Abstract:
The Cu-glutathione (GSH) redox system, essential in biology, is designed here as a supramacromolecular assembly in which the tetrahedral 18e Cu(I) center loses a thiol ligand upon adsorption onto ZIF-8, as shown by EXAFS and DFT calculation, to generate a very robust 16e planar trigonal single-atom Cu(I) catalyst. Synergy between Cu(I) and ZIF-8, revealed by catalytic experiments and DFT calculation, affords CO2 conversion into high-value-added chemicals with a wide scope of substrates by reaction with terminal alkynes or propargyl amines in excellent yields under mild conditions and reuse at least 10 times without significant decrease in catalytic efficiency.
摘要:
Cu-谷胱甘肽(GSH)氧化还原体系,在生物学中必不可少的,在这里设计为超大分子组装体,其中四面体18eCu(I)中心在吸附到ZIF-8上时失去硫醇配体,如EXAFS和DFT计算所示,生成非常稳健的16e平面三角单原子Cu(I)催化剂。催化实验和DFT揭示了Cu(I)和ZIF-8之间的协同作用,通过在温和条件下与末端炔烃或炔丙基胺以优异的产率反应,可以将CO2转化为具有广泛底物的高附加值化学品,并重复使用至少10次而不会显着降低催化效率。