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Evidence of Interfacial Charge Transfer upon UV-Light Irradiation in Novel Titanium Oxide Gel

机译：新型氧化钛凝胶中紫外光照射时界面电荷转移的证据

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We report on the combined magnetization and electron paramagnetic resonance characterization of a novel Ti-O organic-inorganic gel hybrid and the related electron-hole generation process upon UV illumination. We find that electrons are injected into the conduction band of the Ti-O framework, photoreducing Ti~(IV) to Ti~(III). Ti~(III) sites are mainly located on the surface, owing to the nanometric dimensions of the inorganic component. Surprisingly, the symmetry of the TiO_6 octahedra depends on the level of illumination: in the lightly UV-exposed samples Ti~(III) is sited in the weakly distorted TiO_6 octahedra to which methanoate groups are bonded, as suggested by electron spin echo envelope modulation (ESEEM) experiments. Extensive illumination causes structural rearrangements, leading to enhanced tetragonal TiO_6 distortion and shifting the Ti~(III) interaction towards the hydroxide groups or water. The results provide clear evidence for an interfacial charge transfer between the quantum-size TiO lattice and coordinated species upon in situ and ex situ UV illumination at temperatures from room temperature to 5 K.
机译：我们报告了新型Ti-O有机-无机凝胶杂化体的结合磁化和电子顺磁共振表征，以及在紫外线照射下的相关电子空穴生成过程。我们发现电子被注入到Ti-O框架的导带中，从而将Ti〜（IV）光还原为Ti〜（III）。由于无机组分的纳米尺寸，Ti〜（III）位点主要位于表面上。出乎意料的是，TiO_6八面体的对称性取决于光照水平：在轻微紫外线照射的样品中，Ti〜（III）位于结合了甲酸酯基的弱扭曲的TiO_6八面体中，如电子自旋回波包络调制所示（ESEEM）实验。广泛的照明会引起结构重排，导致增强的TiO_6四方晶畸变，并使Ti〜（III）相互作用朝着氢氧根或水转移。结果提供了清晰的证据，证明了在室温至5 K的温度下，原位和非原位UV照射下，量子尺寸TiO晶格与配位物种之间的界面电荷转移。

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