Polydopamine Interfacial Assembly Enables Core-Shell Porous Carbon-confined Cobalt Single Atoms for Efficient Oxygen Reduction

Zhen-zhen Zhu; Jiao-jiao Wu; Yan-qun Shi; Yu Xia; Ran Jin; Ming-jie Wu; Xun Cui; Ying-kui Yang

doi:10.11777/j.issn1000-3304.2025.25214

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Polydopamine Interfacial Assembly Enables Core-Shell Porous Carbon-confined Cobalt Single Atoms for Efficient Oxygen Reduction

Research Article | 更新时间：2025-12-18

- Polydopamine Interfacial Assembly Enables Core-Shell Porous Carbon-confined Cobalt Single Atoms for Efficient Oxygen Reduction
- Acta Polymerica Sinica Vol. 56, Issue 12, Pages: 2406-2417(2025)
- 作者机构：
  
  武汉纺织大学纺织新材料与先进加工全国重点实验室武汉 430200
- 作者简介：
  
  Xun Cui, E-mail: xcui@wtu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25214
  CLC：
- CSTR：32057.14.GFZXB.2025.7499
- Received：30 August 2025，
  
  Accepted：14 October 2025，
  
  Published Online：01 December 2025，
  
  Published：20 December 2025
- 稿件说明：
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朱珍珍, 吴娇娇, 史延群, 夏雨, 靳冉, 武明杰, 崔逊, 杨应奎. 聚多巴胺界面组装构建核壳多孔碳限域钴单原子用于高效氧还原. 高分子学报, 2025, 56(12), 2406-2417

Zhu, Z. Z., Wu, J. J., Shi, Y. Q., Xia, Y., Jin, R., Wu, M. J., Cui, X., Yang, Y. K. Polydopamine interfacial assembly enables core-shell porous carbon-confined cobalt single atoms for efficient oxygen reduction. Acta Polymerica Sinica, 2025, 56(12), 2406-2417
朱珍珍, 吴娇娇, 史延群, 夏雨, 靳冉, 武明杰, 崔逊, 杨应奎. 聚多巴胺界面组装构建核壳多孔碳限域钴单原子用于高效氧还原. 高分子学报, 2025, 56(12), 2406-2417 DOI： 10.11777/j.issn1000-3304.2025.25214. CSTR： 32057.14.GFZXB.2025.7499.

Zhu, Z. Z., Wu, J. J., Shi, Y. Q., Xia, Y., Jin, R., Wu, M. J., Cui, X., Yang, Y. K. Polydopamine interfacial assembly enables core-shell porous carbon-confined cobalt single atoms for efficient oxygen reduction. Acta Polymerica Sinica, 2025, 56(12), 2406-2417 DOI： 10.11777/j.issn1000-3304.2025.25214. CSTR： 32057.14.GFZXB.2025.7499.

摘要

氧还原反应(ORR)是燃料电池和金属-空气电池等新型可持续能源转换装置的关键电极过程，但其缓慢动力学严重限制了器件性能. 本研究提出一种分子介导的聚多巴胺(PDA)界面组装策略：通过Pluronic F127 (F127)与盐酸多巴胺(DA)在1

5-三甲基苯(TMB)分子调控下的协同组装，在碳纳米管(CNT)表面构筑PDA包覆层(CNT@PDA)，经热解后得到分级多孔碳壳层(CNT@HPC). 进一步利用2

2′-联吡啶(bipy)双齿配体螯合钴前驱体，经二次热解将钴单原子稳定锚定于碳基体中，制备出核壳结构分级多孔碳限域钴单原子催化剂(CNT@HPC-Co). 研究表明，钴单原子位点的独特电子结构显著加速了ORR动力学，而CNT内核与多孔碳壳层构成的分级通道有效促进电子传输与氧中间体的扩散传质速率. 电化学测试显示，CNT@HPC-Co在0.1 mol/L KOH中半波电位达0.88 V (versus 可逆氢电极(RHE))，优于商业Pt/C及已报道的同类非贵金属催化剂. 此外，该催化剂在水系和柔性准固态锌-空气电池中均展现出较高功率密度和优异循环稳定性. 本研究通过界面组装与单原子配位化学的协同设计，为构筑低成本、高活性ORR电催化剂提供了新策略.

Abstract

The oxygen reduction reaction (ORR) is a key electrode process in fuel cells and metal-air batteries

but its sluggish kinetics severely restricts device performance. In this work

we proposed a molecularly mediated polydopamine (PDA) interface assembly strategy. By the cooperative assembly of Pluronic F127 (F127) and dopamine hydrochloride (DA) under the regulation of 1

5-trimethylbenzene (TMB)

a PDA coating layer was constructed on the surface of carbon nanotubes (CNT)

yielding CNT@PDA. After pyrolysis

a hierarchical porous carbon shell layer (CNT@HPC) was obtained. Furthermore

the bidentate ligand 2

2′-bipyridine (bipy) was employed to chelate cobalt precursors

and a second pyrolysis step stabilized cobalt single atoms anchored within the carbon matrix

forming a core-shell structured hierarchical porous carbon confined cobalt single-atom catalyst (CNT@HPC-Co). The unique electronic structure of the cobalt single-atom sites markedly accelerated ORR kinetics

while the hierarchical channels composed of the CNT core and porous carbon shell effectively promoted electron transport and oxygen intermediate diffusion. Electrochemical tests revealed that CNT@HPC-Co delivered a half-wave potential of 0.88 V (versus RHE) in 0.1 mol/L KOH

outperforming commercial Pt/C and previously reported non-precious metal catalysts. In addition

the catalyst exhibited high power density and excellent cycling stability in both aqueous and flexible quasi-solid-state zinc-air batteries. This study demonstrated a synergistic design strategy that integrates interfacial assembly and single-atom coordination chemistry

offering a new pathway for the development of low-cost and high-performance ORR electrocatalysts.

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references

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