Chemistry of Mesoporous Organosilica in Nanotechnology: Molecularly Organic–Inorganic Hybridization into Frameworks

Organic–inorganic hybrid materials aiming to combine the individual advantages of organic and inorganic components while overcoming their intrinsic drawbacks have shown great potential for future applications in broad fields. In particular, the integration of functional organic fragments into the framework of mesoporous silica to fabricate mesoporous organosilica materials has attracted great attention in the scientific community for decades. The development of such mesoporous organosilica materials has shifted from bulk materials to nanosized mesoporous organosilica nanoparticles (designated as MONs, in comparison with traditional mesoporous silica nanoparticles (MSNs)) and corresponding applications in nanoscience and nanotechnology. In this comprehensive review, the state‐of‐art progress of this important hybrid nanomaterial family is summarized, focusing on the structure/composition–performance relationship of MONs of well‐defined morphology, nanostructure, and nanoparticulate dimension. The synthetic strategies and the corresponding mechanisms for the design and construction of MONs with varied morphologies, compositions, nanostructures, and functionalities are overviewed initially. Then, the following part specifically concentrates on their broad spectrum of applications in nanotechnology, mainly in nanomedicine, nanocatalysis, and nanofabrication. Finally, some critical issues, presenting challenges and the future development of MONs regarding the rational synthesis and applications in nanotechnology are summarized and discussed. It is highly expected that such a unique molecularly organic–inorganic nanohybrid family will find practical applications in nanotechnology, and promote the advances of this discipline regarding hybrid chemistry and materials.     

白炭黑原位复合聚丙烯酰胺水凝胶的合成及次级网络对流变行为的影响

采用水溶液聚合法,通过丙烯酰胺与白炭黑原位复合,制备出复合聚丙烯酰胺凝胶.采用高级流变仪和红外吸收光谱证实了白炭黑与聚丙烯酰胺形成的次级网络的存在,通过对比不同白炭黑填充量和不同吸水倍数对聚丙烯酰胺水凝胶模量、损耗角正切、零切黏度和流动指数的影响,发现白炭黑的加入对聚丙烯酰胺凝胶力学性能的贡献,随着白炭黑用量在0%～3...     

二氧化硅基多孔块材的制备及其热稳定性

以非离子型表面活性剂P123和三甲基苯的微乳液为模板剂合成介孔SiO2粉体.以此粉体为原料,经干压成型、烧结制备多孔SiO2块材.分别用AlOOH溶胶和TiO2溶胶包覆多孔SiO2粉体,制成多孔SiO2/Al2O3块材和SiO2/TiO2块材.采用XRD、SEM、TEM、N2吸附法和阿基米德排水法对所制粉体和块材进行了表征,并研究了块材的热稳定性.结果表明,600～700℃烧结的多孔SiO2基块材的孔隙率为74%～76%.与多孔SiO2块材相比,在800～1000℃范围内,SiO2/Al2O3块材的热稳定性显著提高,SiO2/TiO2块材的热稳定性在800～900℃范围内有一定改善.     

Superior electrocatalytic activity of mesoporous Au film templated from diblock copolymer micelles

Mesoporous Au films consisting of a network of interconnected Au ligaments around ultra-large pores were found to exhibit a promising electrocatalytic activity towards sluggish reactions. Mesoporous Au films with pore sizes up to 25 nm were successfully fabricated using a polymeric micelle approach. A superior catalytic activity of the mesoporous Au films towards methanol oxidation was confirmed, which was thoroughly analyzed and compared with that of other Au materials. An intrinsic investigation on the high catalytic activity revealed that the superior performance of the as-prepared mesoporous Au film was related to its unique atomic structures around the mesopores with well-crystallized facets and several step/kink sites on the Au surfaces. These findings showcase a strategic and feasible design for preparing highly active Au-based catalysts that could be used as promising candidates in electrocatalytic applications.

