Application of Cu (I) Containing Amino-functionalized SBA-15 in Catalytic Oxidative Homocoupling of Phenylacetylene under Air

• Main Authors: Guan-Ping Chen, 陳冠萍
• Other Authors: Soofin Cheng
• Format: Others
• Language: zh-TW
• Published: 2015
• Online Access: http://ndltd.ncl.edu.tw/handle/48257348847375991579

碩士 === 國立臺灣大學 === 化學研究所 === 103 === SBA-15 mesoporous silica materials with short mesochannels were functionalized with various amino-groups, including NH2-, MeNH-, PholNH, PholNNH-, diamine-, triamine-, guanidine- groups through one-pot co-condensation of tetraethylorthosilicate (TEOS) and amino-containing trimethoxysilane in the presence of P123 as pore-directing agent and appropriate amount of Zr(IV) ions. In situ X-ray scattering was used to find out the optimal prehydrolysis period of TEOS to be around 2 h prior to the addition of the amino-functional groups, in order to prepare platelet SBA-15 materials with well-ordered p6mm pore structure and narrowly distributed pore sizes. The resultant materials were characterized by XRD, N2 sorption isotherm, TGA, SEM, FT-IR, Solid NMR. Cu(I) was anchored with amino-functionalized SBA-15 through complexation, and the resultant Cu-amine-SBA-15-p was examined as the catalysts in the oxidative homocoupling of phenylacetylene at room temperature with air as the oxidant. With organic base as the additive, the yield and selectivity of 1,4-diphenyl-1,3-butadiyne were roughly up to 90% and nearly 100%, respectively. Furthermore, different kinds of base additives were found to have enormous influence on the rates of the reaction. Efforts were made to replace the liquid base additives by designing a Cu-catalyst with strong-basicity groups in order to have a synergistic effect and achieve reusability of the catalysts.