金属硫族非超四面体In—Sn—S团簇的合成、结构及电催化氧还原反应性能

Synthesis,structure,and electrocatalytic oxygen reduction reaction properties of metal chalcogenide non‑supertetrahedral In—Sn—S cluster materials

开发由金属In和Sn参与构筑的金属硫族非超四面体(non-Tn)团簇材料,对于实现该类材料的结构多样性及丰富其光电应用十分重要。利用溶剂热法合成了一系列新的non-Tn团簇化合物(C_(7)H_(13)N_(2))[InS_(2)](1)、(C_(7)H_(13)N_(2))_(4)[In_(2)S_(11)Sn_(3)](2)和(C_(7)H_(13)N_(2))_(3)[In_(3)S_(12)Sn_(3)](3),其中C_(7)H_(13)N_(2)=质子化的1,5-二氮杂双环[4.3.0]壬-5-烯。3种化合物由{SnS4}、{InS4}或{InS5}三个配位单元之间以边共享或顶点共享的方式组合而成。电催化氧还原反应(ORR)研究表明,化合物1~3的还原峰电位分别为0.60、0.64和0.65 V,含有Sn(Ⅳ)的化合物2和3表现出更好的催化性能。不仅如此,Koutecky-Levich图分析表明,化合物中In和Sn的组成比例对其ORR催化路径有明显的调节作用。

The development of metal chalcogenide non-supertetrahedral(non-Tn)cluster materials composed of metal In and Sn is very important for realizing the structural diversity of the materials and enriching their photoelectric applications.Herein,a series of new non-Tn cluster-based compounds C_(7)H_(13)N_(2)[InS_(2)](1),(C_(7)H_(13)N_(2))_(4)[In_(2)S_(11)Sn_(3)](2),and(C_(7)H_(13)N_(2))3[In_(3)S_(12)Sn_(3)](3)were prepared by the solvothermal method,where C_(7)H_(13)N_(2)=protonated 1,5-diazabicyclo[4.3.0]non-5-ene.The three compounds are formed by the combination of{SnS4},{InS4},or{InS5}coordination units in the way of edge-sharing or vertex-sharing.The electrocatalytic oxygen reduction reaction(ORR)study showed that the reduction peak potentials of compounds 1-3 were 0.6,0.64,and 0.65 V,respectively,which indicates that compounds 2 and 3 containing Sn􀃯have better catalytic performance.More than that,the Koutecky-Levich plot analysis showed that the composition ratio of In and Sn in the compounds has a significant modulating effect on the ORR catalytic pathways.