Visible Light‐Driven Hydrogen Evolution from Aqueous Solution in a Noble‐Metal‐Free System Catalyzed by a Cobalt Phthalocyanine
Visible Light‐Driven Hydrogen Evolution from Aqueous Solution in a Noble‐Metal‐Free System Catalyzed by a Cobalt Phthalocyanine
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钴酞菁催化的无贵金属体系中可见光驱动的水溶液析氢
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发表时间：
2016
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影响因子：
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通讯作者：
Jiangli Wang
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文献类型：
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作者：
Geng;Xiaocong Li;Jiangli Wang
太阳能驱动的从水中析氢已成为以化学键储存可再生能源的重要方法。高效的光化学分解水需要高活性和低成本的析氢催化剂，这仍然是一个重大的挑战。通过对一系列金属酞菁（MPcs）的筛选，发现大环酞菁钴（CoPc）在碱性条件下（pH=12.0），以氧杂蒽染料为光敏剂（PS），三乙胺（TEA）为牺牲电子给体，在水/乙醇混合溶剂中，对可见光催化制氢具有良好的催化活性.不含贵金属的系统相对于催化剂给出了2650的最高TON，对应于约1000的TOF。810 h−1。 通过紫外/维斯光谱、荧光光谱、计算研究和电化学等手段，提出了一种可能的非钴配合物的有机配合物催化产氢反应机理。据我们所知，这是利用酞菁钴作为分子催化剂从水中光生氢的第一个例子。
Solar-driven hydrogen evolution from water has emerged as an important methodology for the storage of renewable energy in chemical bonds. Efficient photochemical splitting of water requires the highly active and low-cost hydrogen-evolving catalysts, which remains a significant challenge. After screening a series of metallophthalocyanines (MPcs), the macrocyclic cobalt phthalocyanine (CoPc) is found to be an active catalyst for visible light-driven H2 production under basic conditions (pH=12.0) in water/ethanol mixed solvent when employed with xanthene dyes as the photosensitizers (PSs) and triethylamine (TEA) as the sacrificial electron donor. The noble-metal-free system gives the highest TON of 2650 with respect to the catalyst, corresponding to a TOF of ca. 810 h−1. By means of UV/vis and fluorescent spectroscopy as well as computational studies and electrochemistry, a possible catalytic mechanism of the hydrogen-generating reaction involving organo hydrides not cobalt hydrides was proposed. To the best of our knowledge, this is the first example of utilizing a cobalt phthalocyanine as molecular catalyst for the photogeneration of hydrogen from water.