溶胶-凝胶伴随相分离制备SiO2多孔块体

以正硅酸甲酯(TMOS)为前驱体, 0.01 mol·L^-1盐酸(HCl)为催化剂, 环氧丙烷(PO)为凝胶促进剂, 粘均分子量(M_v)为10000的聚氧化乙烯(PEO)为相分离诱导剂, 采用溶胶-凝胶伴随相分离制备SiO₂多孔块体材料,利用差热分析(DTA)、傅里叶变换红外(FT-IR)光谱、扫描电镜(SEM)、X射线衍射(XRD)、汞压、N₂吸附/脱附等测试技术对所制得的SiO₂多孔块体进行了表征, 探讨了环氧化物调控溶胶-凝胶以及PEO诱导相分离机理. 结果表明, 加入PEO能诱导SiO₂凝胶发生相分离, 当PEO/TMOS摩尔比为0.0018时, 可以获得共连续多孔结构的SiO₂块体材料, 其大孔孔径分布在1-3 μm之间, 比表面积达719 m²·g^-1, 孔体积为0.48 m³·g^-1. 环氧丙烷因其环氧原子的强亲核性和不可逆的开环反应, 促进溶胶-凝胶转换, 同时借助吸附在SiO₂低聚物上的PEO诱导SiO₂凝胶相分离, 从而制备共连续大孔及骨架结构的多孔块体.     

自生纳米纤维增强SiO2气凝胶的制备及性能研究

采用溶胶-凝胶法和乙醇超临界干燥工艺制备ZrO_X/SiO₂复合气凝胶,再经1200℃高温热处理得到自生纳米纤维增强SiO₂复合气凝胶。利用扫描电子显微镜、透射电子显微镜、X射线衍射、热重和氮气吸附等手段对气凝胶的结构和性能进行了分析,并且测试了样品的压缩强度及真密度。实验结果表明：自生纳米纤维增强SiO₂复合气凝胶具有均匀的多孔网络结构,锆氧纳米纤维是以化学键连接复合的方式无序穿插在气凝胶中,对复合气凝胶的机械强度和隔热性能有明显的改善。经1200℃热处理后的ZrO_X/SiO₂复合气凝胶比表面积为827.22m₂·g^-1,压缩强度为9.68MPa,真密度为0.23g·cm^-3。     

添加三甲基乙氧基硅烷制备耐高温硅/铝复合气凝胶

以仲丁醇铝(ASB)和三甲基乙氧基硅烷(TMEO)为前驱体,采用溶胶-凝胶法,经乙醇超临界干燥制备了耐温高、成型性好的硅/铝复合气凝胶。用透射电子显微镜、N₂吸附分析仪、红外光谱仪、X射线衍射仪、hot disk热分析仪等仪器表征了气凝胶的形貌、孔结构、表面基团、晶相、热学等性能。在溶胶-凝胶过程中,通过添加TMEO在氧化铝纳米颗粒表面引入了-Si-(CH₃)₃基团,该基团经高温热处理后会在Al₂O₃表面形成SiO₂纳米颗粒,有效地抑制了Al₂O₃纳米颗粒在高温下的晶体生长,使得该复合气凝胶具有优异的耐温性能。在1 200 ℃高温处理后,线性收缩低至16%,比表面积可达141 m²·g^-1,这将进一步促进气凝胶材料在高温保温隔热、吸附、催化等领域的广泛应用。     

太阳光下高光催化活性Pr-N-P三元掺杂锐钛矿TiO2纳米片

利用溶胶-凝胶和溶剂热联合技术制备了Pr-N-P三元掺杂锐钛矿TiO₂（PrNPTO）纳米片,并采用X射线衍射、透射电镜、N₂吸附、X射线光电子能谱、UV-vis吸收谱和光致荧光光谱分析技术对其进行了表征.当Pr掺杂量为1.75wt%,焙烧温度为550℃时,制得的PrNPTO在可见和紫外光下光催化降解亚甲基蓝（MB）活性最佳.在模拟太阳光照射下,PrNPTO也表现出优越的光催化降解4-氯酚性能（k_app=3.90×10^-2min^-1）,优于未掺杂、单掺杂和双掺杂TiO₂样品,其光活性是P25TiO₂的3.33倍（k_app=1.17×10^-2min^-1）.PrNPTO光活性的提高归因于Pr-N-P三元掺杂增强了紫外和可见光吸收,降低了光生载流子复合,增加了表面羟基以及改善了表面织构特性.在模拟太阳光照射下,PrNPTO光催化效率高且光催化性能稳定,适合于环境净化领域的实际应用.     

