可见光驱动[FeFe]氢化酶模拟物催化分解水产氢性能研究  

Performance of Visible Light-induced[FeFe]Hydrogenase Mimetic in Catalytic Water Splitting for Hydrogen Production

作　　者：郑会勤[1,2] 樊耀亭 ZHENG Huiqin;FAN Yaoting(College of Chemistry,Zhengzhou University,Zhengzhou 450001,China;College of Environment,Henan Finance University,Zhengzhou 450046,China)

机构地区：[1]郑州大学化学学院,河南郑州450001 [2]河南财政金融学院环境学院,河南郑州450046

出　　处：《信阳师范学院学报（自然科学版）》2023年第4期544-549,共6页Journal of Xinyang Normal University(Natural Science Edition)

基　　金：国家自然科学基金项目(21171147);河南省高校青年骨干教师项目(2020GGJS266);河南省高等学校重点科研项目(21B150001)。

摘　　要：以Fe(CO)_(5)和含一个巯基的配体为原料,通过多步反应合成了两个新的[FeFe]氢化酶模拟物1和2;构建了以化合物1和2为光催化剂、藻红B钠盐(EBS^(2-))为光敏剂、三乙胺(TEA)为电子给体和质子源的三组分光催化产氢体系,该体系在pH值为12且体积比为1∶1的CH_(3)CN/H_(2)O溶液中,经可见光(λ>420 nm)照射4 h,最大产氢量为205.0μmol,相对于化合物2的催化转化数(TON)为51.4;研究表明,配体中含有较多的质子捕获位点,有利于形成产氢活性中间体H 2-2Fe2S(η2-H 2-Fe II Fe I)物种,从而提高催化剂的产氢活性,光生电子从1*EBS^(2-)化合物1和2的第一个电子的转移均为热力学可行过程,到化合物1和2的第二个电子转移是热力学不可行过程。Two new mimetics of[FeFe]hydrogenase,1 and 2,were synthesized using Fe(CO)_(5)and a thiol-containing ligand in a multi-step reaction.A three-component homogeneous photocatalytic system was then constructed using complexes 1 or 2 as the photocatalyst,erythrosin B sodium salt(EBS^(2-))as the photosensitizer,and triethylamine(TEA)as the electron donor&proton source for hydrogen production.Under optimal conditions of CH_(3)CN/H_(2)O solution volume ratio of 1∶1,the pH value of 12,and visible light(λ>420 nm)irradiation for 4 h,the maximum hydrogen production was 205.0μmol.The turn over number(TON)for compound 2 in catalytic conversion is 51.4.The results show that the ligands contain more proton capture sites,which is conducive to the formation of the hydrogen-producing active intermediate H 2-2Fe2S(η2-H 2-Fe II Fe I)species,further improving the hydrogen production activity of the catalyst.The initial transfer of the photogenerated electron from 1*EBS^(2-)to complexes 1 and 2 is thermodynamically favorable,whereas the subsequent transfer of the second electron to these catalysts is thermodynamically unfavorable.

关 键 词：[FeFe]氢化酶模拟物 光驱动 产氢 电化学 荧光淬灭 

分 类 号：O641.4[理学—物理化学]