清华大学王定胜团队报道了Co4原子簇的构建实现高度活跃的和持久的氧还原性能Fe-N4基序。相关研究成果发表在2023年5月24日出版的《德国应用化学》。

由于氧还原反应（ORR）的高活性，非常需要具有单原子Fe-N4构型的Fe-N-C催化剂。然而，质子交换膜燃料电池（PEMFCs）的固有活性有限，耐久性不理想，严重制约了其实际应用。

该文中，研究发现构建相邻的金属原子簇（ACs）在提高Fe-N4催化剂的ORR性能和稳定性方面是有效的。通过使用Co4分子簇和Fe（acac）3注入的碳前体的“预约束”策略，在N掺杂的碳衬底上实现了Fe-N4构型与高度均匀的Co4-AC的集成。在H₂-O₂燃料电池测试中，所开发的催化剂具有优异的ORR活性，在酸性介质中的半波电位（E1/2）相对于RHE为0.835V，峰值功率密度为840mW cm^-2。第一性原理计算进一步阐明了用Co4-ACs修饰的已鉴定的Fe-N4的ORR催化机制。

该项工作为精确建立用于高效能源相关催化的原子分散多金属中心催化剂提供了一种可行的策略。

附：英文原文

Title: Construction of Co4 Atomic Clusters to Enable Fe-N4 Motifs with Highly Active and Durable Oxygen Reduction Performance

Author: Ali Han, Wenming Sun, Xin Wan, Dandan Cai, Xijun Wang, Feng Li, Jianglan Shui, Dingsheng Wang

Issue&Volume: 2023-05-24

Abstract: Fe-N-C catalysts with single-atom Fe-N4 configurations are highly needed owing to the high activity for oxygen reduction reaction (ORR). However, the limited intrinsic activity and dissatisfactory durability have significantly restrained the practical application of proton-exchange membrane fuel cells (PEMFCs). Here, we demonstrate that constructing adjacent metal atomic clusters (ACs) is effective in boosting the ORR performance and stability of Fe-N4 catalysts. The integration of Fe-N4 configurations with highly uniform Co4 ACs on the N-doped carbon substrate ([email protected]/[email protected]) is realized through a “pre-constrained” strategy using Co4 molecular clusters and Fe(acac)3 implanted carbon precursors. The as-developed [email protected]/[email protected] catalyst exhibits excellent ORR activity with a half-wave potential (E1/2) of 0.835 V vs. RHE in acidic media and a high peak power density of 840 mW cm2 in a H2-O2 fuel cell test. First-principles calculations further clarify the ORR catalytic mechanism on the identified Fe-N4 that modified with Co4 ACs. This work provides a viable strategy for precisely establishing atomically dispersed polymetallic centers catalysts for efficient energy-related catalysis.

DOI: 10.1002/anie.202303185

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202303185