含膦胺配体的1,2-二芳基乙烯-1,2-二硫醇镍配合物的合成、结构表征与电催化制氢性能  

Synthesis,structural characterization and properties of the electrocatalyticly prepared hydrogen of 1,2-diarylethylene-1,2-dithiolate nickel complexes with bis(diphenylphosphanyl)amine ligand

作　　者：纪润武 何毅 姚博馨 刘梦南 何佳钰 赵文怀 谢斌 JI Runwu;HE Yi;YAO Boxin;LIU Mengnan;HE Jiayu;ZHAO Weihuai;XIE Bin(School of Materials Science and Engineering,Sichuan University of Science and Engineering,Zigong,Sichuan 643000,China;School of Chemistry and Environmental Engineering,Sichuan University of Science and Engineering,Zigong,Sichuan 643000,China;Material Corrosion and Protection Key Laboratory of Sichuan Province,Sichuan University of Science and Engineering,Zigong,Sichuan 643000,China)

机构地区：[1]四川轻化工大学材料科学与工程学院,四川自贡643000 [2]四川轻化工大学化学与环境工程学院,四川自贡643000 [3]四川轻化工大学材料腐蚀与防护四川省重点实验室,四川自贡643000

出　　处：《内江师范学院学报》2024年第4期72-80,共9页Journal of Neijiang Normal University

基　　金：四川省科技厅项目(2023NSFSC0087);化学合成与污染控制四川省重点实验室项目(CSPC202201);四川轻化工大学研究生创新基金项目(y2020076);四川轻化工大学大学生创新创业训练计划项目(CX2023007)。

摘　　要：合成了10种含膦胺配体的1,2-二芳基乙烯-1,2-二硫醇的镍配合物[(p-XC_(6)H_(4)N(PPh_(2))2)Ni(S_(2)C_(2)(C_(6)H_(4)Y-p)2)](1:X=Br,Y=CH_(3)O;2:X=Br,Y=CH 3;3:X=Br,Y=H;4:X=Br,Y=Br;5:X=Br,Y=F;6:X=F,Y=CH_(3)O;7:X=F,Y=CH 3;8:X=F,Y=H;9:X=F,Y=Br;10:X=F,Y=F),通过元素分析、核磁共振谱、红外光谱和紫外-可见吸收光谱对镍配合物的结构进行了表征.配合物l DMF的X-射线单晶衍射分析表明镍原子处于近乎完美的四方平面构型的S_(2)P_(2)配位环境中,通过循环伏安法测定了配合物在DMF溶液中的电化学性质以及在三氟乙酸(TFA)存在时的电催化制氢性能.研究结果表明:0.25 mmol配合物1-10在添加67.317 mM TFA时,其电催化制氢的转换频率和过电位分别为299.3~809.7 s^(-1)和0.867~0.995 V.Ten nickel complexes bearing 1,2-diarylethylene-1,2-dithiolate and bis(diphenylphosphanyl)amine ligands,[(p-XC_(6)H_(4)N(PPh_(2))2)Ni(S_(2)C_(2)(C_(6)H_(4)Y-p)2)](1:X=Br,Y=CH_(3)O;2:X=Br,Y=CH 3;3:X=Br,Y=H;4:X=Br,Y=Br;5:X=Br,Y=F;6:X=F,Y=CH_(3)O;7:X=F,Y=CH 3;8:X=F,Y=H;9:X=F,Y=Br;10:X=F,Y=F),were synthesized and characterized by elemental analysis,nuclear magnetic resonance spectroscopies,infrared spectra,and ultraviolet-visible absorption spectroscopies.The X-ray single crystal diffraction analysis of 1 DMF showed that the nickel atom is located in the S_(2)P_(2)coordination environment with an almost perfectly square planar.The electrochemical properties of the complexes in DMF solution and the electrocatalytic hydrogen evolution performance in the presence of trifluoroacetic acid(TFA)were determined by cyclic voltammetry.The research results indicated that the conversion frequencies and overpotentials of the electrocatalytic hydrogen evolution for 0.25 mmol complexes 1—10 in the presence of 67.317 mM TFA are 299.3-809.7 mmol^(-1) and 0.867-0.995V,respectively.

关 键 词：膦胺 1 2-二芳基乙烯-1 2-二硫醇 镍配合物 合成 电催化制氢 

分 类 号：O621[理学—有机化学]