基于固体光催化剂的降冰片二烯光异构反应研讨.pdfVIP

基于固体光催化剂的降冰片二烯光异构反应研究 * 邹吉军，刘 日失，王莅，张香文 天津大学化工学院，绿色合成与转化教育部重点实验室，天津300072 摘要：降冰片二烯光催化异构为四环庚烷在太阳能利用及航天燃料合成方面具有重要价值。为克服均相光 敏反应的缺点，研究基于TiO 的固体光催化反应路线。合成了Zn 掺杂的TiO ，发现Zn 主要分散在TiO 表 2 2 2 面，抑制颗粒生长、团聚及相转变，获得10 nm 以下的TiO2 颗粒。掺杂Zn 显著增加表面羟基的含量，并使 光吸收发生红移，并使催化剂活性提高。其中 1%-Zn/TiO2 的活性最好，高于均相光敏剂二乙基米氏酮。在 1%-Zn/TiO2 上掺杂La 获得了量子尺寸的纳米颗粒，但表面羟基含量减少。在光异构反应中，3%和 5%的La 可以进一步提高活性。研究结果表明，基于固体光催化剂的反应路线具有更高效率和良好的应用前景。 关键词：降冰片二烯；四环庚烷；光异构；固体光催化剂 Photocatalyic Isomerization of Norbornadiene to Quadricyclane using Solid Photocatalysts ZOU Jijun, LIU Yi, WANG Li, ZHANG Xiangwen (Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, P. R. China) Abstract: Zn-doped and La/Zn co-doped TiO nanoparticles were prepared by sole-gel method 2 and utilized as the photocatalysts for the isomerization of norbornadiene to quadricyclane that has significant potential for solar energy storage and high-energy fuel synthesis. For Zn-doped samples, Zn ions do not enter the TiO2 lattice, but distribute on the particle surface in form of ZnO crystallites. These crystallites can inhibit the agglomeration, growth and anatase-to-rutile phase transformation of TiO2 . The prepared particles contain a considerable amount of surface-bound OHs, especially for 1%Zn/TiO2 . A red shift in the optical absorption is observed due to the electron transfer between TiO2 and ZnO. In the photocatalytic isomerization reaction, Zn-doped TiO exhibits higher activity than homogenous Ethyl Michler’s Keton, and 1%Zn/