协同硼掺杂显著提升Co-N-C催化剂的氧还原反应活性
收稿日期: 2025-06-18
修回日期: 2025-07-09
录用日期: 2025-07-31
网络出版日期: 2025-07-31
Significantly Enhanced Oxygen Reduction Reaction Activity in Co-N-C Catalysts through Synergistic Boron Doping
Received date: 2025-06-18
Revised date: 2025-07-09
Accepted date: 2025-07-31
Online published: 2025-07-31
钴（Co）中心对含氧中间体的弱吸附能，是致使Co-N-C催化剂与昂贵的铂基催化剂在催化氧还原反应（ORR）中存在显著性能差异的主要原因。本研究通过硼酸铵共热解策略实现硼取代，从而对Co-N-C活性位点结构进行精准调控。反应中原位生成的氨气（NH3）气体对表面进行刻蚀形成缺陷，为硼原子取代活性中心的氮原子奠定基础。精心构筑的CoB1N3活性中心可以赋予钴位点更高的电荷密度及与氧物种更强的吸附能，进而加速ORR动力学。如预期所示，所制备的Co-B/N-C催化剂展现出优于Co-N-C的ORR性能：半波电位提升40 mV，转换频率提高五倍。该催化剂优异的ORR活性在膜电极性能测试中同样显著，峰值功率密度达824 mW·cm-2，取得了目前同等条件下钴基催化剂的最高水平。本工作不仅提供了先进催化剂的设计方法，更为燃料电池应用开发了一种极具前景的非贵金属ORR电催化剂。
兰畅 , 柏景森 , 关欣 , 王烁 , 张楠淑 , 程雨晴 , 陶金晶 , 楚宇逸 , 肖梅玲 , 刘长鹏 , 邢巍 . 协同硼掺杂显著提升Co-N-C催化剂的氧还原反应活性[J]. 电化学, 2025 , 31(9) : 2506181 . DOI: 10.61558/2993-074X.3577
The weak adsorption energy of oxygen-containing intermediates on Co center leads to a considerable performance disparity between Co-N-C and costly Pt benchmark in catalyzing oxygen reduction reaction (ORR). In this work, we strategically engineer the active site structure of Co-N-C via B substitution, which is accomplished by the pyrolysis of ammonium borate. During this process, the in-situ generated NH3 gas plays a critical role in creating surface defects and boron atoms substituting nitrogen atoms in the carbon structure. The well-designed CoB1N3 active site endows Co with higher charge density and stronger adsorption energy toward oxygen species, potentially accelerating ORR kinetics. As expected, the resulting Co-B/N-C catalyst exhibited superior ORR performance over Co-N-C counterpart, with 40 mV, and fivefold enhancement in half-wave potential and turnover frequency (TOF). More importantly, the excellent ORR performance could be translated into membrane electrode assembly (MEA) in a fuel cell test, delivering an impressive peak power density of 824 mW·cm-2, which is currently the best among Co-based catalysts under the same conditions. This work not only demonstrates an effective method for designing advanced catalysts, but also affords a highly promising non-precious metal ORR electrocatalyst for fuel cell applications.
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