文献类型：期刊文献

英文题名：Mechanistic study on the formation of the alkyl acrylates from CO2, ethylene and alkyl iodides over nickel-based catalyst

作者：Zhu, Youcai[1];Mu, Yue[1];Sun, Li[1];Zeng, Zuoxiang[1];Liu, Zhen[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China

年份：2023

卷号：25

期号：36

起止页码：24733

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;EI(收录号：20233814749099);WOS:【SCI-EXPANDED(收录号:WOS:001062217200001)】；

基金：We thank the National Natural Science Foundation of China (22171084). The authors thank the financial support by Shanghai Pujiang Program (18PJ1402500), and the Open Project of State Key Laboratory of Chemical Engineering (SKL-ChE-18C01) at the East China University of Science and Technology. We acknowledge the supercomputer at East China University of Science and Technology for generous computing resources.

语种：英文

外文关键词：Catalysts - Charge transfer - Energy barriers - Ethylene - Nickel - Nickel compounds - Propionic acid - Salts

摘要：The catalytic conversion of carbon dioxide (CO2) and olefins into acrylates has been a long standing target, because society attempts to synthesize commodity chemicals in a more economical and sustainable fashion. In this work, two alkylation reaction pathways were investigated to explore the role of methylene linkage (-CH2-) on the formation of alkyl acrylate from coupling of CO2 and ethylene, catalyzed by a nickel catalyst in the presence of different alkyl iodides. The energy barrier of Ni-O bond cleavage decreases with increasing methylene linkage of alkyl iodides, which may be due to NPA charge transfer of alkyl iodides. Meanwhile, the O-1 (ester sp(3)O atom) attack route leading to the formation of alkyl acrylate competes with the O-2 (carboxylic sp(2)O atom) attack route in terms of energy barriers. Further studies on the fluoro-substituted alkyl acrylates show that neither CF3I nor CF3CH2I is effective in releasing trifluoroalkyl acrylates from the nickellacycle, which explains why only negligible amounts of the desired product were detected in the experiment. In addition, we investigated the non-productive pathways leading to byproducts, such as propionic acid, propionates and ion pair complexes, etc. By comparing the results obtained with CH3I, the use of C2H5I as an electrophilic reagent may stabilize the non-productive intermediates. The methylene linkage has little effect on the main productive pathway. However, it has a significant influence on the side reactions, which is detrimental to the formation of alkyl acrylate in competing with the main productive pathway.