Guo, Qing Xu, Chenbiao Ren, Zefeng Yang, Wenshao Ma, Zhibo Dai, Dongxu Fan, Hongjun Minton, Timothy K. Yang, Xueming Stepwise Photocatalytic Dissociation of Methanol and Water on TiO<sub>2</sub>(110) We have investigated the photocatalysis of partially deuterated methanol (CD<sub>3</sub>OH) and H<sub>2</sub>O on TiO<sub>2</sub>(110) at 400 nm using a newly developed photocatalysis apparatus in combination with theoretical calculations. Photocatalyzed products, CD<sub>2</sub>O on Ti<sub>5c</sub> sites, and H and D atoms on bridge-bonded oxygen (BBO) sites from CD<sub>3</sub>OH have been clearly detected, while no evidence of H<sub>2</sub>O photocatalysis was found. The experimental results show that dissociation of CD<sub>3</sub>OH on TiO<sub>2</sub>(110) occurs in a stepwise manner in which the O–H dissociation proceeds first and is then followed by C–D dissociation. Theoretical calculations indicate that the high reverse barrier to C–D recombination and the facile desorption of CD<sub>2</sub>O make photocatalytic methanol dissociation on TiO<sub>2</sub>(110) proceed efficiently. Theoretical results also reveal that the reverse reactions, i.e, O–H recombination after H<sub>2</sub>O photocatalytic dissociation on TiO<sub>2</sub>(110), may occur easily, thus inhibiting efficient photocatalytic water splitting. BBO;calculation;photocatalytic methanol dissociation;Stepwise Photocatalytic Dissociation;Theoretical;TiO;H 2O photocatalytic dissociation;CD 2O;Ti 5c sites;recombination;photocatalytic water splitting;CD 3OH;H 2O photocatalysis 2012-08-15
    https://acs.figshare.com/articles/journal_contribution/Stepwise_Photocatalytic_Dissociation_of_Methanol_and_Water_on_TiO_sub_2_sub_110_/2496193
10.1021/ja304049x.s001