Stepwise Photocatalytic Dissociation of Methanol and Water on TiO<sub>2</sub>(110) Qing Guo Chenbiao Xu Zefeng Ren Wenshao Yang Zhibo Ma Dongxu Dai Hongjun Fan Timothy K. Minton Xueming Yang 10.1021/ja304049x.s001 https://acs.figshare.com/articles/journal_contribution/Stepwise_Photocatalytic_Dissociation_of_Methanol_and_Water_on_TiO_sub_2_sub_110_/2496193 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. 2012-08-15 00:00:00 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