blue (MB) and rhodamine B (RB) were determined to be 222, 833, and 233 mg/g, respectively. The adsorption capacities of the AC for AO8, MB, and RB were determined to be 141, 313, and 185 mg/g, respectively. The OMC demonstrated to be an excellent adsorbent for the removal of MB from wastewater.     

Low‐Temperature Synthesis of Mesoporous SiC Hollow Spheres by Magnesiothermic Reduction

Mesoporous silicon carbide hollow spheres (SiC‐HS) with a large specific surface area (690.2 m² g^?1) are synthesized at a relatively low temperature of 650°C by magnesiothermic reduction using the template of carbon‐coated mesoporous silica hollow spheres and molten salt as the heat absorbent and solvent. The mesoporous SiC‐HS comprising many small primary crystals (2–4 nm) with a well‐maintained microstructure have good thermal stability and adsorption ability, and are promising as adsorbents to remove organic pollution from water. The synthesis technique can be extended to other nanostructured carbide ceramic materials.     

Optimization of Alumina and Aluminosilicate Aerogel Structure for High-Temperature Performance

Alumina and aluminosilicate aerogels offer potential for use at temperatures above 700°C, where silica aerogels begin to sinter. Stability of alumina and aluminosilicate pore structures at high temperatures is governed by the starting aerogel structure, which, in turn is controlled by the synthesis route. Structure, morphology, and crystallization behavior are compared for aerogels synthesized from AlCl₃ and propylene oxide with those synthesized from a variety of boehmite precursors. The aerogels possessing a crystalline boehmite structure in the as-synthesized condition retained mesoporous structures to temperatures of 1200°C, while the AlCl₃-derived aerogels, although exhibiting higher as-synthesized surface areas, crystallized and densified at 980–1005°C.     

Stereolithography-based additive manufacturing of polymer-derived SiOC/SiC ceramic composites

In order to overcome challenges typically encountered during additive manufacturing of ceramics via the polymer precursor route, a novel polymer-derived SiOC/SiC composite system suitable for advanced geometric designs achievable by lithography-based ceramic manufacturing was established. The photoreactive resin system filled with 20 wt% SiC exhibits suitable viscosity characteristics, adequate stability against sedimentation, and a fast photocuring behavior. After printing and pyrolytic conversion, SiC particulates were well-dispersed within the polymer-derived SiOC matrix. A direct comparison with the unfilled polysiloxane-based resin system showed that the addition of particulate SiC increases handleability, reduces shrinkage, and significantly increases critical wall thicknesses up to 5 mm. The biaxial Ball-on-Three-Balls testing methodology yielded a characteristic strength of 325 MPa for SiOC/SiC composites. The results highlight the high potential of particle-filled preceramic polymer systems toward the fabrication of high-performance SiC-based materials by lithography-based additive manufacturing.     

In-situ TEM study of Kr ion irradiation tolerance of SiFeOC nanocomposite

In this work, ion irradiation of polymer derived SiFeOC nanocomposite was carried out using 1.2 MeV Kr ions at room temperature and 600°C. The starting composite was composed of Fe₃Si, SiC, SiOC, SiO₂, and graphitic C. In-situ TEM investigations show uniform distribution of nano-crystalline Fe₃Si and SiC phases in the amorphous SiOC matrix. During ion irradiation, the SiOC bulk microstructure and interfaces between Fe₃Si or SiC crystallites and the SiOC matrix remain defect-free and demonstrate outstanding ion irradiation resistance. At room temperature, the crystalline domains are stable up to 2 dpa. At 600°C, Fe₃Si crystallites are more stable than SiC; SiC crystallites are stable up to 4 dpa while the Fe₃Si crystallites are stable up to 10 dpa. These crystallites also coalescence and amorphize simultaneously during ion irradiation. The exceptional tolerance to defect formation and irradiation of the SiFeOC nanocomposite provides important guidance to developing irradiation resistant fuels for advanced gas cooled reactors.