Metal-free electrocatalytic hydrogen oxidation using frustrated Lewis pairs and carbon-based Lewis acids.
Metal-free electrocatalytic hydrogen oxidation using frustrated Lewis pairs and carbon-based Lewis acids.
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DOI：
10.1039/c5sc04564a
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发表时间：
2016-04-21
期刊：
影响因子：
8.4
通讯作者：
Wildgoose GG
中科院分区：
文献类型：
--
作者：
Lawrence EJ;Clark ER;Curless LD;Courtney JM;Blagg RJ;Ingleson MJ;Wildgoose GG
以碳为中心的路易斯酸和硼烷“氢化物穿梭体”的协同作用为氢氧化提供了一种无金属、耐CO的途径。虽然氢是一种潜在的清洁燃料，用于能源储存和利用技术，但将其转化为电能的能源成本很高。这就需要使用稀有而昂贵的贵金属电催化剂。电化学受挫的路易斯对为氢氧化的电催化提供了一种无金属、耐CO的途径。它们的功能是将受挫路易斯对（FLPs）的氢活化能力与生成的氢化物的电化学氧化结合起来。在这里，我们提出了一种电化学- flp方法，该方法利用了两种不同的刘易斯酸-一种具有优异电化学属性的碳基n-甲基吖啶酸阳离子，以及一种具有快速氢裂解动力学和“氢化物穿梭体”功能的硼烷。这种协同作用提供了一种对碳基Lewis酸具有电催化作用的系统，将氢氧化所需电位降低了1 V，并且可以多次循环使用。
The synergistic interaction of a carbon-centred Lewis acid and borane “hydride shuttle” offers a metal-free, CO tolerant pathway to hydrogen oxidation. Whilst hydrogen is a potentially clean fuel for energy storage and utilisation technologies, its conversion to electricity comes at a high energetic cost. This demands the use of rare and expensive precious metal electrocatalysts. Electrochemical-frustrated Lewis pairs offer a metal-free, CO tolerant pathway to the electrocatalysis of hydrogen oxidation. They function by combining the hydrogen-activating ability of frustrated Lewis pairs (FLPs) with electrochemical oxidation of the resultant hydride. Here we present an electrochemical–FLP approach that utilises two different Lewis acids – a carbon-based N-methylacridinium cation that possesses excellent electrochemical attributes, and a borane that exhibits fast hydrogen cleavage kinetics and functions as a “hydride shuttle”. This synergistic interaction provides a system that is electrocatalytic with respect to the carbon-based Lewis acid, decreases the required potential for hydrogen oxidation by 1 V, and can be recycled multiple times.