Zhu Guiru, Yang Qihua, Zhong Hua, Jiang Dongmei, Li Can
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China.
J Phys Chem B. 2007 Jul 19;111(28):8027-33. doi: 10.1021/jp071913j. Epub 2007 Jun 26.
A phase transformation of mesoporous organosilicas from 2D-hexagonal P6mm to cubic Pm3n phase can be induced by the organotrialkoxysilane with hydrophilic pendant group with the aid of methanol during the co-condensation of 1,2-bis(trimethoxysilyl)ethane (BTME) and (EtO)(3)Si-R (R = L-prolinamide, trans-(1R,2R)-diaminocyclohexane, and gamma-aminopropyl) using the cationic surfactant, octadecyltrimethylammonium chloride (C(18)TMACl), as template in basic medium. Under similar synthesis conditions, no cubic Pm3n phase could be formed in the absence of (EtO)(3)Si-R. Depending on the type of the pendant group, different amounts of methanol were needed for the formation of the cubic Pm3n phase. N-[(triethoxysilyl)propyl]-L-prolinamide (M(L-Pro)) could easily induce the phase changing from 2D-hexagonal P6mm to cubic Pm3n phase probably because L-proline could result in a decreasing of the surfactant packing factor (g) through formation of large architecture on the outer boundary of the surfactant micelles. The organotrialkoxysilane can also help the formation of spherical morphology of the resultant materials.
在碱性介质中,以阳离子表面活性剂十八烷基三甲基氯化铵(C₁₈TMACl)为模板,在1,2-双(三甲氧基硅基)乙烷(BTME)和(EtO)₃Si-R(R = L-脯氨酰胺、反式-(1R,2R)-二氨基环己烷和γ-氨丙基)的共缩合过程中,带有亲水性侧基的有机三烷氧基硅烷借助甲醇可诱导介孔有机硅从二维六方P6mm相转变为立方Pm3n相。在类似的合成条件下,若不存在(EtO)₃Si-R,则无法形成立方Pm3n相。根据侧基类型的不同,形成立方Pm3n相所需的甲醇量也不同。N-[(三乙氧基硅基)丙基]-L-脯氨酰胺(M(L-Pro))能够轻易地诱导从二维六方P6mm相转变为立方Pm3n相,这可能是因为L-脯氨酸通过在表面活性剂胶束的外边界形成大的结构,导致表面活性剂堆积因子(g)降低。有机三烷氧基硅烷也有助于形成所得材料的球形形态。