Bridged Polysilsesquioxane Xerogels Functionalizated by Amine- and Thiol- Groups: Synthesis, Structure, Adsorption Properties

Bridged polysilsesquioxane xerogels containing amine (–NH₂; –NH(CH₂)₂NH₂; —NH) and thiol (–SH) groups were synthesized by hydrolytic polycondensation of 1,2-bis(triethoxysilyl)ethane, 1,4-bis(triethoxysilyl)benzene and appropriate trifunctionalized silanes in the presence of a fluoride-ion catalyst in an ethanol solution. ²⁹Si CP/MAS NMR give indication of the molecular framework of these materials formed by structural T¹, T² and T³ units. 3-aminopropyl or 3-mercaptopropyl groups accessible to proton or metal ions are fixed to the xerogel surface by the siloxane bonds. IR and ¹³C CP/MAS NMR data clearly show that 3-aminopropyl groups form hydrogen bonds. The same data testify that all xerogels contain non-condensed silanol groups and some fraction of non-hydrolyzed ethoxygroups. Functionalized polysilsesquioxane xerogels obtained by means of organic spacers have a porous structure (500–1000 m²/g) and a high content of functional groups (1.0–2.7 mmol/g). AFM data indicate that xerogels are formed by aggregating primary particles—the size of such aggregates is in the range 30–65 nm. It was established that the main factors influencing the structure and adsorption properties considered hybrid materials are: the nature and geometrical size of the functional groups, spacer flexibility and, in some cases, the ratio of the reacting alkoxysilanes and the ageing time of the gel.     

铁掺杂的高比表面二氧化硅的制备及其苯酚降解性能

研究了以聚乙二醇为模板剂、正硅酸乙酯(TEOS)为硅源制备铁掺杂的多孔二氧化硅的方法。开发了一步完成多孔材料制备和掺杂的新工艺。研究了不同的铁元素掺杂量对样品性能的影响。采用低温氮吸附、SEM、FTIR、XRD方法表征了样品的比表面、孔结构和表面基团等信息。最优样品比表面大于700 m²·g^-1、孔容大于1 mL·g^-1。研究了所制备的多孔材料和双氧水共同降解水中苯酚的能力,研究发现负载铁的催化剂可以在很宽的pH值范围内(3~8)和双氧水协同使用,这可能是因为铁元素被牢固负载于多孔二氧化硅的骨架上,避免了其在高pH值下发生的水解反应。     

Large‐Scale Synthesis of MOF‐Derived Superporous Carbon Aerogels with Extraordinary Adsorption Capacity for Organic Solvents

Carbon aerogels (CAs) with 3D interconnected networks hold promise for application in areas such as pollutant treatment, energy storage, and electrocatalysis. In spite of this, it remains challenging to synthesize high‐performance CAs on a large scale in a simple and sustainable manner. We report an eco‐friendly method for the scalable synthesis of ultralight and superporous CAs by using cheap and widely available agarose (AG) biomass as the carbon precursor. Zeolitic imidazolate framework‐8 (ZIF‐8) with high porosity is introduced into the AG aerogels to increase the specific surface area and enable heteroatom doping. After pyrolysis under inert atmosphere, the ZIF‐8/AG‐derived nitrogen‐doped CAs show a highly interconnected porous mazelike structure with a low density of 24 mg cm^?3, a high specific surface area of 516 m² g^?1, and a large pore volume of 0.58 cm^?3 g^?1. The resulting CAs exhibit significant potential for application in the adsorption of organic pollutants.     

