双核钴锰酞菁对SOCl_2还原反应的电催化性能

Electrocatalytic Performance of Binuclear Co-Mn Phthalocyanine for the Reduction of Thionyl Chloride

为了确定双核金属酞菁化合物对亚硫酰氯还原反应是否具有比单核金属酞菁更强的电催化性能,通过循环伏安测试方法,用酞菁钴和酞菁铁作为对比,研究了双核钴锰酞菁在1.5mol·L-1LiAlCl4/SOCl2电解液中的电催化行为,并计算出动力学参数,由此来评估具有平面结构的双核金属酞菁化合物对亚硫酰氯还原的催化活性的影响.通过比较循环伏安曲线发现,与单核酞菁钴(II)和酞菁铁(II)相比,双核钴锰酞菁对SOCl2还原反应具有更好的催化活性,能提高SOCl2还原反应的交换速率常数和SOCl2在玻碳电极上的扩散系数,从而提高SOCl2还原电位和电流.通过ER14250型实体电池10mA放电性能测试验证表明,与单核酞菁钴和酞菁铁催化剂的电池相比,双核钴锰酞菁在低温(-30℃)下可提高放电中点电压0.3V,在常温(25℃)下可以提高放电容量约100mAh,催化效果比单核酞菁钴和酞菁铁显著.

We used cyclic voltammetry to study the electrocatalytic behavior of binuclear Co-Mn phthalocyanine to determine whether binuclear phthalocyanine compounds have better electrocatalytic performance for the reduction of thionyl chloride than the mononuclear phthalocyanine compounds, cobalt phthalocyanine and iron phthalocyanine. Experiments were conducted in 1.5 mol·L^-1 LiAlCl4/SOCl2 electrolyte solution and kinetic parameters were calculated to assess the electrocatalytic performance of the planar binuclear Co-Mn. Cyclic voltammograms showed that by comparison to the mononuclear cobalt phthalocyanine and iron phthalocyanine, the binuclear Co-Mn phthalocyanine had better catalytic activity for the reduction of thionyl chloride. The binuclear Co-Mn phthalocyanine increases the SOCl2 reduction potential and current by improving the exchange rate constant of SOCl2 reduction and the diffusion coefficient of SOCl2 on a glassy carbon electrode. Constant-current （10 mA） discharge curves of real ER14250-type Li/SOCl2 cells demonstrated that the binuclear Co-Mn phthalocyanine catalyst, which has better electrocatalytic activity than the mononuclear cobalt phthalocyanine and iron phthalocyanine, can increase the mid-point voltage to 0.3 V at low temperature （-30℃） and improve the discharge capacity to about 100 mAh at room temperature （25 ℃）.