Chen Zirun, Xiong Yuang, Liu Yanling, Wang Zhanghongyuan, Zhang Binbin, Liang Xingtang, Chen Xia, Yin Yanzhen
Guangxi Key Laboratory of Green Chemical Materials and Safety Technology, Beibu Gulf University, Qinzhou 535011, China.
Guangxi Key Laboratory of Beibu Gulf Marine Biodiversity Conservation, College of Marine Sciences, Beibu Gulf Ocean Development Research Center, Beibu Gulf University, Qinzhou 535011, China.
Molecules. 2024 Aug 10;29(16):3785. doi: 10.3390/molecules29163785.
Fe-N-C materials have been regarded as one of the potential candidates to replace traditional noble-metal-based electrocatalysts for the oxygen reduction reaction (ORR). It is believed that the structure of carbon support in Fe-N-C materials plays an essential role in highly efficient ORR. However, precisely designing the morphology and surface chemical structure of carbon support remains a challenge. Herein, we present a novel synthetic strategy for the preparation of porous carbon spheres (PCSs) with high specific surface area, well-defined pore structure, tunable morphology and controllable heteroatom doping. The synthesis involves Schiff-based polymerization utilizing octaaminophenyl polyhedral oligomeric silsesquioxane (POSS-NH) and heteroatom-containing aldehydes, followed by pyrolysis and HF etching. The well-defined pore structure of PCS can provide the confinement field for ferroin and transform into Fe-N-C sites after carbonization. The tunable morphology of PCS can be easily achieved by changing the solvents. The surface chemical structure of PCS can be tailored by utilizing different heteroatom-containing aldehydes. After optimizing the structure of PCS, Fe-N-C loading on N,S-codoped porous carbon sphere (NSPCS-Fe) displays outstanding ORR activity in alkaline solution. This work paves a new path for fabrication of Fe-N-C materials with the desired morphology and well-designed surface chemical structure, demonstrating significant potential for energy-related applications.
铁氮碳材料被认为是有望替代传统贵金属基氧还原反应（ORR）电催化剂的候选材料之一。据信，铁氮碳材料中碳载体的结构在高效氧还原反应中起着至关重要的作用。然而，精确设计碳载体的形态和表面化学结构仍然是一个挑战。在此，我们提出了一种新颖的合成策略，用于制备具有高比表面积、明确孔结构、可调节形态和可控杂原子掺杂的多孔碳球（PCS）。合成过程包括利用八氨基苯基多面体低聚倍半硅氧烷（POSS-NH）和含杂原子的醛进行席夫碱聚合，随后进行热解和氢氟酸蚀刻。PCS明确的孔结构可为亚铁离子提供限制场，并在碳化后转化为铁氮碳位点。通过改变溶剂可以轻松实现PCS可调节的形态。利用不同的含杂原子醛可以定制PCS的表面化学结构。优化PCS结构后，负载在氮、硫共掺杂多孔碳球（NSPCS-Fe）上的铁氮碳在碱性溶液中表现出出色的氧还原反应活性。这项工作为制备具有所需形态和精心设计的表面化学结构的铁氮碳材料开辟了一条新途径，展示了在能源相关应用中的巨大潜力。
