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.

Cobalt-based MOF nanoribbons with abundant O/N species for cycloaddition of carbon dioxide to epoxides.

Chemical fixation of CO2 with epoxides is an effective option to achieve sustainable synthesis of cyclic organic carbonates. Although metal-organic frameworks (MOFs) are promising catalysts for this reaction, their low stability in aqueous solutions makes this application infeasible. In an effort to overcome this limitation, cobalt-based metal-organic framework (Co(II)MOF) nanoribbons have been prepared by coordinating the Co(II) ions with a new ligand (C16H12N4O4) full of oxygen and nitrogen moieties. Strong chemical interactions occur between the adsorbed CO2 and oxygen/nitrogen atoms in this porous MOF structure. Co(II)-MOF nanoribbons with tetra-n-butylammonium bromide acted as cocatalysts with ∼97% yield of cyclic carbonate (reaction kinetic rate of 14.7 × 106 µmol g-1 h-1) upon the cycloaddition of epichlorohydrin (ECH) to CO2 (>99% reaction selectivity under solvent-free reaction condition at 80 °C, 3 h and 1 MPa CO2 pressure). This work may open a new avenue for chemical fixation of CO2 by rational design of the components and morphology of MOF-based catalysts.