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Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal–nitrogen coordination

机译:无直接金属-氮配位的高活性氧还原非铂族金属电催化剂

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摘要

Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon–nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation.
机译:用过渡金属代替用于阴极氧还原反应的催化剂中的贵金属,通常会基于与非氮配位的碳原子嵌入的金属原子簇紧密结合的氮配位的过渡金属的复合物产生活性位点。在这里,我们报告了一种非活性金属位的非铂族金属电催化剂,该活性位没有与铁的任何直接氮配位,其在碱性介质中的性能优于基准铂基催化剂,并且可与酸性介质中的同时代最佳催化剂媲美。原位X射线吸收光谱结合异位显微镜清楚地显示出,氮化碳纤维中嵌入的铁颗粒并未直接参与氧还原途径。相反,该反应主要发生在氮化碳纤维外皮的碳氮结构上。这意味着可能产生更大的活性位点密度,并且可能消除任何Fenton型过程,该过程涉及暴露的铁离子最终导致过氧化物引发的自由基形成。

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