Deposition of an oxomanganese water oxidation catalyst on TiO2 nanoparticles: computational modeling, assembly and characterization

被引：58

作者：

Li, Gonghu ^{[1
]}

Sproviero, Eduardo M. ^{[1
]}

Snoeberger, Robert C., III ^{[1
]}

Iguchi, Nobuhito ^{[1
]}

Blakemore, James D. ^{[1
]}

Crabtree, Robert H. ^{[1
]}

Brudvig, Gary W. ^{[1
]}

Batista, Victor S. ^{[1
]}

机构：

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

来源：

ENERGY & ENVIRONMENTAL SCIENCE | 2009年 / 2卷 / 02期

基金：

美国国家科学基金会;

关键词：

OXYGEN-EVOLVING CENTER; MOLECULAR-DYNAMICS SIMULATIONS; PHOTOSYSTEM-II; O-2-EVOLVING COMPLEX; TITANIUM-DIOXIDE; MN(II)-TERPYRIDINE COMPLEXES; DIMANGANESE COMPLEX; HYDROGEN GENERATION; MANGANESE CLUSTER; FUNCTIONAL-MODEL;

D O I：

10.1039/b818708h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Inexpensive water oxidation catalysts are needed to develop photocatalytic solar cells that mimic photosynthesis and produce fuel from sunlight and water. This paper reports the successful attachment of a dinuclear di-mu-oxo manganese water oxidation catalyst [H2O(terpy)Mn-III(mu-O)(2) Mn-IV(terpy)H2O](NO3)(3) (1, terpy = 2,2':6'2 ''-terpyridine) onto TiO2 nanoparticles (NPs) via direct adsorption, or in situ synthesis. The resulting surface complexes are characterized by EPR and UV-visible spectroscopy, electrochemical measurements and computational modeling. We conclude that the mixed-valence (III, IV) state of 1 attaches to near-amorphous TiO2 NPs by substituting one of its water ligands by the TiO2 NP, as suggested by low-temperature (7 K) EPR data. In contrast, the analogous attachment onto well-crystallized TiO2 NPs leads to dimerization of 1 forming Mn(IV) tetramers on the TiO2 surface as suggested by EPR spectroscopy and electrochemical studies.

引用

页码：230 / 238

页数：9

共 48 条

[1] Ultrafast photooxidation of Mn(II)-Terpyridine complexes covalently attached to TiO2 nanoparticles [J].