基于非贵金属镍的金属有机大环的光解水放氢性能
Construction of a Noble-Metal-Free Nickel Metal-Organic Macrocycle for Photocatalytic Hydrogen Production
作者单位E-mail
李和川 大连理工大学精细化工重点实验室, 大连 116024  
李明凤 大连理工大学精细化工重点实验室, 大连 116024  
何成 大连理工大学精细化工重点实验室, 大连 116024 hecheng@dlut.edu.cn 
段春迎 大连理工大学精细化工重点实验室, 大连 116024  
摘要: 将具有NN(氮氮)双齿配位点的席夫碱配体L2(L2=1,4-苯二-2'-吡啶腙)与镍构筑得到一例[2+2]型金属有机大环[Ni2(L2)2(CH3CN)4](ClO44·4CH3CN(2),并将其用于可见光条件下的光解水产氢研究。该非贵金属光催化体系由催化剂、光敏剂(荧光素,Fl)和电子牺牲剂(三乙胺)三部分组成。相比于具有相同配位环境的单核配合物[Ni(L1)2(CH3CN)2](ClO421,L1=3-甲酰基苯-2'-吡啶腙),金属有机大环2作为催化剂具有较高的光催化活性,其产氢TON值可以达到3 100 molH2·molcat-1,归因于荧光素分子可能与金属有机大环2形成超分子配合物,提高了光致电子转移效率。
关键词: 金属有机大环    光催化产氢  超分子
基金项目: 国家自然科学基金(No.21531001)资助项目。
Abstract: A nickel based metal-organic macrocycle[Ni2(L2)2(CH3CN)4](ClO4)4·4CH3CN (2) constructed from bidentate Schiff base ligand L2 (L2=1,4-benzenedicarboxaldehyde-bis(2'-pyridinylhydrazone)) with multiple N atoms was utilized to produce hydrogen through splitting of water by visible light (λ>400 nm). This noble-metal-free photocatalytic system consists of a catalyst, photosensitizer (fluorescein, Fl) and sacrificial electron donor (Triethylamine, NEt3). Using the metal-organic macrocycle 2 as a proton reduction catalyst, the activity of the photocatalytic system is high, with a turnover number (TON) of approximately 3 100 molH2·molcat-1. In contrast to the metal-organic macrocycle 2, a mononuclear complex[Ni(L1)2(CH3CN)2](ClO4)2 (1, L1=3-formyl benzaldehyde-2'-pyridylhydrazone) with similar coordination environment has a low efficiency on producing hydrogen. The enhanced efficiency of the catalyst 2 is likely ascribed to the formation of supramolecular complex between fluorescein and the macrocycle which enhances the efficiency of photoinduced electron transfer.
Keywords: metal-organic macrocycle  nickel  light driven H2 production  supramolecular
投稿时间:2017-09-28 修订日期:2017-10-18
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李和川,李明凤,何成,段春迎.基于非贵金属镍的金属有机大环的光解水放氢性能[J].无机化学学报,2018,34(1):11-19.
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