A magic angle spinning NMR study of xerogels functionalized by 3-mercaptopropyl groups

¹H magic angle spinning NMR spectroscopy was used to study xerogels containing the 3-mercaptopropyl group. These xerogels were synthesized using tetraethoxysilane, 1,2-bis(triethoxysilyl)ethane, and 1,4-bis(triethoxysilyl)benzene as structuring agents. The assignment of the NMR signals observed showed the presence of thiol groups introduced during syntheses and organic bridges in the frame of polysilsesquioxane samples. An analysis of the ¹H magic angle spinning NMR spectra also showed the presence of small amounts of alcohols, water participating in H-bonding, and nonhydrolyzed alkoxyl groups in the xerogels. In several instances, the structural units of T ⁿ and Q ^m types present in the xerogels were identified. The ¹H magic angle spinning NMR spectroscopy combined with ¹³C and ²⁹Si solid-state NMR spectroscopy allows the composition of xerogels and the nature of the structural units they contain to be identified more thoroughly and reliably.     

Synthesis of novel Schiff base doped sol–gel silicas

Sulfonamide Schiff bases were doped uniformly in silica sol–gels prepared from liquid precursors by a fast and easy way at room temperature and processed to form xerogels. Schiff bases are efficient chelating agents, bioactive and catalytically active compounds. The structures of the newly synthesized Schiff base doped xerogels were elucidated by their physical (morphology, surface area, porosity), spectral (FTIR) and analytical (CHNSO/Si) data. The powder X-ray diffraction studies were carried out to confirm the formation of single phase. Characterization confirmed that Schiff base molecules are entrapped inside the pores as well as physically bound onto the silica surface. All Schiff base doped xerogels are stable mesoporous materials showing hydrophilic properties. Loadings of Schiff bases from 0.10 to 0.23 g/g of xerogel were obtained resulting amorphous materials. The doping of Schiff bases with xerogel caused change in surface area, pore volume and pore diameter of xerogel without damaging the main framework of siliceous skeleton. Morphology and colour of xerogel was also changed after doping. The entrapment of Schiff bases in xerogel caused increase in their decomposition temperatures. The final Schiff base doped xerogels show remarkable thermal stability.     

Influence of the Er3+ Content on the Luminescence Properties and on the Structure of Er2O3-SiO2 Xerogels

Er₂O₃-SiO₂ xerogels doped with different Er/Si concentrations were annealed at 950°C for 120 h. The Er³⁺ doping level varied from 0 to 40000 Er/Si ppm. The effect of Er₂O₃ content on the sintering behavior of silica gels and on the luminescence properties was studied by Vis-NIR absorption, Raman and luminescence spectroscopies.     

Bithiazole-bridged polysilsesquioxane and its metal complexes: synthesis and magnetic properties

A novel alkoxysilylated derivative based on 2,2′-diamino-4,4′-bithiazole (DABTH) was firstly synthesized. The corresponding polysilsesquioxane (PBSIBTH) and its metal complexes (PBSIBTH-Eu³⁺, PBSIBTH-Tb³⁺ and PBSIBTH-Ni²⁺) were also obtained via sol–gel method, respectively. The morphology of their xerogels was investigated by scanning electron microscopy means. The magnetic measurements of these polymer complexes show all obtained solid materials feature soft ferromagnet properties at low temperature. The metal ions in polymer complexes have a significant influence on both microstructure and magnetic properties.     

Electron Paramagnetic Resonance and Differential Scanning Calorimetry Studies of Thorium and Tin Phosphate Xerogels

Different transparent phosphate xerogels were synthesized using concentrated solutions of metal chlorides and phosphoric acid with a proper mole ratio of both components. By this method we prepared bulk samples of thorium and tin(IV) phosphate xerogels by drying at room temperature or at 350 K. Some properties of these amorphous materials were studied by means of differential scanning calorimetry (DSC) and electron paramagnetic resonance (EPR) techniques. Depending on mole ratio metal/phosphate, these xerogels show, near 180 K, inflection points which we interpret asT _g . Samples dried at 425 K lose their transparency and have noT _g . Thus, it seems that the “glassy” state is due to water molecules remaining in the material. The same properties were confirmed by EPR studies of the xerogels doped with Cr³⁺ and Fe³⁺ ions as probes. These results show the existence of two different phases in the xerogels: a liquid-like one, in the range from 190 K to 350 K and a solid-like one, in the range from 4 K to 190 K.     

