Department of Chemistry, College of Staten Island, City University of New York, 2800 Victory Boulevard, Staten Island, New York 10314, USA.
Langmuir. 2012 Jun 12;28(23):8737-45. doi: 10.1021/la301329c. Epub 2012 Jun 4.
Large-pore ethenylene-bridged (-CH═CH-) and phenylene-bridged (-C(6)H(4)-) periodic mesoporous organosilicas (PMOs) with face-centered-cubic structure (Fm3m symmetry) of spherical mesopores were synthesized at 7 °C at low acid concentration (0.1 M HCl) using Pluronic F127 triblock copolymer surfactant in the presence of aromatic swelling agents (1,3,5-trimethylbenzene, xylenes-isomer mixture, and toluene). In particular, this work reports an unprecedented block-copolymer-templated well-ordered ethenylene-bridged PMO with cubic structure of spherical mesopores and an unprecedented block-copolymer-templated face-centered cubic phenylene-bridged PMO, which also has an exceptionally large unit-cell size and pore diameter. The unit-cell parameters of 30 and 25 nm and the mesopore diameters of 14 and 11 nm (nominal BJH-KJS pore diameters of 12-13 and 9 nm) were obtained for ethenylene-bridged and phenylene-bridged PMOs, respectively. Under the considered reaction conditions, the unit-cell parameters and pore diameters were found to be similar when the three different methyl-substituted benzene swelling agents were employed, although the degree of structural ordering appeared to improve for phenylene-bridged PMOs in the sequence of decreased number of methyl groups on the benzene ring.
大孔乙烯桥联（-CH=CH-）和苯桥联（-C(6)H(4)-）周期性介孔有机硅（PMO）具有面心立方结构（Fm3m 对称）的球形介孔，在 7°C 下、低酸浓度（0.1 M HCl）下、使用 Pluronic F127 三嵌段共聚物表面活性剂和芳香族溶胀剂（1,3,5-三甲苯、二甲苯异构体混合物和甲苯）合成。特别是，这项工作报道了一种前所未有的具有立方结构的球形介孔的乙烯桥联 PMO 和一种前所未有的具有面心立方苯桥联 PMO，它们都具有非常大的晶胞尺寸和孔径。乙烯桥联和苯桥联 PMO 的晶胞参数分别为 30 和 25nm，介孔直径分别为 14 和 11nm（名义上的 BJH-KJS 孔径分别为 12-13nm 和 9nm）。在所考虑的反应条件下，当使用三种不同的甲基取代苯溶胀剂时，发现晶胞参数和孔径相似，尽管苯桥联 PMO 的结构有序度似乎随着苯环上甲基数的减少而提高。
