In this work, we report a dicyandiamide (DCDA)-modified Fe–N–C electrocatalyst (Dicy/Fe–N–C) that effectively addresses the long-standing durability challenges of platinum-group-metal-free catalysts in proton exchange membrane fuel cells (PEMFCs). By introducing DCDA during pyrolysis, we simultaneously regulate the coordination environment of Fe active sites and reinforce the carbon support structure. As a result, the optimized catalyst exhibits enhanced resistance to demetallation, carbon corrosion, and peroxide-induced degradation, while maintaining competitive oxygen reduction reaction (ORR) activity.

Key Insights

• Dicyandiamide promotes formation of stable active sites
  We find that DCDA modification effectively increases the proportion of pyridinic FeN₄ sites, which possess higher energy barriers against demetallation and radical attack, thereby improving intrinsic catalyst stability.
• Graphitized carbon support enhances durability
  The incorporation of DCDA leads to a more graphitized carbon framework, which improves resistance to electrochemical corrosion and helps preserve active site integrity during long-term operation.
• Suppression of H₂O₂ formation mitigates degradation pathways
  The Dicy/Fe–N–C catalyst favors a four-electron ORR pathway, resulting in reduced hydrogen peroxide generation and minimizing the formation of harmful reactive oxygen species.
• Excellent durability demonstrated under both RDE and PEMFC conditions
  We observe minimal performance decay after extended cycling, with stable operation up to 264 h in PEMFC tests and limited power density loss after 30,000 cycles, confirming the robustness of the catalyst under realistic conditions.
• Performance meets and surpasses DOE targets
  The Dicy/Fe–N–C-based membrane electrode assembly delivers a current density of 50.4 mA cm⁻² at 0.9 V, exceeding the U.S. DOE 2025 target for PGM-free catalysts.

Significance of This Work

This study demonstrates that a simple dicyandiamide modification strategy can simultaneously optimize active site structure and carbon support properties in Fe–N–C catalysts. By mitigating key degradation mechanisms—including Fe site demetallation, carbon corrosion, and peroxide attack—we provide a viable pathway toward durable and scalable platinum-free electrocatalysts. We anticipate that this strategy will accelerate the practical deployment of PEM fuel cells in sustainable energy systems.

Authors & Affiliations

Xu Lin†, Zhankuan Lu†, Luojie Zhao†, Mengting Han, Yuting Wang, Shiqing Huang,
Hao Ling*, Yan Huang*, Jimmy Yun, Dapeng Cao*

† These authors contributed equally.

Affiliations:
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, China
College of Chemical Engineering, Xiangtan University, Xiangtan, China
Qingdao International Academician Park Research Institute, Qingdao, China
School of Chemical Engineering, The University of New South Wales, Sydney, Australia

Corresponding Authors:
Hao Ling (haoling@xtu.edu.cn)
Yan Huang (huangyan@buct.edu.cn)
Dapeng Cao (caodp@buct.edu.cn)

How to Cite This Article

Lin, X.; Lu, Z.; Zhao, L.; Han, M.; Wang, Y.; Huang, S.; Ling, H.; Huang, Y.; Yun, J.; Cao, D. (2026).
Boosting the durability of Fe-N-C electrocatalysts for PEM fuel cells by dicyandiamide modification strategy.
Catal, 2, 12. https://doi.org/10.1007/s44422-026-00023-z