摘要
Three 4.8 nm isostructural{M_(72)}(M=Co^(Ⅱ) for CIAC-128,Ni^(Ⅱ) for CIAC-129,Fe^(Ⅱ) for CIAC-130) metal-organic polyhedra(MOPs) are constructed by eighteen M_(4)-p-tert-butylthiacalix[4]arene (M_(4)-TC4A) units bridged via sixteen four-connected 5,5′-(1H-1,2,4-triazole-3,5-diyl) diisophthalic acid (H_(4)TADIPA) linkers.These MOPs are featured with a rarely reported concave coordination cage,which can be simplified as a squeezed double-decker hexagonal prism pressed from the top and bottom hexagonal faces.Furthermore,CIAC-128,CIAC-129 and CIAC-130 are the highest nuclearity discrete clusters of Co,Ni and Fe reported so far.CIAC-128 has higher separation selectivity of C_(3)H_(8) than CH_(4) under ambient conditions,and also exhibits separation selectivity for C_(2)H_(6)/CH_(4),C_(2)H_(2)/CH_(4),and C_(2)H_(4)/CH_(4).In addition,CIAC-128 can provide the cavity for the confined synthesis of noble metal nanoclusters such as Pd nanoclusters and the resulting Pd@CIAC-128 hybrids show higher electrocatalytic activity than commercial Pt/C towards hydrogen evolution reaction (HER).
基金
supported by the National Natural Science Foundation of China(21971233,21571172,51222404)。
