Ultrafast Dynamics of Photongenerated Holes at a CH3OH/TiO2 Rutile Interface

doi:10.1021/jacs.6b08725

	Ultrafast Dynamics of Photongenerated Holes at a CH3OH/TiO2 Rutile Interface
	Chu, Weibin 1,2,3,4; Saidi, Wissam A.5; Zheng, Qijing 1,2,3,4; Xie, Yu6,7 ; Lan, Zhenggang 6,7; Prezhdo, Oleg V.8,9; Petek, Hrvoje 10; Zhao, Jin 1,2,3,4,10
	2016-10-19
发表期刊	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷号	138 期号:41 页码:13740-13749
摘要	Photogenerated charge carrier dynamics near molecule/TiO2 interfaces are important for the photocatalytic and photovoltaic processes. To understand this fundamental aspect, we performed a time-domain ab initio nonadiabatic molecular dynamics study of the photogenerated hole dynamics at the CH3OH/rutile TiO2(110) interface. We studied the forward and reverse hole transfer between TiO2 and CH3OH as well as the hole energy relaxation to the valence band maximum. First, we show that the hole-trapping ability of CH3OH depends strongly on the adsorption structure. Only when the CH3OH is deprotonated to form chemisorbed CH3O will 45% of the hole be trapped by the molecule. Second, we find that strong fluctuations of the HOMO energies of the adsorbed molecules induced by electron phonon coupling provide additional channels, which accelerate the hole energy relaxation. Third, we demonstrate that the charge transfer and energy relaxation processes depend significantly on temperature. When the temperature decreases from 100 to 30 K, the forward hole transfer and energy relaxation processes are strongly suppressed because of the reduction of phonon occupation. These results indicate that the molecule/TiO2 energy level alignment, thermal excitation of a phonon, and electron phonon coupling are the key factors that determine the photogenerated hole dynamics. Our studies provide valuable insights into the photogenerated charge and energy transfer dynamics at molecule/semiconductor interfaces.
文章类型	Article
WOS标题词	Science & Technology ; Physical Sciences
DOI	10.1021/jacs.6b08725
关键词[WOS]	INITIO MOLECULAR-DYNAMICS ; COUPLED ELECTRON-TRANSFER ; SENSITIZED SOLAR-CELLS ; EXPOSED 001 FACETS ; VISIBLE-LIGHT ; TIO2 NANOPARTICLES ; LEVEL ALIGNMENT ; CHARGE-TRANSFER ; PHOTOCATALYTIC ACTIVITY ; HYDROGEN-PRODUCTION
收录类别	SCI
语种	英语
WOS研究方向	Chemistry
项目资助者	Natural Science Foundation of Science of China(11322434 ; Chinese Department of Science Technology(2016YFA0200600 ; National Science Foundation(CHE-1213189 ; Natural Science Foundation of Shandong Province for Distinguished Young Scholars(JQ201504) ; U.S. Department of Energy(DE-SC0014429) ; DOE Office of Biological and Environmental Research ; 21121003 ; 2016YFA0200604) ; CHE-1565704) ; 11620101003 ; 21503248 ; 21543008 ; 21673266)
WOS类目	Chemistry, Multidisciplinary
WOS记录号	WOS:000385992100044
引用统计
文献类型	期刊论文
条目标识符	http://ir.qibebt.ac.cn/handle/337004/9070
专题	先进材料理论与模拟团队（过去）
作者单位	1.Univ Sci & Technol China, ICQD Hefei Natl Lab Phys Sci Microscale, Hefei 230026, Anhui, Peoples R China 2.Univ Sci & Technol China, Key Lab Strongly Coupled Quantum Matter Phys Chin, Acad Sci, Hefei 230026, Anhui, Peoples R China 3.Univ Sci & Technol China, Dept Phys, Hefei 230026, Anhui, Peoples R China 4.Univ Sci & Technol China, Synerget Innovat Ctr Quantum Informat & Quantum P, Hefei 230026, Anhui, Peoples R China 5.Univ Pittsburgh, Dept Mech Engn & Mat Sci, Pittsburgh, PA 15261 USA 6.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Key Lab Biobased Mat, Qingdao 266101, Shandong, Peoples R China 7.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 8.Univ Southern Calif, Dept Chem, Los Angeles, CA 90089 USA 9.Univ Southern Calif, Dept Phys & Astron, Los Angeles, CA 90089 USA 10.Univ Pittsburgh, Dept Phys & Astron, Pittsburgh, PA 15260 USA
推荐引用方式 GB/T 7714	Chu, Weibin,Saidi, Wissam A.,Zheng, Qijing,et al. Ultrafast Dynamics of Photongenerated Holes at a CH3OH/TiO2 Rutile Interface[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2016,138(41):13740-13749.
APA	Chu, Weibin.,Saidi, Wissam A..,Zheng, Qijing.,Xie, Yu.,Lan, Zhenggang.,...&Zhao, Jin.(2016).Ultrafast Dynamics of Photongenerated Holes at a CH3OH/TiO2 Rutile Interface.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,138(41),13740-13749.
MLA	Chu, Weibin,et al."Ultrafast Dynamics of Photongenerated Holes at a CH3OH/TiO2 Rutile Interface".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 138.41(2016):13740-13749.