基于磺酰基杯[4]芳烃的Co16笼簇的合成、结构及电化学性质

Synthesis,Structure and Electrochemical Properties of Sulfonylcalix[4] arene Supported Co16 Cluster

以氯化钴、对叔丁基磺酰杯[4]芳烃(H4TC4A-SO2)和非对称性3-(1H-四唑-5-基)苯甲酸(H2L)为原料,通过溶剂热法合成了一个具有四面体配位笼结构的16核化合物[Co16(TC4A-SO2)4(OH)4(L)8]·[(C8H20N)(C4H12N)2(C2H8N)]·solvent(Co16-TC4A-SO2).采用X射线单晶衍射、X射线粉末衍射、热重分析、红外光谱方法对配合物进行了表征.将Co16-TC4A-SO2笼簇直接负载到碳纸上(Co16-TC4A-SO2/CP)用作工作电极,其对析氧反应(OER)展现出较好的催化性能.在1 mol/L KOH中,Co16-TC4A-SO2/CP在343.8 m V的过电位下达到10.0 m A/cm^2电流密度,Tafel斜率为79.31 m V/dec,并且在20.0 m A/cm2电流密度下表现出长达48 h的催化稳定性.

A new sulfonylcalix[4]arene-supported tetrahedral Co16cage cluster[Co16(TC4A-SO2)4(OH)4·(L)8][(C8H20N)(C4H12N)2(C2H8N)]·solvent(Abbr.Co16-TC4A-SO2)was synthesized from Co Cl2·6H2O,p-tert-butylsulfonylcalix[4]arene(H4TC4A-SO2)and asymmetric 3-(1H-tetrazol-5-yl)benzoic acid(H2L)under solvothermal condition.The complex was characterized by single crystal X-ray diffraction(XRD),powder X-ray diffraction(PXRD),thermogravimetric analysis(TGA),and infrared spectroscopy(FTIR).Directly loading Co16-TC4A-SO2onto carbon paper(Co16-TC4A-SO2/CP)as a working electrode exhibited efficient oxygen evolution reaction(OER)catalytic performance.In 1 mol/L KOH,Co16-TC4A-SO2/CP gained a current density of 10.0 m A/cm2at a catalytic reaction overpotential of 343.8 m V,a Tafel slope of 79.31 m V/dec,and catalytic stability for 48 h at 20.0 m A/cm2.