Mechanisms of isomerization and hydration reactions of typicalβ-diketone at the air-droplet interface  

作　　者：Yuemeng Ji Weiyong Luo Qiuju Shi Xiaohui Ma Ziqi Wu Weina Zhang Yanpeng Gao Taicheng An 

机构地区：[1]Guangdong-Hong Kong-Macao Joint Laboratory for Contaminants Exposure and Health,Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control,Institute Environmental Health and Pollution Control,Guangdong University of Technology,Guangzhou 510006,China [2]Guangzhou Key Laboratory of Environmental Catalysis and Pollution Control,Key Laboratory for City Cluster Environmental Safety and Green Development of the Ministry of Education,School of Environmental Science and Engineering,Guangdong University of Technology,Guangzhou 510006,China

出　　处：《Journal of Environmental Sciences》2024年第7期225-234,共10页环境科学学报（英文版）

基　　金：supported by the Guangdong Basic and Applied Basic Research Foundation(No.2019B151502064);the National Natural Science Foundation of China(Nos.42077189,42020104001,and 42277081);the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01Z032);the Science and Technology Key Project of Guangdong Province;China(No.2019B110206002);the Guangdong Provincial Key R&D Program(No.2022-GDUT-A0007)。

摘　　要：Acetylacetone(AcAc)is a typical class ofβ-diketones with broad industrial applications due to the property of the keto-enol isomers,but its isomerization and chemical reactions at the air-droplet interface are still unclear.Hence,using combined molecular dynamics and quantum chemistry methods,the heterogeneous chemistry of AcAc at the air-droplet interface was investigated,including the attraction of AcAc isomers by the droplets,the distribution of isomers at the air-droplet interface,and the hydration reactions of isomers at the air-droplet interface.The results reveal that the preferential orientation of two AcAc isomers(keto-and enol-AcAc)to accumulate and accommodate at the acidic air-droplet interface.The isomerization of two AcAc isomers at the acidic air-droplet interface is more favorable than that at the neutral air-droplet interface because the“water bridge”structure is destroyed by H_(3)O^(+),especially for the isomerization from keto-Ac Ac to enol-AcAc.At the acidic air-droplet interface,the carbonyl or hydroxyl O-atoms of two AcAc isomers display an energetical preference to hydration.Keto-diol is the dominant products to accumulate at the air-droplet interface,and excessive keto-diol can enter the droplet interior to engage in the oligomerization.The photooxidation reaction of AcAc will increase the acidity of the air-droplet interface,which indirectly facilitate the uptake and formation of more keto-diol.Our results provide an insight into the heterogeneous chemistry ofβ-diketones and their influence on the environment.

关 键 词：ACETYLACETONE Air-droplet interface Theoretical simulation ISOMERIZATION Hydration reaction mechanism 

分 类 号：TQ224.24[化学工程—有机化工]