Raman Spectroscopic Investigations of the Effects of Ag+ and Ce3 + Doping on the Densification of Nanoporous Silica Xerogels

Doped and undoped 50 Å porous silica xerogels were heat-treated at various annealing temperatures ranging from 800°C to 1150°C. The heating was performed in air for 1 hour at each temperature. Raman spectroscopy was used to follow the structural changes occurring at various stages of the gel-to-glass transformation, as well as to investigate the effects of metal ions on the densification of these nanoporous silica xerogels. Raman data and density measurements showed that while densification is completely achieved at 1050°C for undoped xerogels, it occurs at 950°C for Ag⁺-doped samples. On the other hand, Ce^{3 +} doping was found to slow down the densification process, with complete densification occurring at 1100°C.     

Three‐Dimensional Nitrogen‐Doped Hierarchical Porous Carbon as an Electrode for High‐Performance Supercapacitors

A facile and sustainable procedure for the synthesis of nitrogen‐doped hierarchical porous carbons with a three‐dimensional interconnected framework (NHPC‐3D) was developed. The strategy, based on a colloidal crystal‐templating method, utilizes nitrogenous dopamine as the precursor due to its unique properties, including self‐polymerization under mild alkaline conditions, coating onto various surfaces, a high carbonization yield, and well‐preserved nitrogen doping after heat treatment. The obtained NHPC‐3D possesses a high surface area of 1056 m² g^?1, a large pore volume of 2.56 cm³ g^?1, and a high nitrogen content of 8.2 wt %. The NHPC‐3D is implemented as the electrode material of a supercapacitor and exhibits a specific capacitance as high as 252 F g^?1 at a current density of 2 A g^?1. The device also shows a high capacitance retention of 75.7 % at a higher current density of 20 A g^?1 in aqueous electrolyte due to a sufficient surface area for charge accommodation, reversible pseudocapacitance, and minimized ion‐transport resistance, as a result of the advantageous interconnected hierarchical porous texture. These results showcase NHPC‐3D as a promising candidate for electrode materials in supercapacitors.     

Xerogels doped with 1-(2-pyridylazo)-2-naphthol and Xylenol Orange: Indicator tubes and indicator powders for determining copper(II) and iron(III) in solution

Silica-based xerogels doped with l-(2-pyrilylazo)-2-naphthol and Xylenol Orange were prepared. The xerogels differ in the specific surface and the reagent concentration. Modified xerogels were used as indicator powders for determining copper(II) and iron(III) using indicator tubes. The effects of the reagent concentration in the indicator powder and its specific surface on the length of the colored zone were studied. Indicator tubes were developed for determining 0.3–300.0 mg/L copper(II) and 1.0–120.0 mg/L iron(III) in solutions. The results of determining copper(II) in plant mineral food and iron(III) in natural waters and ashed milk powder are presented.     

Electrical Conductivity and Physical Properties of Poly(Dipropargylsilane Derivatives) Doped with Electron Acceptors

Abstract

Films of poly(dipropargylsilane derivatives) were easily prepared by solvent casting. The resulting red-black films were relatively flexible and ductile. By doping with electron acceptors, the electrical conductivity increased up to the order of 10^?1-10⁰ S/cm. The activation energy for the conduction of doped film was 4 kcal/mol. The change in Raman, IR, and UV-visible spectra by doping suggests electron transfer from the poly(dipropargylsilane derivatives) to the dopant, leading to the formation of polaron. It also was observed that doping with I₂ drastically destroys the crystallinity of the polymer.     

