Investigations on metal–organic frameworks (MOFs) as direct catalysts have been well documented, but direct catalysis of the chemical conversion of terminal alkynes and CO₂ as chemical feedstock by MOFs into valuable chemical products has never been reported. We report here two cluster-based MOFs I and II assembled from a multinuclear Gd-cluster and Cu-cluster, displaying high thermal and solvent stabilities. I and II as heterogeneous catalysts possess active catalytic centers [Cu₁₂I₁₂] and [Cu₃I₂], respectively, exhibiting excellent catalytic performance in the carboxylation reactions of CO₂ with 14 kinds of terminal alkynes under 1 atm and mild conditions. For the first time catalysis of the carboxylation reaction of terminal alkynes with CO₂ by MOF materials without any cocatalyst/additive is reported. This work not only reduces greenhouse gas emission but also provides highly valuable materials, opening a wide space in seeking recoverable catalysts to accelerate the chemical conversion of CO₂.

中文翻译：

---

基于团簇的MOF，通过CC键的形成可加速CO _2的化学转化

关于金属-有机骨架（MOFs）作为直接催化剂的研究已经有充分的文献记载，但是从未报道过将MOFs直接催化末端炔烃和CO ₂作为化学原料的化学转化成有价值的化学产物的报道。我们在这里报告了由多核Gd团簇和Cu团簇组装而成的两个基于簇的MOF I和II，显示出高的热稳定性和溶剂稳定性。作为非均相催化剂的I和II分别具有活性催化中心[Cu ₁₂ I ₁₂ ]和[Cu ₃ I ₂ ]，在CO ₂的羧化反应中表现出优异的催化性能。在1个大气压和温和条件下具有14种末端炔烃。首次报道了MOF材料在没有任何助催化剂/添加剂的情况下催化末端炔烃与CO ₂的羧化反应。这项工作不仅减少了温室气体的排放，而且还提供了极有价值的材料，为寻求可回收的催化剂以加速CO ₂的化学转化打开了广阔的空间。