Stepwise Photocatalytic Dissociation of Methanol and Water on TiO2(110)

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• 作者：Qing Guo ; Chenbiao Xu ; Zefeng Ren ; Wenshao Yang ; Zhibo Ma ; Dongxu Dai ; Hongjun Fan ; Timothy K. Minton ; Xueming Yang
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：August 15, 2012
• 年：2012
• 卷：134
• 期：32
• 页码：13366-13373
• 全文大小：499K
• 年卷期：v.134,no.32(August 15, 2012)
• ISSN：1520-5126

文摘

We have investigated the photocatalysis of partially deuterated methanol (CD₃OH) and H₂O on TiO₂(110) at 400 nm using a newly developed photocatalysis apparatus in combination with theoretical calculations. Photocatalyzed products, CD₂O on Ti_5c sites, and H and D atoms on bridge-bonded oxygen (BBO) sites from CD₃OH have been clearly detected, while no evidence of H₂O photocatalysis was found. The experimental results show that dissociation of CD₃OH on TiO₂(110) occurs in a stepwise manner in which the O鈥揌 dissociation proceeds first and is then followed by C鈥揇 dissociation. Theoretical calculations indicate that the high reverse barrier to C鈥揇 recombination and the facile desorption of CD₂O make photocatalytic methanol dissociation on TiO₂(110) proceed efficiently. Theoretical results also reveal that the reverse reactions, i.e, O鈥揌 recombination after H₂O photocatalytic dissociation on TiO₂(110), may occur easily, thus inhibiting efficient photocatalytic water splitting.