亚磷酸三苯酯臭氧化合物分解产生单重态氧的研究  

Generation of Singlet Oxygen by Decomposition of Triphenyl Phosphite Ozonide

作　　者：刘明[1] 沈关林[1] 杨何平[1] 沙国河[1] 张存浩[1] 

机构地区：[1]中国科学院大连化学物理研究所分子反应动力学国家重点实验室,大连116023

出　　处：《Chinese Journal of Chemical Physics》2004年第2期113-115,共3页化学物理学报（英文）

基　　金：Projectsupportedby 973program (19990 75 30 3)andtheKnowledgeInnovationProgramoftheChineseAcademyofSciences(DICPk2 0 0 3F2 )

摘　　要：This letter reports a study on producing gas-phase O 2(a 1Δ) by decomposition of triphenyl phosphite ozonide ((C 6H 5O) 3PO 3, TPPO 3) under a number of reaction conditions. For the first time, the cooperative emission at wavelengths 634 and 703 nm of O 2(a 1Δ) generated by TPPO 3 decomposition are observed. Specifically, under the condition of catalyzed decomposition by pyridine of TPPO 3 solution in CFCl 3 at low temperature, the emission spectrum is the same as that from the basic hydrogen peroxide plus chlorine reaction. This shows the feasibility of developing a new source for singlet delta oxygen. However, in the experiments of spontaneous decomposition of solid TPPO 3 and thermal decomposition of TPPO 3 solution on a high temperature surface, the spectra have a wide emission background around the 634 and 703 nm peaks, which indicates the production of some excited species than O 2(a 1△). Besides, there are about 2%～3%CO and 1.5%～2%CO 2 in the gaseous products together with a small amount of insoluble in acetone solid product, which imply that other than the formation of O 2(a 1△) and TPPO by unimolecular decomposition of TPPO 3, more complicated reactions may take place. The study of the reaction mechanism, the optimization of the expertise of O 2(a 1△) generation by TPPO 3 decomposition as well as measurement of absolute concentration of O 2(a 1△) are under way.This letter reports a study on producing gas-phase O 2(a 1Δ) by decomposition of triphenyl phosphite ozonide ((C 6H 5O) 3PO 3, TPPO 3) under a number of reaction conditions. For the first time, the cooperative emission at wavelengths 634 and 703 nm of O 2(a 1Δ) generated by TPPO 3 decomposition are observed. Specifically, under the condition of catalyzed decomposition by pyridine of TPPO 3 solution in CFCl 3 at low temperature, the emission spectrum is the same as that from the basic hydrogen peroxide plus chlorine reaction. This shows the feasibility of developing a new source for singlet delta oxygen. However, in the experiments of spontaneous decomposition of solid TPPO 3 and thermal decomposition of TPPO 3 solution on a high temperature surface, the spectra have a wide emission background around the 634 and 703 nm peaks, which indicates the production of some excited species than O 2(a 1△). Besides, there are about 2%～3%CO and 1.5%～2%CO 2 in the gaseous products together with a small amount of insoluble in acetone solid product, which imply that other than the formation of O 2(a 1△) and TPPO by unimolecular decomposition of TPPO 3, more complicated reactions may take place. The study of the reaction mechanism, the optimization of the expertise of O 2(a 1△) generation by TPPO 3 decomposition as well as measurement of absolute concentration of O 2(a 1△) are under way.

关 键 词：亚磷酸三苯酯臭氧化合物 氧碘化学激光 单重态氧 

分 类 号：O644.18[理学—物理化学]