Composite catalyst for the photocatalytic isomerisation of norbornadiene to prepare quadricyclane and process for making the catalyst

Patent metadata

Field	Value
Publication number	US-10137443-B2
Application number	US-201414648896-A
Country	US
Kind code	B2
Filing date	May 23, 2014
Priority date	Feb 17, 2014
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

Abstract

The present invention discloses a composite catalyst for the photocatalytic isomerization of norbornadiene to prepare quadricyclane, comprising: a solid photocatalyst, selected from the group consisting of TiO 2 , Ti-MCM-41, Ti-SBA-15, ZnO, WO 3 , Ta 2 O 5 or SrTiO 3 ; and an organic photo-sensitizer loaded on the surface or in the channel of said solid photocatalyst, selected from benzophenone, acetophenone, Michler's Ketone, tetraethyl Michler's Ketone, and diethyl Michler's Ketone, where the organic photo-sensitizer is present in the solid photocatalyst in an amount of 0.5% to 20% by weight. The catalyst of the invention can catalyze a target reaction under the condition that no solvent is used, and the yield of the target product quadricyclane is higher. Furthermore, the catalyst of the invention has a stable activity, and it can be recycled. The invention further discloses a process for preparing the composite catalyst.

First claim

The invention claimed is:

1. A process of preparing a composite catalyst for photocatalytic isomerisation of norbornadiene to prepare quadricyclane, comprising the steps:
(a) mixing a solution obtained by dissolving an organic photo-sensitizer in an organic solvent with a solid photocatalyst under sufficient stirring, wherein the weight ratio of the organic photo-sensitizer to the solid photocatalyst ranging from 0.5% to 20%, so that the organic photo-sensitizer is adsorbed onto a surface or a channel of the solid photocatalyst, wherein the solid photocatalyst is selected from WO 3 , Ta 2 O 5 or SrTiO 3 ; and the organic photo-sensitizer is selected from benzophenone, acetophenone, Michler's Ketone, tetraethyl Michler's Ketone, or diethyl Michler's Ketone; and
(b) filtering off redundant solution and vacuum drying the solid photocatalyst which adsorbed the organic photo-sensitizer;
wherein in the step (a), the organic photo-sensitizer is present in the solution in a concentration of 20% by weight, and the solid photocatalyst is dried at 100° C., and the stirring continues for 24 hours; and in the step (b), the vacuum drying is carried out at 100° C. for 5 hours.

Assignees

• Univ Tianjin

Inventors

• Zou Jijun
• Zhang Xiangwen
• Wang Li
• Wang Qingfa

Classifications

• C07C2603/86

  containing four rings · CPC title

• C07C5/2213

  with metal oxides · CPC title

• C07C2523/20

  Vanadium, niobium or tantalum · CPC title

• C07C2523/06

  of zinc, cadmium or mercury · CPC title

• C07C2523/02

  of the alkali- or alkaline earth metals or beryllium · CPC title