Hierarchically Ordered Nanoporous-Macroporous Materials

1970年，D.J. Pine教授和B.F. Chmelka教授将开发新的单片多孔材料，其中包含平均直径在2-50 nm和0.1-10微米之间的孔隙组合。双孔结构将通过两种工艺相结合的方法来实现：可聚合无机前驱体的单分散乳液模板制备大孔，以及两亲性表面活性剂引导前驱体的自组装制备中孔。随后的凝胶化、干燥和热处理将会导致这种巨石。等级有序孔隙结构的合成方法将允许独立控制每个范围的大小和几何形状，以及广泛的无机氧化物成分（二氧化硅，氧化铝，二氧化钛，氧化锆，锑，钨，铁，锌，镁，锰，镍，钴，铅和镓的氧化物）。模板技术还允许对框架表面进行功能性修改。可能会产生新的催化衬底、传感器、无源或有源滤波器或光学材料。合成材料的物理化学表征将涉及核磁共振、x射线散射、气体吸附和光学测量。化学反应表征将包括丁苯在分散的Pt介孔上的加氢反应，以及丙烯在金属锆功能化介孔上的聚合反应。加入不饱和碳氢化合物或阳离子位点（分别增加对芳香或卤素基团的亲和力）或加入巯基烷基硅烷（以强烈吸附重金属）将影响材料的分离性能。光学和传感器性能将通过在大孔结构内与II-VI半导体物种进行功能化来调整（以创建红外光子光学材料）。这笔拨款还将支持加州大学圣母院与波尔多之间的国际交流，与Jerome Bibette教授的实验室进行交流，Jerome Bibette教授在配方生产和单分散乳剂加工方面具有专业知识。合作的主要机制将是通过研究生的长期互访。

ABSTRACT - Pine - 9871970 Professors D.J. Pine and B.F. Chmelka will develop new monolithic porous materials containing a combination of pores of mean diameter ranges 2-50 nm and 0.1-10 micron. The dual pore construction will be achieved with a method that combines two processes: monodisperse emulsion templating of polymerizable inorganic precursors to fabricate the macropores, and amphiphilic surfactant-guided self-assembly of the precursors to produce the mesopores. Subsequent gelation, drying, and heat treatment will lead to the monoliths. The synthetic methods for the hierarchically ordered pore structures will allow control of the size and geometry for each range independently, and for a wide spectrum of inorganic oxide compositions (silica, alumina, titania, zirconia, oxides of antimony, tungsten, iron, zinc, magnesium, manganese, nickel, cobalt, lead, and gallium). The templating technique will also permit functional modification of the framework surfaces. Novel catalytic substrates, sensors, passive or active filters, or optical materials, may result. Physicochemical characterization of the synthesized materials will involve NMR, x-ray scattering, gas adsorption and optical measurements. Chemical reaction characterization will consist of the hydrogenation of styrene-butadiene over dispersed Pt in the mesopores, and the polymerization of propylene over Zr-metallocene-functionalized mesopores. The separation properties of the materials will be affected by incorporating unsaturated hydrocarbon or cationic sites (to increase affinity to aromatic or halogen groups, respectively), or by incorporating mercaptoalkylsilanes (to strongly adsorb heavy metals). The optical and sensor properties will be tuned by functionalization with II-VI semiconductor species within the large pore structure (to create infrared photonic optical materials). The grant will also support an international exchange between UCSB and Bordeaux, with the laboratory of Prof. Jerome Bibette, which has expertise in formulat ion production, and processing of monidisperse emulsions. The primary mechanism of cooperation will be through graduate student extended reciprocal visits.