Li Zhiwen, Wang Hezhen, Xie Yan, Zhang Yifei, Gao Jianxin, Xu Yinghao, Chen Li, Xu Liangliang, Wang Erdong, Li Gao
State Key Laboratory of Catalysis & Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China; University of Chinese Academy of Sciences, Beijing, China.
State Key Laboratory of Catalysis & Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
J Colloid Interface Sci. 2025 Mar;681:16-24. doi: 10.1016/j.jcis.2024.11.150. Epub 2024 Nov 22.
It is of great significance but remains challenging to simultaneously development cost-effective and efficient non-noble metal electrocatalysts (NNMEs) for oxygen reduction reaction (ORR) in both alkaline and acidic solutions. In current work, a multi-component synergism system is developed, which is comprised of molybdenum phosphide (MoP) shell onto iron phosphide clusters anchored on carbon matrixes that embedded with numerous FeN species (MoP/FeP-FeN). The optimized MoP/FeP-FeN electrocatalyst delivers a synergistic enhancement in both alkaline and acidic ORR performances: E: 0.885 V (0.1 M KOH electrolyte) and E: 0.742 V (0.1 M HClO electrolyte). Furthermore, the equipped zinc-air batteries (ZABs) of MoP/FeP-FeN exhibit a power density of 140.6 mW cm@219.6 mA cm, which surpasses the corresponding FeP-FeN and commercial Pt/C catalyst. The computational calculations reveal that MoP/FeP-FeN shows a relative increase of d-band center closer to Fermin level than FeP-FeN, tuning the rate-determining step to conversion of *O to *OOH intermediate, thus significant reducing the energy barrier and enhancing ORR activity. This strategy opens new opportunities to rational design of Fe-based nanocomposites for stimulated ORR and further ZAB activities.
同时开发在碱性和酸性溶液中用于氧还原反应（ORR）的具有成本效益且高效的非贵金属电催化剂（NNMEs）具有重要意义，但仍具有挑战性。在当前工作中，开发了一种多组分协同体系，该体系由磷化钼（MoP）壳层包覆在锚定在碳基体上的磷化铁簇上组成，碳基体中嵌入了大量的FeN物种（MoP/FeP-FeN）。优化后的MoP/FeP-FeN电催化剂在碱性和酸性ORR性能方面都实现了协同增强：E：0.885 V（0.1 M KOH电解质）和E：0.742 V（0.1 M HClO电解质）。此外，配备MoP/FeP-FeN的锌空气电池（ZABs）表现出140.6 mW cm@219.6 mA cm的功率密度，超过了相应的FeP-FeN和商业Pt/C催化剂。计算结果表明，MoP/FeP-FeN的d带中心相对于FeP-FeN更接近费米能级，将速率决定步骤调整为O向OOH中间体的转化，从而显著降低了能垒并提高了ORR活性。该策略为合理设计用于促进ORR和进一步提高ZAB活性的铁基纳米复合材料开辟了新机会。
