Visible-Light Induced High-Yielding Benzyl Alcohol-to-Benzaldehyde Transformation over Mesoporous Crystalline TiO2: A Self-Adjustable Photo-oxidation System with Controllable Hole-Generatio

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• 作者：Renhong Li ; Hisayoshi Kobayashi ; Junfang Guo ; Jie Fan
• 刊名：Journal of Physical Chemistry C
• 出版年：2011
• 出版时间：December 1, 2011
• 年：2011
• 卷：115
• 期：47
• 页码：23408-23416
• 全文大小：1131K
• 年卷期：v.115,no.47(December 1, 2011)
• ISSN：1932-7455

文摘

High-yielding benzyl alcohol-to-benzaldehyde (BA-to-BAD) transformation has been achieved over mesoporous crystalline TiO₂ at mild conditions under visible-light irradiation with/without molecular oxygen. DFT calculations show that the antibonding 蟺 molecular orbitals (MOs) of BA can hybridize with the O2p atomic orbitals (AOs) of TiO₂, leading to the appearance of new energy levels located in the band gap where holes can be generated under visible-light irradiation. However, the oxidative product, BAD, is not stable when adsorbed on TiO₂ surface. This fact is supposed to prevent BAD from overoxidation by ceasing the hole formation. As a result, the hole generation becomes controllable in this type of photoreaction system, and a so-labeled 鈥?i>self-adjustable photo-oxidation system鈥?(denoted as SAPS) can be established. In addition, we also found that lattice oxygen (O_L) and Ti atoms within TiO₂ frameworks serve as the efficient reservoir for hydrogen and electrons in anaerobic reaction.