Yuan Bowen, Liu Bin, Liu Jin, Meng Xin, Xie Jiahao, Song Yidong, Gu Peng, Chen Yanjie, Han Chunmiao, Zou Jinlong
Heilongjiang Provincial Key Laboratory of Environmental Nanotechnology and Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People's Republic of China, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China.
Heilongjiang Provincial Key Laboratory of Environmental Nanotechnology and Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People's Republic of China, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China.
J Colloid Interface Sci. 2025 Feb;679(Pt A):75-89. doi: 10.1016/j.jcis.2024.09.213. Epub 2024 Sep 27.
Transition metal alloys can exhibit synergistic intermetallic effects to obtain high activities for oxygen reduction/evolution reactions (ORR/OER). However, due to the insufficient stability of active sites in alkaline electrolytes, conventional alloy catalysts still do not meet practical needs. Herein, by using polypyrrole tubes and cobalt-iron (CoFe) Prussian blue analogs as precursors, CoFe sulfides is in-situ formed on CoFe alloys to construct (CoFe)(S)/CoFe heterostructure in sulfur (S) and nitrogen (N) co-doped carbon nanotubes (CoFe@NCNTs-nS) via a low-temperature sulfidation strategy. The as-marked CoFe@NCNTs-12.5S exhibits a comparable ORR activity (half-wave potential of 0.901 V) to Pt/C (0.903 V) and a superior OER activity (overpotential of 272 mV at 10 mA cm) to RuO (299 mV). CoFe@NCNTs-12.5S also exhibits ultralow charge transfer resistances (ORR-6.36 Ω and OER-0.21 Ω) and an excellent potential difference of 0.617 V. The sulfidation-induced (CoFe)(S)/CoFe heterojunctions can accelerate interfacial charge transfer process. Tubular structure not only disperses the (CoFe)(S)/CoFe heterostructure, but also reduces the corrosion of active-sites to enhance catalysis stability. Zinc-air battery with CoFe@NCNTs-12.5S achieves a high specific capacity (718.1 mAh g), maintaining a voltage gap of 0.957 V after 400 h. This work reveals the potential of interface engineering for boosting ORR/OER activities of alloys via in-situ heterogenization.
过渡金属合金可展现协同金属间化合物效应，以获得用于氧还原/析氧反应（ORR/OER）的高活性。然而，由于碱性电解质中活性位点稳定性不足，传统合金催化剂仍无法满足实际需求。在此，通过使用聚吡咯管和钴铁（CoFe）普鲁士蓝类似物作为前驱体，CoFe硫化物原位形成于CoFe合金上，以通过低温硫化策略在硫（S）和氮（N）共掺杂的碳纳米管（CoFe@NCNTs - nS）中构建（CoFe）（S）/CoFe异质结构。所标记的CoFe@NCNTs - 12.5S展现出与Pt/C（0.903 V）相当的ORR活性（半波电位为0.901 V）以及优于RuO₂（299 mV）的OER活性（在10 mA cm⁻²时过电位为272 mV）。CoFe@NCNTs - 12.5S还展现出超低的电荷转移电阻（ORR为6.36 Ω，OER为0.21 Ω）以及0.617 V的优异电位差。硫化诱导的（CoFe）（S）/CoFe异质结可加速界面电荷转移过程。管状结构不仅分散了（CoFe）（S）/CoFe异质结构，还减少了活性位点的腐蚀以增强催化稳定性。采用CoFe@NCNTs - 12.5S的锌空气电池实现了高比容量（718.1 mAh g⁻¹），在400 h后保持0.957 V的电压间隙。这项工作揭示了通过原位异质化提升合金ORR/OER活性的界面工程潜力。
