Deposition of an oxomanganese water oxidation catalyst on TiO2 nanoparticles: computational modeling, assembly and characterization
Deposition of an oxomanganese water oxidation catalyst on TiO2 nanoparticles: computational modeling, assembly and characterization
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DOI：
10.1039/b818708h
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发表时间：
2009-01-01
影响因子：
32.5
通讯作者：
Batista, Victor S.
中科院分区：
文献类型：
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作者：
Li, Gonghu;Sproviero, Eduardo M.;Batista, Victor S.
开发模拟光合作用并利用阳光和水生产燃料的光催化太阳能电池需要廉价的水氧化催化剂。本文报道了通过直接吸附或原位合成将双核二-mu-氧锰水氧化催化剂 [H2O(terpy)Mn-III(mu-O)(2) Mn-IV(terpy)H2O](NO3)(3) (1, terpy = 2,2':6'2 ''-terpyridine) 成功附着到 TiO2 纳米粒子 (NPs) 上。所得表面复合物通过 EPR 和紫外可见光谱、电化学测量和计算建模进行表征。我们得出结论，如低温 (7 K) EPR 数据所示，1 的混合价（III、IV）态通过用 TiO2 NP 取代其水配体之一而附着在近无定形 TiO2 NP 上。相反，EPR 光谱和电化学研究表明，在结晶良好的 TiO2 纳米颗粒上的类似附着导致 1 在 TiO2 表面上二聚形成 Mn(IV) 四聚体。
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.