Oxygen reduction reaction performance of Fe-N-C catalyst with dual nitrogen source

Abstract

Fe-N-C catalysts are potential substitutes to displace electrocatalysts containing noble chemical elements in the oxygen reduction reaction (ORR). However, their application is hampered by unsatisfactory activity and stability issues. The structures and morphologies of Fe-N-C catalysts have been found to be crucial for the number of active sites and local bonding structures. In this work, dicyandiamide (DCDA) and polyaniline (PANI) are shown to act as dual nitrogen sources to tune the morphology and structure of the catalyst and facilitate the ORR process. The dual nitrogen sources not only increase the amount of nitrogen doping atoms in the electrocatalytic Fe-C-N material, but also maintain a high nitrogen-pyrrole/nitrogen-graphitic: (N-P)/(N-G) value, improving the distribution density of catalytic active sites in the material. With a high surface area and amount of N-doping, the Fe-N-C catalyst developed can achieve an improved half-wave potential of 0.886 V (vs. RHE) in alkaline medium, and a better stability and methanol resistance than commercial Pt/C catalyst.

Graphical abstract

Keywords

Fe-N-C / oxygen reduction reaction / nitrogen-doped / dual nitrogen source

References

[1] Kiani M , Tian X Q , Zhang W . Non-precious metal electrocatalysts design for oxygen reduction reaction in polymer electrolyte membrane fuel cells: Recent advances, challenges and future perspectives. Coordination Chemistry Reviews, 2021, 441: 213954

[2] Zhang J , Yang H , Liu B . Coordination engineering of single-atom catalysts for the oxygen reduction reaction: A review. Advanced Energy Materials, 2021, 11(3): 2002473

[3] Shao M , Chang Q , Dodelet J P . . Recent advances in electrocatalysts for oxygen reduction reaction. Chemical Reviews, 2016, 116(6): 3594–3657

[4] Osmieri L , Pezzolato L , Specchia S . Recent trends on the application of PGM-free catalysts at the cathode of anion exchange membrane fuel cells. Current Opinion in Electrochemistry, 2018, 9: 240–256

[5] Wu J , Yang H . Platinum-based oxygen reduction electrocatalysts. Accounts of Chemical Research, 2013, 46(8): 1848–1857

[6] LeiCYangRZhaoJ, . Highly efficient and active Co-N-C catalysts for oxygen reduction and Zn–air batteries. Frontiers in Energy, 2024, early access, https://doi.org/10.1007/s11708-024-0928-6

[7] Chen Y , Zhang J , Yang L . . Recent advances in non-precious metal–nitrogen–carbon single-site catalysts for CO₂ electroreduction reaction to CO. Electrochemical Energy Reviews, 2022, 5(4): 11

[8] Fang C , Tang X , Wang J . . Performance of iron-air battery with iron nanoparticle-encapsulated C–N composite electrode. Frontiers in Energy, 2024, 18(1): 42–53

[9] Shen H , Thomas T , Rasaki S A . . Oxygen reduction reactions of Fe-NC catalysts: Current status and the way forward. Electrochemical Energy Reviews, 2019, 2(2): 252–276

[10] Bates J S , Johnson M R , Khamespanah F . . Heterogeneous MNC catalysts for aerobic oxidation reactions: Lessons from oxygen reduction electrocatalysts. Chemical Reviews, 2023, 123(9): 6233–6256

[11] Luo E , Chu Y , Liu J . . Pyrolyzed M–N_x catalysts for oxygen reduction reaction: Progress and prospects. Energy & Environmental Science, 2021, 14(4): 2158–2185

[12] Wang W , Jia Q , Mukerjee S . . Recent insights into the oxygen-reduction electrocatalysis of Fe/N/C materials. ACS Catalysis, 2019, 9(11): 10126–10141

[13] Tian H , Song A , Zhang P . . High durability of Fe-N-C single-atom catalysts with carbon vacancies toward the oxygen reduction reaction in alkaline media. Advanced Materials, 2023, 35(14): 2210714

[14] Luo Y , Zhang J , Chen J . . Dual-template construction of iron-nitrogen-codoped hierarchically porous carbon electrocatalyst for oxygen reduction reaction. Energy & Fuels, 2020, 34(12): 16720–16728

[15] Wang S , Wang H , Huang C . . Trifunctional electrocatalyst of N-doped graphitic carbon nanosheets encapsulated with CoFe alloy nanocrystals: The key roles of bimetal components and high-content graphitic-N. Applied Catalysis B: Environmental, 2021, 298: 120512

[16] Xu H , Jia H , Li H . . Dual carbon-hosted Co-N₃ enabling unusual reaction pathway for efficient oxygen reduction reaction. Applied Catalysis B: Environmental, 2021, 297: 120390

[17] Han A , Sun W , Wan X . . Construction of CO₄ atomic clusters to enable Fe-N₄ motifs with highly active and durable oxygen reduction performance. Angewandte Chemie, 2023, 62(30): e202303185

[18] Qin J , Yang Z , Xing F . . Two-dimensional mesoporous materials for energy storage and conversion: Current status, chemical synthesis and challenging perspectives. Electrochemical Energy Reviews, 2023, 6(1): 9

