DFT study on the reaction mechanisms behind the catalytic oxidation of benzyl alcohol into benzaldehyde by O2 over anatase TiO2 surfaces with hydroxyl groups: Role of visible-light irradiation
DFT study on the reaction mechanisms behind the catalytic oxidation of benzyl alcohol into benzaldehyde by O2 over anatase TiO2 surfaces with hydroxyl groups: Role of visible-light irradiation
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DOI：
10.1016/j.apcatb.2015.01.035
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发表时间：
2015-07-01
影响因子：
22.1
通讯作者：
Higashimoto, Shinya
中科院分区：
文献类型：
--
作者：
Kobayashi, Hisayoshi;Higashimoto, Shinya
通过DFT计算，对TiO2表面的分子氧（O-2）催化氧化苯甲醇进行了理论研究。用Ti16O32和Ti16O32(OH)H平板分别模拟了表面羟基缺失和存在时锐钛矿型TiO2的晶面。计算了苯甲醇与Ti16O32和Ti16O32(OH)H的相互作用。结果表明，TiO2表面羟基在醇氧化合物[Ti]-O-CH2-ph]的形成中起着重要作用。在TiO2的价带（VB）中发现醇氧化合物的轨道与O2p轨道杂化。光催化体系中可见光响应的起源可归因于醇类化合物产生的电子从施主能级到导带（CB）的跃迁。在TiO2表面上确定了苯甲醇合成苯甲醛的整体催化反应的反应座标，并讨论了可见光照射的作用。(C) 2015 Elsevier B.V.版权所有
Theoretical study on the catalytic oxidation of benzyl alcohol by molecular oxygen (O-2) on the TiO2 surface was performed by DFT calculations. The anatase TiO2 crystal faces in the absence and presence of surface hydroxyl groups were modeled with a slab of Ti16O32 and Ti16O32(OH)H, respectively. The interaction of benzyl alcohol with Ti16O32 and Ti16O32(OH)H was calculated. It was clearly demonstrated that the surface hydroxyl groups on the TiO2 surface play a significant role in the formation of the alkoxide [Ti]-O-CH2-ph) species. The orbitals of the alkoxide species was found to be hybridized with the O2p orbital in the valence band (VB) of the TiO2. The origin of the visible-light response in the photo catalytic system can be attributed to the electronic transition from the donor levels created by the alkoxide species to the conduction band (CB). Furthermore, reaction coordinates in the overall catalytic reaction of benzyl alcohol into benzaldehyde on the TiO2 surface were demonstrated, and the role of the visible-light irradiation was also discussed. (C) 2015 Elsevier B.V. All rights reserved.