Design of Metal-to-Metal Charge-Transfer Chromophores for Visible-Light Activation of Oxygen-Evolving Mn Oxide Catalysts in a Polymer Film
Design of Metal-to-Metal Charge-Transfer Chromophores for Visible-Light Activation of Oxygen-Evolving Mn Oxide Catalysts in a Polymer Film
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DOI：
10.1021/acs.chemmater.7b01669
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发表时间：
2017-08
影响因子：
8.6
通讯作者：
A. Yamaguchi;T. Takashima;K. Hashimoto;Ryuhei Nakamura
中科院分区：
文献类型：
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作者：
A. Yamaguchi;T. Takashima;K. Hashimoto;Ryuhei Nakamura
为了构建光响应的单向电荷转移单元用于放氧锰氧化物(MnOx)催化剂的活化，在聚合物基质中合成了由CeIII或CoII离子和Keggin型多氧钨酸盐(PW12O403-)组成的金属氧化物纳米团簇作为可见光吸收发色团。聚合物基质的利用使得PW12O403-态分子分散，有利于实现产物可分离的能量转换体系。在聚合物基质中，PW12O403-与Ce(NO3)3或CoCl2反应产生了从紫外区延伸到可见光区的新的宽吸收峰，这与氧桥双核WVI-O-CeIII和WVI-O-CoII单元的金属-金属电荷转移(MMCT)跃迁有关。循环伏安分析表明，CoIII/CoII具有比CeIV/CeIII高300 mV的正氧化还原电位，并能从MnOx中提取电子。
To construct photoresponsive unidirectional charge transfer units for the activation of oxygen-evolving manganese oxide (MnOx) catalyst, metal-oxide nanoclusters consisting of cerium (CeIII) or cobalt (CoII) ions and Keggin-type polyoxotungstate (PW12O403–) were synthesized in a polymer matrix as visible-light-absorbing chromophores. The utilization of the polymer matrix enabled the molecularly dispersed PW12O403– states and was advantageous to achieve product-separable energy conversion systems. The reaction of PW12O403– with Ce(NO3)3 or CoCl2 in the polymer matrix generated the new broad absorption tails extending from the UV to visible region, assignable to metal-to-metal charge transfer (MMCT) transitions of oxo-bridged binuclear WVI–O–CeIII and WVI–O–CoII units. Cyclic voltammetry analysis of the oxo-bridged binuclear units in the polymer membrane revealed that the CoIII/CoII couple had a 300 mV more positive redox potential than that of CeIV/CeIII and was capable of extracting electrons from MnOx ca...