双膦配体桥联的四铁配合物的电催化产氢性能  

Electrocatalytic hydrogen evolution performance of tetra⁃iron complexes with bridging diphosphine ligands

作　　者：朱霖洁 刘旭锋[1] ZHU Linjie;LIU Xufeng(School of Materials and Chemical Engineering,Ningbo University of Technology,Ningbo,Zhejiang 315211,China)

机构地区：[1]宁波工程学院材料与化学工程学院,宁波315211

出　　处：《无机化学学报》2025年第2期321-328,共8页Chinese Journal of Inorganic Chemistry

基　　金：浙江省自然科学基金(No.LY19B020002)资助。

摘　　要：通过配体取代反应合成了2个双膦配体桥联的四铁配合物[Fe_(4)(CO)_(10)(μ-SCH_(2)CH(CH_(3))S)_(2)(dppa)](1)和[Fe_(4)(CO)_(10)(μ-SCH_(2)CH(CH_(3))S)_(2)(trans-dppv)](2),其中dppa=双(二苯基膦)乙炔,trans-dppv=trans-1,2-双(二苯基膦)乙烯。配合物的结构经过元素分析、红外光谱、核磁共振氢谱、磷谱以及单晶X射线衍射等方法的表征。用循环伏安法研究了新配合物的电化学性质,结果表明它们均可以在乙腈溶液中催化醋酸中的质子还原产生氢气。其中配合物2的催化效率要明显优于配合物1。Two tetra-iron complexes with bridging diphosphine ligands,named[Fe_(4)(CO)_(10)(μ-SCH_(2)CH(CH_(3))S)_(2)(dppa)](1)and[Fe_(4)(CO)_(10)(μ-SCH_(2)CH(CH_(3))S)_(2)(trans-dppv)](2),wheredppa=bis(diphenylphosphino)acetyleneand trans-dppv=trans-1,2-bis(diphenylphosphino)ethylene,were prepared by the reaction of complex[Fe_(2)(CO)_(6)(μ-SCH_(2)CH(CH_(3))S)]with dppa or trans-dppv.Both complexes were structurally identified by elemental analysis,FTIR spectra,1H NMR,and 31P NMR,together with single-crystal X-ray diffraction analysis.X-ray crystallographic studies revealed that complex 1 consists of two di-iron propane-1,2-dithiolate pentacarbonyl sub-units connected by a linear dppa ligand whereas a zigzag trans-dppv ligand is found in complex 2.The electrochemical properties were probed by cyclic voltammetry,showing that two irreversible reductions and one irreversible oxidation were found for both complexes.Furthermore,electrocatalytic studies were carried out by adding acetic acid as a proton source into the solution.The results demonstrated that both complexes can catalyze proton reduction to evolve hydrogen.For comparison,the catalytic efficiency of complex 2 was better than complex 1.CCDC:2358741,1;2358742,2.

关 键 词：四铁配合物 晶体结构 循环伏安 电催化产氢 

分 类 号：O614.811[理学—无机化学]