Influence of 3d transition-metal substitution on the oxygen reduction reaction electrocatalysis of ternary nitrides in acid
Influence of 3d transition-metal substitution on the oxygen reduction reaction electrocatalysis of ternary nitrides in acid
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DOI：
10.1007/s12274-019-2440-6
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发表时间：
2019-09
期刊：
影响因子：
9.9
通讯作者：
Kevin E. Fritz;Yichen Yan;Jin Suntivich
中科院分区：
文献类型：
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作者：
Kevin E. Fritz;Yichen Yan;Jin Suntivich
非贵金属、酸稳定的氧还原反应（ORR）电催化剂的开发可以显著地帮助质子交换膜燃料电池（PEMFC）的商业化。本文报道了3d金属取代（M = Mn，Fe，Co）的氮化钼和氮化钨在酸性环境中的氧化还原电催化性能。我们发现双金属催化剂比钨酸盐更有活性，其比活性取决于取代的3d金属的化学性质。在这两个家族中，更多的电负性3d金属导致更高的ORR活性（即，Co > Fe > Mn）。我们将这一结果归因于电负性更强的3d金属从Mo或W基活性位点撤回电子的能力，从而有效地氧化催化剂的金属中心。基于我们的观察，未来的氮化物ORR电催化剂可以通过例如添加甚至更多的负电性掺杂剂金属或引入阴离子空位来进一步氧化Mo位点而进一步优化。
The development of non-precious, acid-stable, oxygen reduction reaction (ORR) electrocatalysts can significantly aid the commercialization of proton exchange membrane fuel cells (PEMFCs). We report a survey of the ORR electrocatalysis on 3d metal substituted (M = Mn, Fe, Co) molybdenum and tungsten nitrides in acidic environments. We find that molybdate catalysts are more active than tungstates, with the specific activity depending on the chemistry of the substituted 3d metal. In both families, more electronegative 3d metals led to higher ORR activity (i.e., Co > Fe > Mn). We attribute this result to the ability of the more electronegative 3d metal to withdraw electrons from the Mo- or W-based active sites, effectively oxidizing the metal centers of the catalysts. Based on our observation, future nitride ORR electrocatalysts can be further optimized by oxidizing the Mo sites further by, for example, adding even more electronegative dopant metals or incorporating anion vacancies.