文献类型：期刊文献

英文题名：Cooperative Motion in Water-Methanol Clusters Controls the Reaction Rates of Heterogeneous Photocatalytic Reactions

作者：Xu, Bei-Bei[1,2];Zhou, Min[3,4];Ye, Man[1,2];Yang, Ling-Yun[5];Wang, Hai-Feng[3,4];Wang, Xue Lu[1,2];Yao, Ye-Feng[1]

机构：[1]East China Normal Univ, Sch Phys & Elect Sci, Phys Dept, Shanghai 200062, Peoples R China;[2]East China Normal Univ, Sch Phys & Elect Sci, Shanghai Key Lab Magnet Resonance, Shanghai 200062, Peoples R China;[3]East China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[5]ShanghaiTech Univ, iHuman Inst, Shanghai 201210, Peoples R China

年份：2021

卷号：143

期号：29

起止页码：10940

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20213110698521);WOS:【SCI-EXPANDED(收录号:WOS:000679913600020)】；

基金：This work was supported by the National Natural Science Foundation of China (Grant nos. 21603073, 21574043, 21873028, and 22072045) and the Shanghai Shuguang Program (Grant 17SG30).

语种：英文

外文关键词：Methanol - Nuclear magnetic resonance - Molecules - Reaction rates - Molecular dynamics - Hydrogen bonds - Molar ratio - Density functional theory - Calculations - Oxide minerals - Titanium dioxide

摘要：Detailed information about the influences of the cooperative motion of water and methanol molecules on practical solid-liquid heterogeneous photocatalysis reactions is critical for our understanding of photocatalytic reactions. The present work addresses this issue by applying operando nuclear magnetic resonance (NMR) spectroscopy, in conjunction with density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations, to investigate the dynamic behaviors of heterogeneous photocatalytic systems with different molar ratios of water to methanol on rutile-TiO2 photocatalyst. The results demonstrate that methanol and water molecules are involved in the cooperative motions, and the cooperation often takes the form of methanol-water clusters that govern the number of methanol molecules reaching to the active sites of the photocatalyst per unit time, as confirmed by the diffusion coefficients of the methanol molecule calculated in the binary methanol-water solutions. Nuclear Overhauser effect spectroscopy experiments reveal that the clusters are formed by the hydrogen bonding between the -OH groups of CH3OH and H2O. The formation of such methanol-water clusters is likely from an energetic standpoint in low-concentration methanol, which eventually determines the yields of methanol reforming products.