Wu Lingmin, Wang Yinghua, Shao Chunfeng, Sun Fanfei, Wang Liming, Li Baitao
Guangdong Provincial Key Laboratory of Fuel Cell Technology, School of Chemistry and Chemical Engineering, South China University of Technology Guangzhou 510640 China
Anhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation, Department of Materials Science and Engineering, Huaibei Normal University Huaibei 235000 China.
Chem Sci. 2025 Apr 8;16(18):8082-8091. doi: 10.1039/d5sc00944h. eCollection 2025 May 7.
The important effect of microstructure in Fe-Cu bimetallic catalysts on the mechanism of the oxygen reduction reaction (ORR) was theoretically and experimentally investigated. Three types of Fe sites regulated by Cu were constructed: Fe clusters modified with Cu-N, Fe-Cu dimers, and isolated Fe/Cu single atoms. A theoretical study revealed that although copper could reduce the d-band center of Fe, the Fe-Cu dimer displayed unique attributes. Notably, the dimer increased the energy of *π antibonding orbitals combined with Fe/Fe-3d and *OH-2p, accelerated *OH removal and produced the lowest predicted overpotential (0.48 V). Three catalysts featuring the above models were experimentally embedded on porous nitrogen-doped carbon. FeCu-NC-2 with Fe-Cu dimers exhibited the most positive half-wave potentials of 0.904 V in alkaline and 0.720 V in neutral solutions. A Zn-air battery and a microbial fuel cell equipped with FeCu-NC-2 as the cathodic catalyst produced stable and high power densities of 568.6 mW cm and 2467 mW m, respectively.
从理论和实验两方面研究了铁铜双金属催化剂的微观结构对氧还原反应（ORR）机理的重要影响。构建了三种由铜调控的铁位点：用Cu-N修饰的铁簇、Fe-Cu二聚体和孤立的Fe/Cu单原子。理论研究表明，虽然铜会降低铁的d带中心，但Fe-Cu二聚体具有独特的性质。值得注意的是，二聚体增加了与Fe/Fe-3d和OH-2p结合的π反键轨道的能量，加速了*OH的去除，并产生了预测的最低过电位（0.48 V）。实验将具有上述模型的三种催化剂嵌入多孔氮掺杂碳中。具有Fe-Cu二聚体的FeCu-NC-2在碱性溶液中的半波电位最正，为0.904 V，在中性溶液中为0.720 V。以FeCu-NC-2作为阴极催化剂的锌空气电池和微生物燃料电池分别产生了稳定且高的功率密度，分别为568.6 mW cm和2467 mW m。
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