Metal Microporous Aromatic Polymers with Improved Performance for Small Gas Storage

A novel metal‐doping strategy was developed for the construction of iron‐decorated microporous aromatic polymers with high small‐gas‐uptake capacities. Cost‐effective ferrocene‐functionalized microporous aromatic polymers (FMAPs) were constructed by a one‐step Friedel–Crafts reaction of ferrocene and s‐triazine monomers. The introduction of ferrocene endows the microporous polymers with a regular and homogenous dispersion of iron, which avoids the slow reunion that is usually encountered in previously reported metal‐doping procedures, permitting a strong interaction between the porous solid and guest gases. Compared to ferrocene‐free analogues, FMAP‐1, which has a moderate BET surface area, shows good gas‐adsorption capabilities for H₂ (1.75 wt % at 77 K/1.0 bar), CH₄ (5.5 wt % at 298 K/25.0 bar), and CO₂ (16.9 wt % at 273 K/1.0 bar), as well as a remarkably high ideal adsorbed solution theory CO₂/N₂ selectivity (107 v/v at 273 K/(0–1.0) bar), and high isosteric heats of adsorption of H₂ (16.9 kJ mol^?1) and CO₂ (41.6 kJ mol^?1).     

双金属(Sn/Ni)掺杂多孔硅微球的液相合成与电化学储锂性能

使用廉价的硅铝合金前驱体,通过简单的化学沉积方法制备了新型双金属(Sn/Ni)掺杂多孔硅微球(pSi@SnNi)。pSi@SnNi复合材料的三维多孔结构可以缓冲硅在锂化过程中的巨大体积膨胀,增加储锂活性位点。双金属(Sn/Ni)的掺杂可以提高硅的电子导电性,改进pSi的结构稳定性。由于其独特的组成和微观结构,具有适当Sn/Ni含量的pSi@SnNi复合材料显示了较大的可逆储锂容量(0.1 A·g^-1下为2 651.7 mAh·g^-1)、较高的电化学循环稳定性(1 A·g^-1下400次循环后为1 139 mAh·g^-1)和优异的倍率性能(2.5 A·g^-1下为1 235.8 mAh·g^-1)。     

Surface modification of malonic acid‐catalyzed carbon xerogels and their high performance for adsorption of Cu (II) ions

The preparation of malonic acid‐catalyzed carbon xerogels modified with nitric acid and their high performance for adsorption of Cu²⁺ were investigated. The treated and untreated carbon xerogels (nitrogen‐doped carbon xerogel and carbon xerogel) are mainly microporous with high surface areas (1150.18 and 1201.46 m² g^?1) based on the analysis of N₂ adsorption isotherm. Fourier transform infrared spectroscopy study demonstrates that modification process generates a number of functional groups such as carboxyl, carbonyl, and nitrate groups. X‐ray photoelectron spectra analysis shows an increase in the content of O and N after oxidation. The adsorption performance for Cu²⁺ using different process parameters like initial concentration, contact time, and temperature was investigated. The result indicates that the pseudo‐second order correlates with the experimental data, and the activation energy of Cu²⁺ adsorption onto nitrogen‐doped carbon xerogel and carbon xerogel is calculated as 15.62 kJ mol^?1 and 2.79 kJ mol^?1, respectively, indicating the coexistence of chemisorption and ion‐exchange. Langmuir and Freundlich isotherms were used to describe the adsorption behavior of Cu²⁺. The adsorption of Cu²⁺ by carbon xerogels modified with nitric acid was fast and had noticeable adsorption capacity, with a higher adsorption capacity than the original carbon xerogels (299.41 vs 260.42 mg g^?1). Copyright © 2013 John Wiley & Sons, Ltd.     

Photoluminescence Properties of Silica Xerogels Co‐doped with Eu3+ Ions and CdS Nanoparticles

Silica xerogels doped with Eu³⁺ ions and co‐doped with Eu³⁺ ions and CdS nanoparticles were prepared using a two‐step hydrolysis process. The effect of temperature on photoluminescence properties of Eu³⁺‐doped silica xerogel was investigated. The results showed that the photoluminescence of Eu³⁺‐doped silica xerogel was significantly dependent on the temperature of heat treatment. The study of the photoluminescence of co‐doped xerogels showed that the defect emission of silica was weakened due to competition among defects, CdS nanoparticles, and Eu³⁺ ions.     

