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学科主题: 物理化学
题名: Asymmetric catalysis in nanopore materials
作者: Yang QH(杨启华)
会议文集: Organometallic Chemistry
会议名称: Gordon Research Conference (GRC) on Organometallic Chemistry
会议日期: 2011-7-10
出版日期: 2011
会议地点: 阿岗
其他题名: 纳米笼中的不对称催化
通讯作者: 杨启华
出版者: 待补充
出版地: 待补充
合作性质: 分会口头报告
部门归属: 506
主办者: 美国阿岗国家实验室
摘要: Heterogeneous chiral catalysts, mostly solid catalysts possess inherent features of practical advantages for industrial processes, such as simple separation and reuse of chiral catalysts, easy purification of products, and convenient operation processes. Therefore heterogeneous asymmetric catalysis is becoming a fascinating area for both the academic research and the commercial applications. However, the activity and enantioselectivity of most chiral solids is not high which impedes the practical applications of heterogeneous asymmetric catalysis. Recently, the novel chiral porous materials, the chiral periodic mesoporous organosilicas, were synthesized by our group and these materials show application potentials in heterogeneous asymmetric catalysis [1]. Moreover, our group developed an efficient method for the preparation of nanoreactors for asymmetric catalysis by encapsulating transition metal complexes in the nanocage of mesoporous silicas [2-5]. For example, chiral [Co(Salen)] complexes have been confined in the nanocage of SBA-16 by reducing the pore entrance size through a silylation method, resulting in a solid catalyst for the hydrolytic kinetic resolution (HKR) of epoxides. It was found that the activity of the solid catalysts increased with the number of [Co(Salen)] molecules per nanocage increasing, and the solid catalyst with more than two chiral [Co(Salen)] molecules in one nanocage of SBA-16 exhibits much higher activity and enantioselectivity than the homogeneous [Co(Salen)] catalyst in the HKR of epoxides at low substrate/catalyst ratio. The significantly improved activity of the solid catalyst is due to a high local concentration of [Co(Salen)] in nanospace because of the enhanced cooperative activation effect of [Co(Salen)] molecules. This work provides a new opportunity for the design of efficient solid catalysts for the asymmetric reactions as well as many other reactions, which involve cooperative activation by separate catalytic centers or second-order kinetic dependence on the local concentration of catalysts.
英文摘要: Heterogeneous chiral catalysts, mostly solid catalysts possess inherent features of practical advantages for industrial processes, such as simple separation and reuse of chiral catalysts, easy purification of products, and convenient operation processes. Therefore heterogeneous asymmetric catalysis is becoming a fascinating area for both the academic research and the commercial applications. However, the activity and enantioselectivity of most chiral solids is not high which impedes the practical applications of heterogeneous asymmetric catalysis. Recently, the novel chiral porous materials, the chiral periodic mesoporous organosilicas, were synthesized by our group and these materials show application potentials in heterogeneous asymmetric catalysis [1]. Moreover, our group developed an efficient method for the preparation of nanoreactors for asymmetric catalysis by encapsulating transition metal complexes in the nanocage of mesoporous silicas [2-5]. For example, chiral [Co(Salen)] complexes have been confined in the nanocage of SBA-16 by reducing the pore entrance size through a silylation method, resulting in a solid catalyst for the hydrolytic kinetic resolution (HKR) of epoxides. It was found that the activity of the solid catalysts increased with the number of [Co(Salen)] molecules per nanocage increasing, and the solid catalyst with more than two chiral [Co(Salen)] molecules in one nanocage of SBA-16 exhibits much higher activity and enantioselectivity than the homogeneous [Co(Salen)] catalyst in the HKR of epoxides at low substrate/catalyst ratio. The significantly improved activity of the solid catalyst is due to a high local concentration of [Co(Salen)] in nanospace because of the enhanced cooperative activation effect of [Co(Salen)] molecules. This work provides a new opportunity for the design of efficient solid catalysts for the asymmetric reactions as well as many other reactions, which involve cooperative activation by separate catalytic centers or second-order kinetic dependence on the local concentration of catalysts.
语种: 英语
内容类型: 会议论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/115962
Appears in Collections:中国科学院大连化学物理研究所_会议论文

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Recommended Citation:
Yang QH. Asymmetric catalysis in nanopore materials[C]. 见:Gordon Research Conference (GRC) on Organometallic Chemistry. 阿岗. 2011-7-10.
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