Open image in new window

     

纤维增强二氧化硅气凝胶复合材料的制备和低温性能

以正硅酸四乙酯(TEOS)为前驱体制备SiO2溶胶,并分别与玄武岩纤维和玻璃纤维复合,经超临界干燥工艺制备了疏水耐低温SiO2气凝胶复合材料。利用傅里叶红外光谱仪、接触角分析仪、激光法导热仪、万能试验机、氮气吸附法对SiO2气凝胶复合材料的结构和性能进行了表征。结果表明:两种纤维增强SiO2气凝胶复合材料在常温及低温下均具有良好的疏水性能和隔热性能,玄武岩纤维增强SiO2气凝胶复合材料和玻璃纤维增强SiO2气凝胶复合材料的接触角分别为148°和142°,常温热导率分别为0.030 W·m-1·K-1和0.026 W·m-1·K-1,-50℃时的热导率分别为0.027 W·m-1·K-1和0.024 W·m-1·K-1,在低温条件下,体积无明显收缩。纤维的加入提供了力学支撑,两种材料不仅在常温下具有良好的力学性能,而且在低温下的力学性能有所增强。     

溶胶凝胶法制备具有介孔结构的聚酰亚胺/SiO_2多孔复合微球

采用反相乳液法,以水溶性聚酰胺酸三乙胺盐(PAAS)、正硅酸乙酯(TEOS)为前驱体,通过溶胶凝胶法制备了具有介孔结构的聚酰亚胺(PI)/SiO_2多孔复合微球。将PAAS水溶液和TEOS水解液的混合溶液在液体石蜡中形成反相乳液,TEOS经水解缩合形成无机三维骨架,通过化学酰亚胺化使复合体系中的PAAS转变为PI,成功制备了含有介孔结构的PI/SiO_2多孔复合微球。研究发现,随着SiO_2含量的增加,复合微球的规整性不断提高,其比表面积由20.5 m~2/g增加至521.8 m~2/g。同时发现,调节TEOS水解液的pH值,微球的比表面积也会发生相应的变化。此外,热重分析结果显示该复合微球的热分解温度超过500℃,表明其具有优异的热稳定性。     

锡掺杂介孔分子筛在木材阻燃中的烟气转化作用

以水热晶化法合成了锡掺杂的介孔分子筛, 并采用XRD、N₂吸附-脱附、TEM、锥形量热等测试手段对其介观结构和物化性质进行了表征, 同时研究了该分子筛与聚磷酸铵(APP)复合在木材燃烧过程中的阻燃性能和烟气转化作用。结果表明, 该分子筛具有二维六方(P6mm)介观结构、高的比表面积, 与APP复合使用能有效降低杨木的热释放速率(HRR)、总热释放量(THR)、烟生成速率(SPR)和总烟释放量(TSP), 可促进炭的生成, 表现出优异的阻燃与抑烟特性。同时, 该分子筛对阻燃过程中释放的烟气具有转化作用, 能够有效地降低CO的浓度, 具有减毒作用。     

ATRP法在纳米硅胶粒子表面接枝聚甲基丙烯酸缩水甘油酯

将原子转移自由基聚合(ATRP)引发剂2-溴基异丁酰溴(BSB)化学键合在纳米硅胶微粒表面,以CuBr为催化剂,2,2′-联吡啶(byp)为配体,并加入少量自由(牺牲性)引发剂2-溴丙酸乙酯(BRA),在BSB-SiO2粒子表面进行了甲基丙烯酸缩水甘油酯(GMA)的接枝聚合反应。采用凝胶色谱(GPC)与热重分析(TGA)等手段对活性接枝聚合进行了确认。研究结果表明,接枝聚合反应呈现一级反应的动力学规律,接枝聚合物分子量及接枝度与单体转化率之间呈直线关系,反应过程中接枝聚合物链的密度恒定,充分显示了可控聚合的特征,成功地实现了功能单体GMA在纳米硅胶微粒表面的可控接枝聚合。     

气相二氧化硅聚集体的网络结构对硅橡胶性能的影响

采用RPA橡胶加工分析仪,在一定的温度和频率下,分析不同性质结构的气相二氧化硅在高温硅橡胶中的聚集体网络结构差异及聚集体网络对填充胶Payne效应的影响。研究发现,高分支结构聚集体的填充胶具有明显的Payne效应,补强效果好。原子力显微镜（AFM）表明,高分支结构的聚集体在高温胶基体中分散均匀,呈三维链网结构,聚集体橡胶约为100-200nm。示差扫描量热（DSC）分析表明,在-42℃左右,填充胶结晶而失去弹性。