Sodium‐Doped Mesoporous Ni2P2O7 Hexagonal Tablets for High‐Performance Flexible All‐Solid‐State Hybrid Supercapacitors

A simple hydrothermal method has been developed to prepare hexagonal tablet precursors, which are then transformed into porous sodium‐doped Ni₂P₂O₇ hexagonal tablets by a simple calcination method. The obtained samples were evaluated as electrode materials for supercapacitors. Electrochemical measurements show that the electrode based on the porous sodium‐doped Ni₂P₂O₇ hexagonal tablets exhibits a specific capacitance of 557.7 F g^?1 at a current density of 1.2 A g^?1. Furthermore, the porous sodium‐doped Ni₂P₂O₇ hexagonal tablets were successfully used to construct flexible solid‐state hybrid supercapacitors. The device is highly flexible and achieves a maximum energy density of 23.4 Wh kg^?1 and a good cycling stability after 5000 cycles, which confirms that the porous sodium‐doped Ni₂P₂O₇ hexagonal tablets are promising active materials for flexible supercapacitors.     

Controllable Sulfur,Nitrogen Co‐doped Porous Carbon for Ethylbenzene Oxidation: The Role of Nano‐CaCO3

Heteroatom‐doped porous carbon materials have exhibited promising applications in various fields. In this work, sulfur, nitrogen co‐doped carbon materials (SNCs) with abundant pore structure were prepared by pyrolysis of sulfur, nitrogen‐containing porous organic polymers (POPs) mixed with nano‐CaCO₃ at high temperature. Among the resultant materials, SNC‐Ca‐850 possesses a relatively high level of doped heteroatoms and exhibits an excellent catalytic performance for the selective oxidation of benzylic C?H bonds. It is noteworthy that nano‐CaCO₃ increases the doped sulfur content in the synthesized carbon materials to a large extent and impacts the existence modes of sulfur. In addition, it enhances the porous structure and specific surface area of the resultant SNCs significantly. This work provides a viable strategy to promote the doping of sulfur into carbon materials during the pyrolysis process.     

Reduction of Cu2+ to Cu+ in Xerogels Prepared from (3-Aminopropyl)Trimethoxysilane

Silica gels doped with Cu²⁺ ions were prepared from the (3-aminopropyl) trimethoxysilane (APTMOS)/tetraethoxysilane (TEOS) systems. Sols showed a broad absorption peak at 640 nm, suggesting 3–5 coordination of the aminopropyl groups to Cu²⁺. For gels prepared from APTMOS and dried at room temperature, the 640 nm peak decreased and a red-shifted absorption appeared below 400 nm within a few months. The luminescence spectra of the xerogels showed emission bands at 430–470 and 510 nm. The former and latter bands are ascribed to Cu⁺ monomer and dimer emissions, respectively. These results indicate that Cu²⁺ ions are reduced to Cu⁺. When xerogels were prepared from APTMOS/TEOS = 1 (vol/vol), the color of xerogels was blue with an absorption peak at around 670 nm, indicating no reduction of Cu²⁺ ions.     

双金属(Sn/Ni)掺杂多孔硅微球的液相合成与电化学储锂性能

使用廉价的硅铝合金前驱体,通过简单的化学沉积方法制备了新型双金属(Sn/Ni)掺杂多孔硅微球(pSi@SnNi)。pSi@SnNi复合材料的三维多孔结构可以缓冲硅在锂化过程中的巨大体积膨胀,增加储锂活性位点。双金属(Sn/Ni)的掺杂可以提高硅的电子导电性,改进pSi的结构稳定性。由于其独特的组成和微观结构,具有适当Sn/Ni含量的pSi@SnNi复合材料显示了较大的可逆储锂容量(0.1 A·g^-1下为2 651.7 mAh·g^-1)、较高的电化学循环稳定性(1 A·g^-1下400次循环后为1 139 mAh·g^-1)和优异的倍率性能(2.5 A·g^-1下为1 235.8 mAh·g^-1)。