基于磺酰基杯[4]芳烃的Co16笼簇的合成、结构及电化学性质

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 mV的过电位下达到10.0 mA/cm ²电流密度, Tafel斜率为79.31 mV/dec, 并且在20.0 mA/cm ²电流密度下表现出长达48 h的催化稳定性.

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

A new sulfonylcalix4]arene-supported tetrahedral Co₁₆ cage cluster Co₁₆(TC4A-SO₂)₄(OH)₄·(L)₈](C₈H₂₀N)(C₄H₁₂N)₂(C₂H₈N)]·solvent(Abbr. Co₁₆-TC4A-SO₂) was synthesized from CoCl₂·6H₂O, p-tert-butylsulfonylcalix4]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-SO₂ onto 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 mA/cm ² at a catalytic reaction overpotential of 343.8 mV, a Tafel slope of 79.31 mV/dec, and catalytic stability for 48 h at 20.0 mA/cm ².