混合溶剂对溶胶-凝胶法制备的Li3V2(PO4)3/C高倍率性能的影响

以有机-水为混合溶剂, 采用溶胶-凝胶法制备锂离子电池正极材料Li₃V₂(PO₄)₃/C, 选取乙醇、乙二醇和1,2-丙二醇为有机溶剂, 聚丙烯酸(PAA)为碳源和螯合剂. 通过X射线衍射(XRD)、扫描电镜(SEM)、恒流充放电以及循环伏安测试等方法, 研究了产物的结构形貌及电化学性能. XRD测试结果表明所有溶剂制备的样品结晶良好, 有机溶剂的加入不影响Li₃V₂(PO₄)₃材料的晶型结构. 恒流充放电结果表明有机溶剂的加入改善了材料的电化学性能. 以1,2-丙二醇-水为溶剂的样品电化学性能最好, 在3.0-4.5 V电压范围内, 0.1C (1C=150 mA·g^-1)倍率首次放电比容量为132.89 mAh·g^-1, 10C倍率首次放电比容量达125.42 mAh·g^-1, 循环700周后容量保持率为95.79%, 具有良好的倍率性能与循环性能; 在3.0-4.8 V电压范围内倍率性能较差. 扫描电镜结果表明混合溶剂制备的样品呈片状和针状, 这种形状有利于锂离子的扩散, 因此提高了材料的电化学性能.     

介孔SiO2气凝胶的常压干燥制备研究

以廉价的水玻璃为硅源，用乙醇(EtOH) / 三甲基氯硅烷(TMCS) / 庚烷(Heptane)溶液对湿凝胶进行改性，采用一种新的常压干燥工艺合成了SiO₂气凝胶。通过TMCS与乙醇、湿凝胶孔隙水及Si-OH基团之间的反应，使湿凝胶的溶剂交换和表面改性得以在一步完成。所合成的SiO₂气凝胶为轻质透明的块状固体，密度为0.128～0.136 g·cm^-3，孔隙率93.8%～94.2%。利用FTIR、SEM、TEM和BET吸附对气凝胶的微观结构、形貌和性质进行了研究。结果表明，气凝胶为海绵状结构，粒子直径和孔径分布均匀，比表面积559～618 m²·g^-1，表面带有较多的Si-CH₃基团，呈现出明显的疏水性。     

Cu掺杂TiO2及其纳米管的制备、表征与光催化性能

通过溶胶-凝胶法和水热法制备了Cu掺杂TiO₂纳米粉末及其纳米管,并通过XRD、TEM、FE-SEM、EDS、UV-Vis/DRS等手段分析了样品的结构。发现以Cu掺杂TiO₂纳米粉末为水热反应原料制备的纳米管中不含Cu,对其原因进行了分析讨论并通过Zn掺杂TiO₂纳米粉末证实：以金属掺杂TiO₂纳米粉末为原料,通过水热法制备TiO₂纳米管中不含有相应金属离子,这是由于金属离子在强碱水热条件下形成金属配离子,使金属离子溶解于水中而不能形成金属掺杂TiO₂纳米管。对所得样品进行了光催化性能测试,发现：Cu掺杂TiO₂粉末的光催化产氢效率为0.75 μmol·(g·h)^-1,高于由其本身及P25通过水热法制备的TiO₂纳米管(分别为：0.42 μmol·(g·h)^-1,0.25 μmol·(g·h)^-1)的光催化产氢效率。     

溶剂热法制备Ag/TiO2纳米材料及其光催化性能

以乙醇为溶剂, 钛酸四丁酯为前驱体, 用溶剂热法制备了Ag表面修饰的负载型纳米二氧化钛光催化剂. 利用X射线衍射(XRD)、N₂吸附-脱附(BET)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、紫外-可见(UV-Vis)光谱等技术对其进行了系统的表征, 以亚甲基蓝(MB)溶液的脱色降解为模型反应, 考察了不同Ag含量样品的光催化性能. 结果表明: 用溶剂热法制备的样品中TiO₂皆为锐钛矿相, 金属Ag颗粒沉积在TiO₂表面, 粒径为2 nm左右, 比表面积较溶胶凝胶法制备的样品大大增加, 最高可达151.44 m²·g^-1; UV-Vis光谱和光催化实验表明: Ag修饰使TiO₂对光的吸收能力大大增强, 吸收带边红移至可见光区, 亚甲基蓝在该复合材料上的光催化降解反应遵循一级反应动力学模型; 溶剂热法制备样品的光催化性能明显好于溶胶凝胶法制备的样品, 在紫外光和可见光下, Ag摩尔分数为5%的样品表现出最佳的光催化活性.     

