Catalytic fixation of greenhouse gas CO₂ into value-added chemicals under mild conditions was deemed as an effective pathway for carbon emissions mitigation, though facing big challenges. Herein, a novel hydroxyl-ionic liquid functionalized metalloporphyrin (ZnTpyp-IL) catalyst bearing hydrogen bond donor (HBD), Lewis acidic and nucleophilic sites was fabricated and invested in the CO₂ cycloaddition without additive or solvent. The integration of ionic liquid endowed the framework with strong surface affinity to enrich CO₂ molecules, while the cooperative interplay of multiple active sites further promoted the high-selective conversion of epichlorohydrin (ECH). Under optimal conditions (100 °C, 1 MPa, 4 h), the yield of corresponding chloropropene carbonate (CPC) reached 97.1 % (turnover frequency (TOF) = 52.4 h^-1), far superior to that of bare Tpyp (17.4 %). The preliminary kinetic studies revealed the lower activation energy (59.54 kJ/mol) needed to be overcome in the ring-opening process over ZnTpyp-IL. Moreover, a plausible dual-activation mechanism of hydrogen bonds and Zn centers for epoxides was proposed based on the density functional theory calculation (DFT) to explain the acceleration of rate-determining step. Coupled with the satisfactory reusability and substrate expansibility, the developed ZnTpyp-IL demonstrated its great potential as robust heterogeneous catalyst in the efficient utilization of C₁ resource.

_{尽管面临巨大挑战，但在温和条件下将温室气体 CO 2}催化固定为增值化学品被认为是减缓碳排放的有效途径。在此，制备了一种新型羟基离子液体功能化金属卟啉 (ZnTpyp-IL) 催化剂，该催化剂具有氢键供体 (HBD)、路易斯酸性和亲核位点，并在没有添加剂或溶剂的情况下投入到 CO _{2环加成反应中。}离子液体的整合赋予骨架强表面亲和力以富集CO ₂分子，而多个活性位点的协同相互作用进一步促进了环氧氯丙烷（ECH）的高选择性转化。在最佳条件下（100 ℃、1 MPa、4 h），相应的氯丙烯碳酸酯（CPC）收率达到97.1%（周转频率（TOF）=52.4 h ^-1)，远远优于裸 Tpyp (17.4 %)。初步动力学研究表明，在 ZnTpyp-IL 的开环过程中需要克服较低的活化能 (59.54 kJ/mol)。此外，基于密度泛函理论计算（DFT），提出了环氧化物氢键和Zn中心的双活化机制来解释速率决定步骤的加速。再加上令人满意的可重复使用性和底物可扩展性，所开发的 ZnTpyp-IL 在高效利用 C ₁资源方面显示出其作为稳健多相催化剂的巨大潜力。