Hydroxyl and amino dual-functionalized core-shell molecular sieves featuring hydrogen bond donor groups for efficient CO2 cycloaddition

In CO2 cycloaddition reactions, hydrogen bond donor (HBD) groups are considered environmentally friendly substitutes for metals to promote epoxide ring-opening through interactions with nucleophilic anions. A core-shell structured ILs-based catalyst (mSiO2@MCM-NH2-OH) with dual hydrogen bond donors (–OH and –NH2) was synthesized by copolymerization strategy. Through in-depth characterization, it has been demonstrated that the catalyst (mSiO2@MCM-NH2-OH) possesses multiple catalytic active sites including –OH, –NH2, Br- groups, and the synergistic effect of double HBD groups (–OH and –NH2) and Lewis base (Br-) significantly improved the catalytic activity. Meanwhile, the core-shell structure of the catalyst effectively prevents the loss of active components, which makes the yield remain at about 94 % after 10 cycles. Based on Density Functional Theory (DFT) calculations, a synergistic catalytic mechanism, which involves dual hydrogen-bond donors (–OH and –NH2) and Lewis bases (Br-) was proposed. The cooperative interaction between –OH/–NH2 and Br- reduced the ring-opening barrier of epoxide from 58.6 to 32.0 kcal mol−1 significantly, and thereby facilitated the CO2 cycloaddition reaction.