溶剂热法制备Ag/TiO2纳米材料及其光催化性能

以乙醇为溶剂, 钛酸四丁酯为前驱体, 用溶剂热法制备了Ag表面修饰的负载型纳米二氧化钛光催化剂. 利用X射线衍射(XRD)、N₂吸附-脱附(BET)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、紫外-可见(UV-Vis)光谱等技术对其进行了系统的表征, 以亚甲基蓝(MB)溶液的脱色降解为模型反应, 考察了不同Ag含量样品的光催化性能. 结果表明: 用溶剂热法制备的样品中TiO₂皆为锐钛矿相, 金属Ag颗粒沉积在TiO₂表面, 粒径为2 nm左右, 比表面积较溶胶凝胶法制备的样品大大增加, 最高可达151.44 m²·g^-1; UV-Vis光谱和光催化实验表明: Ag修饰使TiO₂对光的吸收能力大大增强, 吸收带边红移至可见光区, 亚甲基蓝在该复合材料上的光催化降解反应遵循一级反应动力学模型; 溶剂热法制备样品的光催化性能明显好于溶胶凝胶法制备的样品, 在紫外光和可见光下, Ag摩尔分数为5%的样品表现出最佳的光催化活性.     

溶剂热法制备Ag/TiO2纳米材料及其光催化性能

以乙醇为溶剂, 钛酸四丁酯为前驱体, 用溶剂热法制备了Ag表面修饰的负载型纳米二氧化钛光催化剂. 利用X射线衍射(XRD)、N₂吸附-脱附(BET)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、紫外-可见(UV-Vis)光谱等技术对其进行了系统的表征, 以亚甲基蓝(MB)溶液的脱色降解为模型反应, 考察了不同Ag含量样品的光催化性能. 结果表明: 用溶剂热法制备的样品中TiO₂皆为锐钛矿相, 金属Ag颗粒沉积在TiO₂表面, 粒径为2 nm左右, 比表面积较溶胶凝胶法制备的样品大大增加, 最高可达151.44 m²·g^-1; UV-Vis光谱和光催化实验表明: Ag修饰使TiO₂对光的吸收能力大大增强, 吸收带边红移至可见光区, 亚甲基蓝在该复合材料上的光催化降解反应遵循一级反应动力学模型; 溶剂热法制备样品的光催化性能明显好于溶胶凝胶法制备的样品, 在紫外光和可见光下, Ag摩尔分数为5%的样品表现出最佳的光催化活性.     

Fabrication and characterization of composition-gradient CuO/SiO2 composite aerogel

With tetramethoxysilane as the silica precursor, CuCl₂·2H₂O as the copper–oxide precursor, acetonitrile as the solvent and gelled by PO via a sol–gel process, the CuO/SiO₂ composite aerogel was fabricated. By adjusting the amount of CuCl₂·2H₂O, CuO/SiO₂ composite aerogels with different molar ratio of Cu/Si such as 1, 5, 10, 20, 30 and 35 % was prepared. Finally, via a self-built device and sol-co-gelation technic, a continuous formation process was developed to fabricate the composition-gradient CuO/SiO₂ composite aerogel. Density of these aerogels was about 200 mg/cm³, the composition-gradient CuO/SiO₂ composite aerogel was cylindrical and about 2.5 cm in height. Scanning electron microscope was used to characterize its microstructure at different position. X-ray diffraction, energy dispersive spectrometer and Fourier transform infrared spectrometer were used to characterize its composition and composition distribution, the results showed that the cylindrical CuO/SiO₂ composite aerogel’s molar ratio of Cu/Si changed from 31.06 to 4.43 % as the measure point from the bottom up, the whole sample displayed obvious composition-gradient.     

