Determining the TiO2-Photocatalytic Aryl-Ring-Opening Mechanism in Aqueous Solution Using Oxygen-18 Labeled O-2 and H2O

doi:10.1021/ja5031936

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	Determining the TiO2-Photocatalytic Aryl-Ring-Opening Mechanism in Aqueous Solution Using Oxygen-18 Labeled O-2 and H2O
	Pang, Xibin; Chang, Wei; Chen, Chuncheng; Ji, Hongwei; Ma, Wanhong; Zhao, Jincai
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2014-06-18
卷号	136 期号:24 页码:8714-8721
ISSN号	0002-7863
DOI	10.1021/ja5031936
英文摘要	The molecules O-2 and H2O dominate the cleavage of aromatic sp(2) C-C bonds, a crucial step in the degradation of aromatic pollutants in aqueous TiO2 photocatalysis, but their precise roles in this process have remained elusive. This can be attributed to the complex oxidative species involved and to a lack of available models for reactions with a high yield of direct products. Here, we used oxygen-18 isotope labeled O-2 and H2O to observe the aromatic ring-opening reaction of the model compound 3,5-di-tert-butylcatechol (DTBC), which was mediated by TiO2 photocatalysis in an aqueous acetonitrile solution. By analyzing the primary intermediate products (similar to 75% yield), especially the seven-membered ring anhydrides that were formed, we obtained direct evidence for the oxygen atom of dioxygen insertion into a C-C bond of the aromatic ring. This indicates that molecular oxygen is the ultimate ring-opening agent in TiO2 photocatalysis and that it undergoes single O atom incorporation rather than the previously proposed molecular oxygen 1,2-addition processes. The ratio of intradiol to extradiol products depends on the particle size of TiO2 catalysts used, which suggests that the O-2 activation is correlated with the available coordination sites on the TiO2 surface in the photocatalytic cleavage of the aromatic ring.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000337720200036
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/52303]
专题	中国科学院化学研究所
通讯作者	Ma, Wanhong
作者单位	Chinese Acad Sci, Inst Chem, Key Lab Photochem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
推荐引用方式 GB/T 7714	Pang, Xibin,Chang, Wei,Chen, Chuncheng,et al. Determining the TiO2-Photocatalytic Aryl-Ring-Opening Mechanism in Aqueous Solution Using Oxygen-18 Labeled O-2 and H2O[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2014,136(24):8714-8721.
APA	Pang, Xibin,Chang, Wei,Chen, Chuncheng,Ji, Hongwei,Ma, Wanhong,&Zhao, Jincai.(2014).Determining the TiO2-Photocatalytic Aryl-Ring-Opening Mechanism in Aqueous Solution Using Oxygen-18 Labeled O-2 and H2O.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,136(24),8714-8721.
MLA	Pang, Xibin,et al."Determining the TiO2-Photocatalytic Aryl-Ring-Opening Mechanism in Aqueous Solution Using Oxygen-18 Labeled O-2 and H2O".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 136.24(2014):8714-8721.