中国科学院机构知识库网格
Chinese Academy of Sciences Institutional Repositories Grid
首页 机构 成果 学者
  
  1. CAS IR Grid
  2. 大连化学物理研究所
  3. 中国科学院大连化学物理研究所
Deuterium Kinetic Isotope Effect in the Photocatalyzed Dissociation of Methanol on TiO2(110)

文献类型：期刊论文

作者Wang, Tianjun2,3,7; Hao, Qunqing4; Wang, Zhiqiang1; Mao, Xinchun5; Ma, Zhibo3; Ren, Zefeng3; Dai, Dongxu3; Zhou, Chuanyao3; Yang, Xueming3,6
刊名JOURNAL OF PHYSICAL CHEMISTRY C
出版日期2018-11-22
卷号122期号:46页码:26512-26518
ISSN号1932-7447
DOI10.1021/acs.jpcc.8b09077
通讯作者Zhou, Chuanyao(chuanyaozhou@dicp.ac.cn) ; Yang, Xueming(xmyang@dicp.ac.cn)
英文摘要Deuterium kinetic isotope effect (KIE) in the photochemistry of methanol on TiO2(110) has been studied to find the rate determining step (RDS) and understand the reaction mechanism using two-photon photoemission spectroscopy. Deuterium substitution of the methyl hydrogen has little effect on the kinetics of this reaction, suggesting that neither the break of the C-H(D) bond nor the transfer of the H(D) atoms to the bridging sites is the RDS in the transformation of methanol into formaldehyde. In contrast, the reaction rate of MeOH is similar to 1.3 times that of MeOD, suggesting that the cleavage of O-H(D) is the RDS in the photocatalyzed dissociation of methanol on TiO2(110). The results contradict the common fact that C-H(D) is more difficult to break than O-H(D) based on ground-state energetics, implying the involvement of photogenerated charge carriers in the reaction of the C-H breakage, whereas the cleavage of O-H is likely a thermal reaction. Difference in the activation energy of O-H and O-D dissociation reaction in the methanol/TiO2(110) system has been calculated based on the KIE measurements. Our work is consistent with the fact that methoxy is photocatalytically more reactive than methanol and suggests that the conversion of methanol into methoxy is crucial in the photochemistry of methanol on TiO2(110) and probably other metal oxide semiconductor surfaces.
WOS关键词HYDROGEN-PRODUCTION ; CHEMICAL-REACTIONS ; RUTILE TIO2(110) ; SURFACE SCIENCE ; REDUCED RUTILE ; TIO2 ; CHEMISTRY ; ADSORPTION ; ALCOHOLS ; HOLES
资助项目National Natural Science Foundation of China[21573225] ; National Natural Science Foundation of China[21688102] ; National Natural Science Foundation of China[21703164] ; National Key Research and Development Program of China[2016YFA0200600] ; National Key Research and Development Program of China[2018YFA0208700] ; Youth Innovation Promotion Association of CAS[2017224] ; Strategic Pilot Science and Technology Project[XDB17000000]
WOS研究方向Chemistry ; Science & Technology - Other Topics ; Materials Science
语种英语
出版者AMER CHEMICAL SOC
WOS记录号WOS:000451495600025
资助机构National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Key Research and Development Program of China ; National Key Research and Development Program of China ; Youth Innovation Promotion Association of CAS ; Youth Innovation Promotion Association of CAS ; Strategic Pilot Science and Technology Project ; Strategic Pilot Science and Technology Project ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Key Research and Development Program of China ; National Key Research and Development Program of China ; Youth Innovation Promotion Association of CAS ; Youth Innovation Promotion Association of CAS ; Strategic Pilot Science and Technology Project ; Strategic Pilot Science and Technology Project ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Key Research and Development Program of China ; National Key Research and Development Program of China ; Youth Innovation Promotion Association of CAS ; Youth Innovation Promotion Association of CAS ; Strategic Pilot Science and Technology Project ; Strategic Pilot Science and Technology Project ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Key Research and Development Program of China ; National Key Research and Development Program of China ; Youth Innovation Promotion Association of CAS ; Youth Innovation Promotion Association of CAS ; Strategic Pilot Science and Technology Project ; Strategic Pilot Science and Technology Project
源URL[http://cas-ir.dicp.ac.cn/handle/321008/166580]  
专题大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者Zhou, Chuanyao; Yang, Xueming
作者单位1.Xidian Univ, Sch Phys & Optoelect Engn, Xian 710071, Shaanxi, Peoples R China
2.Chinese Acad Sci, Shanghai Adv Res Inst, 99 Haike Rd,Zhangjiang Hitech Pk, Shanghai 201210, Peoples R China
3.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, 457 Zhongshan Rd, Dalian 116023, Liaoning, Peoples R China
4.Sci & Technol Surface Phys & Chem Lab, POB 9-35, Jiangyou 621908, Sichuan, Peoples R China
5.China Acad Engn Phys, Inst Mat, 596 Yinhe Rd 7th Sect, Chengdu 610200, Sichuan, Peoples R China
6.Southern Univ Sci & Technol, Dept Chem, 1088 Xueyuan Rd, Shenzhen 518055, Guangdong, Peoples R China
7.Univ Chinese Acad Sci, 19A Yuquan Rd, Beijing 100049, Peoples R China
推荐引用方式
GB/T 7714		 Wang, Tianjun,Hao, Qunqing,Wang, Zhiqiang,et al. Deuterium Kinetic Isotope Effect in the Photocatalyzed Dissociation of Methanol on TiO2(110)[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2018,122(46):26512-26518.
APA Wang, Tianjun.,Hao, Qunqing.,Wang, Zhiqiang.,Mao, Xinchun.,Ma, Zhibo.,...&Yang, Xueming.(2018).Deuterium Kinetic Isotope Effect in the Photocatalyzed Dissociation of Methanol on TiO2(110).JOURNAL OF PHYSICAL CHEMISTRY C,122(46),26512-26518.
MLA Wang, Tianjun,et al."Deuterium Kinetic Isotope Effect in the Photocatalyzed Dissociation of Methanol on TiO2(110)".JOURNAL OF PHYSICAL CHEMISTRY C 122.46(2018):26512-26518.

入库方式： OAI收割

来源：大连化学物理研究所

浏览0
下载0
收藏0
其他版本

除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。