Influence of supercritical drying fluids on structures and properties of low-density Cu-doped SiO2 composite aerogels

The Cu-doped SiO₂ composite aerogels were successfully prepared by sol–gel process and subsequently supercritical drying with ethanol and CO₂. The Cu-doped SiO₂ composite aerogels had porous texture, low density (<100 mg cm^?3) and high specific surface area (>800 m² g^?1), which were investigated by FESEM and nitrogen adsorption desorption porosimetry. The FTIR spectra of the aerogels showed that the ethanol-dried aerogels had been modified by ethyl while the corresponding CO₂-dried aerogels had more Si–OH groups. The phase structure and thermal stability were investigated by XRD and TGA, respectively. Due to the reducibility of ethanol, the copper was crystalline in ethanol-dried sample. The Cu-doped SiO₂ composite aerogels dried with supercritical ethanol had larger pore diameter and better thermal stability under 400 °C in comparison with CO₂-dried composite aerogels. The structures and properties of Cu-doped SiO₂ composite aerogels are obviously affected by supercritical drying conditions. The effect research could instruct the synthesis of different state of Cu in composite aerogels.     

Catalytic Performance of Amorphous Ti/SiO2 in the Gas-Phase Epoxidation of Propylene with H2O2

The epoxidation of propylene with dilute H₂O₂ aqueous solution over titanium silicalite-1 (TS-1) zeolite catalyst is a green chemical reaction for propylene oxide (PO) production. Carrying out the reaction in gas-phase can get rid of problems caused by using methanol solvent. This paper reports an attempt of using non-zeolite catalyst for the gas-phase epoxidation. Amorphous Ti/SiO₂, obtained by grafting amorphous SiO₂ with TCl₄ in ethanol solvent in a chemical liquid-phase deposition (CLD) process, has been used as the catalyst. Results show that the CLD Ti/SiO₂ with appropriate Si/Ti molar ratio is an active catalyst for gas-phase epoxidation, achieving 9.8 % propylene conversion and 66.9 % PO selectivity with 40.3 % H₂O₂ utilization, which indicates that this amorphous Ti/SiO₂ catalyst deserves extensive studies in the future.     

Synthesis of TiO2–SiO2 aerogel via ambient pressure drying: effects of sol pre-modification on the microstructure and pore characteristics

TiO₂–SiO₂ composite aerogels were prepared via ambient pressure drying by sol–gel and surface modification for both the sol and gel samples. The organosilane reagents of decamethyltetrasiloxane (DMTSO)/trimethylchlorosilane (TMCS) and hexamethyldisiloxane (HMDSO)/TMCS were introduced into the TiO₂–SiO₂ composite sol for pre-modification respectively, and subsequently the TMCS/hexane solution was used for surface modification of the obtained TiO₂–SiO₂ composite gel. The effects of sol pre-modification on the microstructure and pore characteristics of TiO₂–SiO₂ composite aerogels were investigated. The results indicate that HMDSO/TMCS coupling reagents is more appropriate for the pre-modification of TiO₂–SiO₂ composite sol than the DMTSO/TMCS reagents. The best volume ratio of HMDSO/TMCS/composite sol for preparing mesoporous TiO₂–SiO₂ composite aerogels is in the range of 1:0.33:10–1:1.0:10, with which the specific surface area and pore volume of the obtained TiO₂–SiO₂ composite aerogels are 492–645 m²/g and 2.63–2.85 m³/g, respectively. The results of adsorption and photocatalytic degradation of rhodamine B show that the as-prepared TiO₂–SiO₂ composite aerogels have higher adsorption/photocatalysis. Particularly, the as-prepared TiO₂–SiO₂ composite aerogels with HMDSO/TMCS showed prominent adsorption capability with the adsorption rate attaining to 89.4 % within 60 min.     

Reduction of NO2 in Flue Gas by CO and Propylene over CuO‐CeO2/SiO2 in the Presence of O2

Catalytic reduction of NO₂ with CO and/or propylene in the presence of NO and excess oxygen, a model mixture for flue gas, was studied over a series of CuO‐CeO₂/SiO₂ catalysts between 120–260 °C. The effect of HCl, an impurity in flue gas, on the activity of the catalysts was evaluated. It was found that a binary oxide catalyst, 2% CuO‐8% CeO₂/SiO₂, was active for the reduction of NO₂ by CO and/or propylene. CO was effective for selective reduction of NO₂ in the presence of NO and O₂ in a temperature window between 160–200 °C while propylene was effective at temperature higher than 200 °C. In the presence of HCl, the activity of the catalyst for reduction of NO₂ with CO was irreversibly deactivated. However, the activity for reduction of NO₂ with propylene was not influenced by HCl.     

