Metal-Nitrogen-Carbon Cluster Decorated Titanium Carbide is a Durable and Inexpensive Oxygen Reduction Reaction Electrocatalyst
Metal-Nitrogen-Carbon Cluster Decorated Titanium Carbide is a Durable and Inexpensive Oxygen Reduction Reaction Electrocatalyst
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金属-氮-碳簇装饰碳化钛是一种耐用且廉价的氧还原反应电催化剂
DOI：
10.1002/cssc.202101341
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发表时间：
2021
期刊：
影响因子：
8.4
通讯作者：
Cho, S. B.
中科院分区：
文献类型：
--
作者：
Cho, S. B.
分散在碳基质中的氮碳配位过渡金属簇合物(如 g，Fe−N−C)已成为一类廉价的氧还原反应电催化剂。结果表明，与Fe-−-N-−-C催化剂相比，优化嵌入在更稳定和耐腐蚀的碳化物基质中的氮配位过渡金属团簇之间的相互作用可以得到具有更高活性和稳定性的ORR电催化剂。利用第一性原理计算，确定了一个基于静电的催化活性描述符，并预测嵌入在TiC基质中的氮配位铁(FeN4)团簇是一种有效的无铂族金属(PGM)ORR电催化剂。在理论的指导下，合成了选定的催化剂配方，并证明了实验观察到的活性趋势与描述符导出的理论预测完全一致。与传统的Fe−N−C催化剂相比，Fe N−TiC催化剂具有更高的活性(20−%)和更高的耐用性(3.5倍)。基于静电的描述符为设计活性稳定的无PGM电催化剂和用于其他电化学反应的多相单原子催化剂提供了一个强有力的平台。
Clusters of nitrogen‐ and carbon‐coordinated transition metals dispersed in a carbon matrix (e. g., Fe−N−C) have emerged as an inexpensive class of electrocatalysts for the oxygen reduction reaction (ORR). Here, it was shown that optimizing the interaction between the nitrogen‐coordinated transition metal clusters embedded in a more stable and corrosion‐resistant carbide matrix yielded an ORR electrocatalyst with enhanced activity and stability compared to Fe−N−C catalysts. Utilizing first‐principles calculations, an electrostatics‐based descriptor of catalytic activity was identified, and nitrogen‐coordinated iron (FeN4) clusters embedded in a TiC matrix were predicted to be an efficient platinum‐group metal (PGM)‐free ORR electrocatalyst. Guided by theory, selected catalyst formulations were synthesized, and it was demonstrated that the experimentally observed trends in activity fell exactly in line with the descriptor‐derived theoretical predictions. The Fe−N−TiC catalyst exhibited enhanced activity (20 %) and durability (3.5‐fold improvement) compared to a traditional Fe−N−C catalyst. It was posited that the electrostatics‐based descriptor provides a powerful platform for the design of active and stable PGM‐free electrocatalysts and heterogenous single‐atom catalysts for other electrochemical reactions.