Metalloporphyrin-based porous organic polymers that behave as advanced biomimetic nanoreactors have drawn continuous attention for heterogeneous CO₂ cycloaddition conversion in the past decades. However, the use of homogeneous onium salts, usually acting as nucleophilic cocatalysts, may increase the cost of product purification and cause additional environmental problems. In this contribution, a new aluminum porphyrin-based porous hyper-cross-linked polymer modified by imidazolium salts (denoted as Im@Al-HCP) has been successfully constructed for the first time. The two-step process of hyper-cross-linking reaction combined with postsynthetic modification endows the catalyst with a large surface area (about 213 m²·g^–1), good CO₂ adsorption capacity (up to 1.45 mmol·g^–1), and highly dispersed cooperative active sites. Accordingly, bifunctional Im@Al-HCP exhibits an outstanding catalytic activity, good recyclability, and broad substrate generality without cocatalysts and solvents under mild conditions. In particular, a high turnover frequency (TOF) value of up to 5000 h^–1 can be acquired, which far exceeds that of most reported heterogeneous catalysts under identical conditions. In addition, the as-made heterogeneous catalyst can be recycled for at least six times without an obvious loss in catalytic activity. This work not only bring some inspirations for the construction of multifunctional catalysts but also provides great potential for industrial applications of CO₂ cycloadditions.

中文翻译：

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一种新型铝卟啉基多孔超交联聚合物，经咪唑盐改性，可在温和条件下协同将 CO2 转化为环状碳酸盐


在过去的几十年里，作为高级仿生纳米反应器的金属卟啉基多孔有机聚合物引起了异质 CO₂ 环加成转化的持续关注。然而，使用通常充当亲核助催化剂的均相鎓盐可能会增加产品纯化成本并导致额外的环境问题。在这项贡献中，首次成功构建了一种由咪唑盐 （表示为 Im@Al-HCP） 修饰的新型铝卟啉基多孔超交联聚合物。超交联反应结合合成后改性的两步过程赋予了催化剂较大的表面积（约 213 m²·g^–1）、良好的 CO₂ 吸附能力（高达 1.45 mmol·g^–1）和高度分散的协同活性位点。因此，双功能 Im@Al-HCP 在温和条件下表现出出色的催化活性、良好的可回收性和广泛的底物通用性，无需助催化剂和溶剂。特别是，可以获得高达 5000 ^h-1 的高周转频率 （TOF） 值，这远远超过了相同条件下大多数已报道的非均相催化剂。此外，所制备的非均相催化剂可以回收至少六次，而不会明显损失催化活性。这项工作不仅为多功能催化剂的构建带来了一些启发，也为 CO₂ 环加成反应的工业应用提供了巨大的潜力。