Partially Reduced Graphite Oxide as an Electrode Material for Electrochemical Double‐Layer Capacitors

Partially reduced graphite oxide was prepared from graphite oxide by using synthetic graphite as precursor. The reduction of graphite oxide with a layer distance of 0.57 nm resulted in a reduction of the layer distance depending on the degree of reduction. Simultaneously the amount of oxygen functionalities in the graphite oxide was reduced, which was corroborated by elemental analysis and EDX. The electrochemical activation of the partially reduced graphite oxide was investigated for tetraethylammonium tetrafluoroborate in acetonitrile and in propylene carbonate. The activation potential depends significantly on the degree of reduction, that is, on the graphene‐layer distance and on the solvent used. The activation potential decreased with increasing layer distance for both positive and negative activation. The resulting capacitance after activation was found to be affected by the layer distance, the oxygen functionalities and the used electrolyte. For a layer distance of 0.43 nm and with acetonitrile as the solvent, a differential capacitance of 220 Fg^?1 was achieved for the discharge of the positive electrode near the open‐circuit potential and 195 Fg^?1 in a symmetric full‐cell assembly.     

One-pot synthesis,characterization and properties of acid-catalyzed resorcinol/formaldehyde cross-linked silica aerogels and their conversion to hierarchical porous carbon monoliths

A rapid and facile synthesis of resorcinol/formaldehyde cross-linked silica (RF/SiO₂) aerogels was carried out in one pot based on an acid-catalyzed route, instead of the previously reported base-catalyzed ones. The gelation time was reduced to several hours at room temperature while it took several days even under heating conditions in the base-catalyzed ones. The interpenetrating network of RF/SiO₂ aerogels showed similar porous structures with those of silica aerogels or RF aerogels. Their thermal conductivity was as low as that of the typical glass wool materials. The mechanical properties are characterized by dynamic mechanical analysis and compression testing. At room temperature, the results of compression testing show that the compressive Young’s modulus or ultimate failure strength of RF/SiO₂ aerogel specimen is higher than that of native SiO₂ aerogels with a similar density. The one-pot method improves the efficiency and reduces the cost of RF/SiO₂ aerogels. The hierarchical porous carbon monoliths are also converted from carbonized RF/SiO₂ aerogels by an additional HF treatment. Hence, they could be further explored as multifunctional candidate materials for thermal, mechanical, and electrochemical applications.     

Synthesis characterization and catalytic evaluation of Ni/ZrO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> aerogels catalysts

The Ni/ZrO₂/SiO₂ aerogels catalysts were synthesized via three different routes: (i) impregnation ZrO₂–SiO₂ composite aerogels with a aqueous solution of Ni(NO₃)₂, (ii) impregnation SiO₂ aerogels with a mixed aqueous solution of Ni(NO₃)₂ and ZrO(NO₃)₂ · 2H₂O, (iii) one-pot sol–gel procedure from precursors Ni(NO₃)₂/ZrO(NO₃)₂ · 2H₂O/Si(OC₂H₅)₄. These catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), ammonia temperature-programmed desorption (NH₃-TPD), N₂ adsorption–desorption isotherms and Fourier transform infrared (FT-IR). The Liquid-phase hydrogenation of maleic anhydride (MA) was performed over these catalysts. The results revealed that the different preparation routes result in a difference between the obtained samples, concerning the crystal structure and composition, surface acidity, mixed level of each component, texture, and catalytic selectivity.     

The ethanol to acetaldehyde conversion activated by microwave radiation

The reaction of nonoxidative conversion of ethanol to acetaldehyde under conditions of thermal and microwave heating was studied on mixed ZnO—CuO—SiO₂ oxide catalysts modified with additives of Nb and Ta carbides. It is suggested that microwave heating promotes the appearance of “hot” zones at points where the metal-rich nanoparticles of metal carbides intensively absorbing the microwave energy contact active sites of the mixed oxide catalyst ZnO—CuO—SiO₂. Formation of these zones increases ethanol conversion and selectivity for acetaldehyde at moderate (<300°C) temperatures.