Yu Wei-Bin, He Qing-Ya, Ma Xiu-Fang, Shi Hua-Tian, Wei Xianwen
Analysis and Testing Central Facility, School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002, P. R. China.
Dalton Trans. 2015 Jan 7;44(1):351-8. doi: 10.1039/c4dt03097d.
A new azo-complex [(L)Cu(II)(NO3)] [L = (E)-3-(pyridin-2-yldiazenyl)naphthalen-2-ol (HL)], was prepared via a one-pot synthetic method at 60 °C and was structurally characterized by IR, EA, PXRD and single crystal X-ray diffraction. In addition, TGA studies indicated that the complex was stable in air. The redox properties were determined by cyclic voltammetry, which revealed that the complex could be utilized as a catalyst for water oxidation under mild conditions. Subsequently, the complex was employed as a catalyst to take part in water oxidation reaction in the presence of a Ce(IV) salt utilized as an oxidant at pH 11 in PBS (Phosphate Buffered Saline) solution. The results suggested that the catalyst exhibited a high stability and activity toward water oxidation reaction under these conditions with an initial TOF of 4.0 kPa h(-1). Calculation methodology was performed to study the mechanism of the reaction, which revealed that in this catalytic process, the initial oxidation of Cu(II) to Cu(III) occurred by the formation of an intermediate "Cu(III)-O-O-Cu(III)". The formation of this intermediate, resulted in a release of oxygen and closing of the catalytic cycle.
通过一锅法在60℃制备了一种新型偶氮配合物[(L)Cu(II)(NO3)] [L = (E)-3-(吡啶-2-基重氮基)萘-2-醇(HL)],并通过红外光谱、元素分析、粉末X射线衍射和单晶X射线衍射对其结构进行了表征。此外,热重分析研究表明该配合物在空气中稳定。通过循环伏安法测定了其氧化还原性质,结果表明该配合物可在温和条件下用作水氧化催化剂。随后,该配合物在pH为11的磷酸盐缓冲盐水(PBS)溶液中,以Ce(IV)盐作为氧化剂,用作催化剂参与水氧化反应。结果表明,该催化剂在这些条件下对水氧化反应表现出高稳定性和活性,初始转化频率为4.0 kPa h(-1)。通过计算方法研究了反应机理,结果表明在该催化过程中,Cu(II)首先通过形成中间体“Cu(III)-O-O-Cu(III)”氧化为Cu(III)。该中间体的形成导致氧气释放并使催化循环闭合。