Photoelectrochemical Hole Injection Revealed in Polyoxotitanate Nanocrystals Functionalized with Organic Adsorbates

被引：65

作者：

Negre, Christian F. A. ^{[1
,2
]}

Young, Karin J. ^{[1
,2
]}

Oviedo, Ma Belen ^{[3
]}

Allen, Laura J. ^{[1
,2
]}

Sanchez, Cristian G. ^{[4
]}

Jarzembska, Katarzyna N. ^{[5
,6
]}

Benedict, Jason B. ^{[5
]}

Crabtree, Robert H. ^{[1
,2
]}

Coppens, Philip ^{[5
]}

Brudvig, Gary W. ^{[1
,2
]}

Batista, Victor S. ^{[1
,2
]}

机构：

[1] Yale Univ, Dept Chem, New Haven, CT 06520 USA

[2] Yale Univ, Energy Sci Inst, New Haven, CT 06520 USA

[3] Drexel Univ, Dept Chem, Philadelphia, PA 19104 USA

[4] Univ Nacl Cordoba, INFIQC, Fac Ciencias Quim, Dept Matemat & Fis, RA-5000 Cordoba, Argentina

[5] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA

[6] Univ Warsaw, Dept Chem, PL-02093 Warsaw, Poland

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 46期

关键词：

INTERFACIAL ELECTRON-TRANSFER; QUANTUM DYNAMICS; TIO2; SIMULATIONS; TOOL;

D O I：

10.1021/ja509270f

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We find that crystallographically resolved Ti17O24(OPri)(20) nanoparticles, functionalized by covalent attachment of 4-nitrophenyl-acetylacetonate or coumarin 343 adsorbates, exhibit hole injection into surface states when photoexcited with visible light (lambda = 400-680 nm). Our findings are supported by photo-electrochemical measurements, EPR spectroscopy, and quantum dynamics simulations of interfacial charge transfer. The underlying mechanism is consistent with measurements of photocathodic currents generated with visible light for thin layers of functionalized polyoxotitanate nanocrystals deposited on FTO working electrodes. The reported experimental and theoretical analysis demonstrates for the first time the feasibility of p-type sensitization of TiO2 solely based on covalent binding of organic adsorbates.

引用

页码：16420 / 16429

页数：10

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