CAS OpenIR  > 多相复杂系统国家重点实验室
Superoxide radical-mediated photocatalytic oxidation of phenolic compounds over Ag+/TiO2: Influence of electron donating and withdrawing substituents
Xiao, Jiadong1,2; Xie, Yongbing1; Han, Qingzhen3; Cao, Hongbin1,4; Wang, Yujiao5; Nawaz, Faheem1,2; Duan, Feng1,2
2016-03-05
Source PublicationJOURNAL OF HAZARDOUS MATERIALS
ISSN0304-3894
Volume304Issue:MARPages:126-133
AbstractA comparative study was constructed to correlate the electronic property of the substituents with the degradation rates of phenolic compounds and their oxidation pathways under UV with Ag+/TiO2 suspensions. It was verified that a weak electron withdrawing substituent benefited photocatalytic oxidation the most, while an adverse impact appeared when a substituent was present with stronger electron donating or withdrawing ability. The addition of p-benzoquinone dramatically blocked the degradation, confirming superoxide radicals (O-center dot(2)-) as the dominant photooxidant, rather than hydroxyl radicals, singlet oxygen or positive holes, which was also independent of the substituent. Hammett relationship was established based on pseudo-first-order reaction kinetics, and it revealed two disparate reaction patterns between center dot O-2(-) and phenolic compounds, which was further verified by the quantum chemical computation on the frontier molecular orbitals and Mulliken charge distributions of center dot O-2(-) and phenolic compounds. It was found that electron donating group (EDG) substituted phenols were more likely nucleophilically attacked by center dot O-2(-), while center dot O-2(-) preferred to electrophilically assault electron withdrawing group (EWG) substituted phenols. Exceptionally, electrophilic and nucleophilic attack by center dot O-2(-) could simultaneously occur in p-chlorophenol degradation, consequently leading to its highest rate constant. Possible reactive positions on the phenolic compounds were also detailedly uncovered. (C) 2015 Elsevier B.V. All rights reserved.
KeywordTio2 Photocatalysis Substituent Phenolic Compounds Superoxide Radical Mechanism
SubtypeArticle
WOS HeadingsScience & Technology ; Technology ; Life Sciences & Biomedicine
DOI10.1016/j.jhazmat.2015.10.052
Indexed BySCI
Language英语
WOS KeywordVISIBLE-LIGHT IRRADIATION ; TIO2 AQUEOUS SUSPENSIONS ; DOPED TIO2 ; HYDROTHERMAL SYNTHESIS ; TITANIUM-DIOXIDE ; METAL-IONS ; DEGRADATION ; CARBON ; 4-CHLOROPHENOL ; PHOTODEGRADATION
WOS Research AreaEngineering ; Environmental Sciences & Ecology
WOS SubjectEngineering, Environmental ; Engineering, Civil ; Environmental Sciences
Funding OrganizationNational Natural Science Foundation of China(21207133) ; National Science Fund for Distinguished Young Scholars(51425405) ; Major Science and Technology Program for Water Pollution Control and Treatment(2013ZX07209-001 ; 2015ZX07202013-002)
WOS IDWOS:000367699200015
Citation statistics
Document Type期刊论文
Identifierhttp://ir.ipe.ac.cn/handle/122111/20259
Collection多相复杂系统国家重点实验室
Affiliation1.Chinese Acad Sci, Beijing Engn Res Ctr Proc Pollut Control, Key Lab Green Proc & Engn,Inst Proc Engn, Natl Engn Lab Hydromet Cleaner Prod Technol, Beijing 100190, Peoples R China
2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
3.Chinese Acad Sci, Inst Proc Engn, State Key Lab Multiphase Complex Syst, Beijing 100190, Peoples R China
4.Collaborat Innovat Ctr Chem Sci & Engn Tianjin, Tianjin 300072, Peoples R China
5.Univ Sci & Technol Beijing, Dept Chem & Biomed Engn, Beijing, Peoples R China
Recommended Citation
GB/T 7714
Xiao, Jiadong,Xie, Yongbing,Han, Qingzhen,et al. Superoxide radical-mediated photocatalytic oxidation of phenolic compounds over Ag+/TiO2: Influence of electron donating and withdrawing substituents[J]. JOURNAL OF HAZARDOUS MATERIALS,2016,304(MAR):126-133.
APA Xiao, Jiadong.,Xie, Yongbing.,Han, Qingzhen.,Cao, Hongbin.,Wang, Yujiao.,...&Duan, Feng.(2016).Superoxide radical-mediated photocatalytic oxidation of phenolic compounds over Ag+/TiO2: Influence of electron donating and withdrawing substituents.JOURNAL OF HAZARDOUS MATERIALS,304(MAR),126-133.
MLA Xiao, Jiadong,et al."Superoxide radical-mediated photocatalytic oxidation of phenolic compounds over Ag+/TiO2: Influence of electron donating and withdrawing substituents".JOURNAL OF HAZARDOUS MATERIALS 304.MAR(2016):126-133.
Files in This Item:
File Name/Size DocType Version Access License
Superoxide radical-m(2666KB)期刊论文出版稿限制开放CC BY-NC-SAApplication Full Text
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[Xiao, Jiadong]'s Articles
[Xie, Yongbing]'s Articles
[Han, Qingzhen]'s Articles
Baidu academic
Similar articles in Baidu academic
[Xiao, Jiadong]'s Articles
[Xie, Yongbing]'s Articles
[Han, Qingzhen]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[Xiao, Jiadong]'s Articles
[Xie, Yongbing]'s Articles
[Han, Qingzhen]'s Articles
Terms of Use
No data!
Social Bookmark/Share
All comments (0)
No comment.
 

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.