Amino-functionalized organic polymer loaded with highly dispersed CuI for efficient catalytic conversion of CO2 with PA.

The conversion of CO 2 into high value-added chemicals through efficient catalysis is an ideal strategy to reduce atmospheric CO 2 pollution and achieve carbon neutrality. Therefore, amino-functionalized organic polymer Cu@Co-PIL-N 4 loaded with highly dispersed CuI as a novel catalyst was developed. The functionalization of the surface and the high dispersion of the active phase integrate CO 2 capture and conversion into one catalytic system. The locally enriched CO 2 is converted to the easily activated carbon-oxygen negative ion by the action of primary or secondary amines. Thus, it is easier to achieve efficient preparation of α-alkylidene cyclic carbonates (STY = 20.8 h−1) by CO 2 carboxylative cyclization under mild conditions (25 °C, CO 2 pressure of 1 bar). The addition of a small amount of water to the cyclization system boosted domino reaction to convert the α-alkylidene cyclic carbonates to α-hydroxy ketones. The domino reaction also exhibited efficient catalytic activity and outstanding regioselectivity. In addition, the Cu@Co-PIL-N 4 catalyst exhibited excellent substrate expansion and cyclic regeneration for both reactions. This work promises great significance for further developing cost-effective and high-performance catalysts for the chemical conversion of CO 2. [Display omitted] • A novel Cu@Co-PIL-N 4 catalyst was prepared via ion-exchange deposition route. • Cu@Co-PIL-N 4 integrates CO 2 adsorption and capture into one catalytic system. • The novel catalysts exhibited high catalytic efficiency and diversity for CO 2 conversion. • Cu@Co-PIL-N 4 remained highly active for four successive reuses. Typically, the CO 2 concentration in flue gas is very low (around 15%), thus capturing CO 2 from flue gas requires high energy consumption and various purification processes [ 49 , 50 ]. Attributed to the excellent ability of Cu@Co-PIL-N 4 catalyst for CO 2 gas capture, it was applied for the carboxylative cyclization under dilute gas and achieved α-alkylidene cyclic carbonate yield of 68%. Therefore, attributed to these intriguing characteristics, this newly developed catalytic system provides a new strategy for CO 2 capture and flue gas utilization in the field of CCUS (Fig. 5). α-hydroxy ketone is a very important and widely used compound [ 52 , 53 ] as biologically active natural product, pharmaceutical intermediate, and a photoinitiator in UV-curable coatings [ 54 ]. Therefore, the synthesis of α-hydroxy ketones via the triple component reaction of PA-CO 2 -H 2 O is a fascinating strategy bearing the advantages of easy availability of raw materials and green sustainability [ 55 ]. This domino synthesis strategy was further developed by adding a small amount of water to the existing carboxylative cyclization catalytic reaction system. Instead of α-alkylidene cyclic carbonate, 87% of the downstream product α-hydroxy ketone was obtained without any other by-products (Fig. 7). The PAs with different substituents as substrates also generated the corresponding hydroxyl ketones. [ABSTRACT FROM AUTHOR]