Spontaneous N2 formation by a diruthenium complex enables electrocatalytic and aerobic oxidation of ammonia
Spontaneous N2 formation by a diruthenium complex enables electrocatalytic and aerobic oxidation of ammonia
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DOI：
10.1038/s41557-021-00797-w
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发表时间：
2021-11-08
期刊：
影响因子：
21.8
通讯作者：
Berry, John F.
中科院分区：
文献类型：
--
作者：
Trenerry, Michael J.;Wallen, Christian M.;Berry, John F.
在直接氨燃料电池（DAFC）中，氨电化学转化为二氮是实现氮经济的必要技术。以前的努力，催化这种反应的分子复合物需要添加外源性氧化剂或应用的电位大于热力学电位的氧还原反应的DAFC的阴极过程。我们报道了一种稳定的金属-金属键合的双钌络合物，它在环境条件下自发地从氨中产生二氮。所得到的还原的二钌材料可以用氧气再氧化，用于随后与氨的反应，证明了其自发促进DAFC所需的两个半反应的能力。二钌络合物还充当用于在相对于Fc（0/+）低至-255mV的电位下将氨电催化氧化成二氮的氧化还原介体，并且在碱性条件下在低于氧还原反应电位下操作，从而实现与DAFC的未来发展相关的热力学可行性。
The electrochemical conversion of ammonia to dinitrogen in a direct ammonia fuel cell (DAFC) is a necessary technology for the realization of a nitrogen economy. Previous efforts to catalyse this reaction with molecular complexes required the addition of exogenous oxidizing reagents or application of potentials greater than the thermodynamic potential for the oxygen reduction reaction-the cathodic process of a DAFC. We report a stable metal-metal bonded diruthenium complex that spontaneously produces dinitrogen from ammonia under ambient conditions. The resulting reduced diruthenium material can be reoxidized with oxygen for subsequent reactions with ammonia, demonstrating its ability to spontaneously promote both half-reactions necessary for a DAFC. The diruthenium complex also acts as a redox mediator for the electrocatalytic oxidation of ammonia to dinitrogen at potentials as low as -255 mV versus Fc(0/+) and operates below the oxygen reduction reaction potential in alkaline conditions, thus achieving a thermodynamic viability relevant for the future development of DAFCs.