Low-Temperature Aldol Condensation of Aldehydes on R-TiO2(100)-(1 x 1): Exceptional Selectivity for alpha,beta-Unsaturated Enal Production

Li, Fangliang1,2; Wang, Binli1,3; Chen, Xiao2; Fan, Hongjun1; Yang, Xueming1,2; Guo, Qing2

2021-02-18

10.1021/acs.jpclett.0c03801

Journal of Physical Chemistry Letters   影响因子和分区

1948-7185

Selective C-C coupling of oxygenates via aldol condensation has the potential to produce useful chemicals from aldehydes and ketones. Here we report a combined experimental and theoretical study on the aldol condensation of unbranched aldehydes (CnH2n+1-CHO, n = 1-4) on rutile (R)-TiO2(100)-(1 x 1). Experimental results show that the R-TiO2(100)-(1 x 1) surface has a very high reactivity and selectivity for aldol product formation from tested aldehydes at room temperature. Theoretical calculations indicate that the CH3CHO enolization and the aldol dehydration occur with low energy barriers, and the 3-butanolal intermediate adsorbs on R-TiO2(100)-(1 x 1) stably, suggesting that the surface has a "modest" acid-base strength for efficient crotonaldehyde formation. The adsorption configuration of CH3CHO and surface structure of R-TiO2(100)(1 x 1) may contribute to the exclusive selectivity of (E)-crotonaldehyde formation, which provides us a deep insight into the high selectivity of aldol condensation of aldehydes on the TiO2 catalyst.

SCI ; EI

英语

NI期刊 ; NI论文

通讯

National Key R&D Program of China[2018YFE0203002] ; National Natural Science Foundation of China[21673235,21873096] ; Strategic Priority Research Program of Chinese Academy of Sciences[XDB17000000] ; Shenzhen Science and Technology Innovation Committee[JCYJ2019080914021660] ; Guangdong Innovative & Entrepreneurial Research Team Program["2019ZT08L455","2019JC01X091"] ; International Partnership Program of Chinese Academy of Science[121421KYSB20170012]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Atomic, Molecular & Chemical

WOS:000621419900018

AMER CHEMICAL SOC

20210910009746

Aldehydes ; Condensation ; Condensation reactions ; Ketones ; Low temperature production ; Oxide minerals ; Surface structure ; Temperature ; Titanium dioxide

Minerals:482.2 ; Thermodynamics:641.1 ; Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Physical Properties of Gases, Liquids and Solids:931.2

Web of Science

1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
3.Univ Chinese Acad Sci, Beijing 100049, Peoples R China

Li, Fangliang,Wang, Binli,Chen, Xiao,et al. Low-Temperature Aldol Condensation of Aldehydes on R-TiO2(100)-(1 x 1): Exceptional Selectivity for alpha,beta-Unsaturated Enal Production[J]. Journal of Physical Chemistry Letters,2021,12(6):1708-1717.

Li, Fangliang,Wang, Binli,Chen, Xiao,Fan, Hongjun,Yang, Xueming,&Guo, Qing.(2021).Low-Temperature Aldol Condensation of Aldehydes on R-TiO2(100)-(1 x 1): Exceptional Selectivity for alpha,beta-Unsaturated Enal Production.Journal of Physical Chemistry Letters,12(6),1708-1717.

Li, Fangliang,et al."Low-Temperature Aldol Condensation of Aldehydes on R-TiO2(100)-(1 x 1): Exceptional Selectivity for alpha,beta-Unsaturated Enal Production".Journal of Physical Chemistry Letters 12.6(2021):1708-1717.