Abstract:

Carbon dioxide conversion to value-added chemicals is one of the effective strategies to achieve the “carbon neutral” target. Carboxylation of unsaturated hydrocarbons with CO₂ as carboxyl source and transition metal as catalyst is a new technology for valuable utilization of CO₂ to synthesize acrylic acid derivatives. This review summarizes the application of different metal catalysts (Ni, Pd, Cu, etc.) in the carboxylation of CO₂ with olefins, alkynes, and allenes, which focuses on the metal-ligand optimization and the regulation of reaction conditions in different catalytic systems. The catalytic characteristics and mechanism of different catalysts are systematically compared, and some key issues such as the rate-controlling step in the catalytic reaction cycle and catalyst regeneration are discussed. Finally, the future research directions and applications of the catalytic reaction systems involving the above three unsaturated hydrocarbons are prospected. It is speculated that the process of coupling carboxylation of CO₂ and ethylene to prepare acrylic acid has industrial prospects, while the development and optimization of the related reactions in the reductive carboxylation systems of CO₂ with alkynes or allenes would provide new ideas for the efficient synthesis of highly regioselective unsaturated carboxylic acid derivatives.

Key words: acrylic acid, carbon dioxide, metal catalysis, carboxylation, carbon neutral

摘要：

CO₂高值转化是“双碳”目标大背景下碳利用的有效方式。过渡金属络合物催化的CO₂与不饱和烃羧化反应是合成丙烯酸及其衍生物的新路线，也是CO₂高值利用的新途径。本文总结了多种金属络合物（Ni、Pd、Cu等）在催化CO₂与烯烃偶联羧化、CO₂与炔烃或联烯还原羧化制丙烯酸及其衍生物中的应用，着重概述了不同催化体系中的金属-配体优化和反应条件调控，系统对比了不同催化剂的催化特点和作用机制，并论述了其催化反应循环中的控速步骤以及催化剂再生等关键问题。最后，对过渡金属络合物催化CO₂与乙烯偶联羧化制备丙烯酸及CO₂与炔烃或联烯还原羧化合成高区域选择性不饱和羧酸衍生物的后续研究方向和应用前景进行了展望。

关键词: 丙烯酸, 二氧化碳, 金属催化, 羧化反应, 碳中和