铂-钴双核配合物:合成、光物理性质及可见光驱动分解水制氢(英文)  

Platinum-Cobalt Dinuclear Complex:Synthesis, Photophysical Properties and Visible Light-Driven Hydrogen Production from Water

作　　者：韩阿丽[1] 杜平武[1] 

机构地区：[1]中国科学技术大学化学与材料科学学院,合肥230026

出　　处：《无机化学学报》2013年第8期1703-1709,共7页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21271166)资助项目

摘　　要：合成了一种铂钴双核配合物,[Pt(tBu3tpy)([C≡C-C6H4N])-Co(dmgH)2PyCl,(5)](tBu3tpy为4,4′,4″-叔丁基-2,2″6′,2″三联吡啶,C6H4N为吡啶基,dmgH为丁二酮肟,Py为吡啶),并研究其光物理和光化学性质。通过对配合物进行紫外、荧光光谱表征,表明该铂配合物在可见光区显示金属到配体电荷转移(MLCT)的特点及钴配合物猝灭其发光的性质。在电子给体三乙醇胺(TEOA)存在下,这种双核配合物可实现光驱动分解水产氢,光催化产氢性质受很多因素影响,比如pH值,溶剂等。通过质谱和紫外光谱表征表明这种双金属核分子催化剂不稳定,铂光敏剂和钴催化剂会在光照过程会分离。A platinum sensitizer-cobah dinuclear complex, [PtfBu3tpy）（[C = C-C6H4N]）-Co（dmgH）2PyC1, 5] （tBu3tpy= 4,4＇,4″-tri （tert-butyl）-2,2＇：6＇,2″-terpyridine, C6H4N=4-pyridyl, dmgH=dimethylglyoxime, Py=pyridine）, has been synthesized and characterized. The complex 5 shows absorption spectra in the visible region, which are assigned to mainly metal-to-ligand charge transfer （MLCT） character from the platinum sensitizer part. The cobalt moiety in complex 5 could quench the luminescence of the platinum part, indicating a possible process of intramolecular electron transfer. This dinuclear complex has been used for light-driven catalytic hydrogen production from water in the presence of triethanolamine （TEOA）. The hydrogen production is affected by many factors, such as pH value and solvent. And the results show that this molecular catalyst could be decomposed to release the platinum based photosensitizer, as confirmed by absorption spectra and mass spectrometry.

关 键 词：铂 光敏剂 钴 产氢 

分 类 号：O614.826[理学—无机化学] O614.812[理学—化学]