[19] Chen S , Xiang S , Tan Z . . Exploration of the oxygen transport behavior in non-precious metal catalyst-based cathode catalyst layer for proton exchange membrane fuel cells. Frontiers in Energy, 2023, 17(1): 123–133

[20] Zhang Y , Qian L , Zhao W . . Highly efficient Fe-NC nanoparticles modified porous graphene composites for oxygen reduction reaction. Journal of the Electrochemical Society, 2018, 165(9): H510–H516

[21] Zhang Z , Sun J , Wang F . . Efficient oxygen reduction reaction (ORR) catalysts based on single iron atoms dispersed on a hierarchically structured porous carbon framework. Angewandte Chemie, 2018, 130(29): 9176–9181

[22] Hu Y , Lu Y , Zhao X . . Highly active N-doped carbon encapsulated Pd–Fe intermetallic nanoparticles for the oxygen reduction reaction. Nano Research, 2020, 13(9): 2365–2370

[23] Wu G , More K L , Johnston C M . . High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science, 2011, 332(6028): 443–447

[24] Sudarsono W , Wong W Y , Loh K S . . Elucidating the roles of the Fe-N_x active sites and pore characteristics on Fe-PANI-biomass-derived RGO as oxygen reduction catalysts in PEMFCs. Materials Research Bulletin, 2022, 145: 111526

[25] Zhang R , Liu L , Zhang J . . Fabrication of the pyrolyzing carbon-supported cobalt–dicyandiamide electrocatalysts and study on the active sites and mechanism for oxygen reduction in alkaline electrolyte. Journal of Solid State Electrochemistry, 2015, 19(6): 1695–1707

[26] Gao Y , Hou M , Qi M . . New insight into effect of potential on degradation of Fe-NC catalyst for ORR. Frontiers in Energy, 2021, 15(2): 421–430

[27] Lee W H , Lee D W , Kim H . Development of nitrogen-doped carbon catalysts using melamine-based polymer as a nitrogen precursor for the oxygen reduction reaction. Journal of the Electrochemical Society, 2015, 162(7): F744–F749

[28] Mahmood A , Xie N , Zhao B . . Optimizing surface N-doping of Fe-N-C catalysts derived from Fe/melamine-decorated polyaniline for oxygen reduction electrocatalysis. Advanced Materials Interfaces, 2021, 8(13): 2100197

[29] Wang D , Hu J , Yang J . . Fe and N co-doped carbon derived from melamine resin capsuled biomass as efficient oxygen reduction catalyst for air-cathode microbial fuel cells. International Journal of Hydrogen Energy, 2020, 45(4): 3163–3175

[30] Gupta S , Zhao S , Ogoke O . . Engineering favorable morphology and structure of Fe-N-C oxygen-reduction catalysts through tuning of nitrogen/carbon precursors. ChemSusChem, 2017, 10(4): 774–785

[31] Qiao Z , Zhang H , Karakalos S . . 3D polymer hydrogel for high-performance atomic iron-rich catalysts for oxygen reduction in acidic media. Applied Catalysis B: Environmental, 2017, 219: 629–639

[32] Wu M , Yang X , Cui X . . Engineering Fe-N₄ electronic structure with adjacent Co-N₂C₂ and Co Nanoclusters on carbon nanotubes for efficient oxygen electrocatalysis. Nano-Micro Letters, 2023, 15(1): 232

[33] Gupta S , Zhao S , Ogoke O . . Engineering favorable morphology and structure of Fe-NC oxygen reduction catalysts via tuning nitrogen/carbon precursors. ChemSusChem, 2017, 10(4): 774–785

[34] Xie H , Du B , Huang X . . High density single fe atoms on mesoporous N-doped carbons: Noble metal-free electrocatalysts for oxygen reduction reaction in acidic and alkaline media. Small, 2023, 19(32): 2303214

[35] Sun X , Wei P , Gu S . . Atomic-level Fe-N-C coupled with Fe₃C-Fe nanocomposites in carbon matrixes as high-efficiency bifunctional oxygen catalysts. Small, 2020, 16(6): 1906057

[36] Jiang W , Gu L , Li L . . Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe₃C nanoparticles boost the activity of Fe–N_x. Journal of the American Chemical Society, 2016, 138(10): 3570–3578

[37] He J , Zheng T , Wu D . . Insights into the determining effect of carbon support properties on anchoring active sites in Fe-N-C catalysts toward the oxygen reduction reaction. ACS Catalysis, 2022, 12(3): 1601–1613

[38] Zhu G , Yang H , Jiang Y . . Modulating the electronic structure of FeCo nanoparticles in N-doped mesoporous carbon for efficient oxygen reduction reaction. Advanced Science, 2022, 9(15): 2200394

[39] Qiao M , Wang Y , Wang Q . . Hierarchically ordered porous carbon with atomically dispersed FeN₄ for ultraefficient oxygen reduction reaction in proton-exchange membrane fuel cells. Angewandte Chemie International Edition, 2020, 59(7): 2688–2694

[40] Luo X , Wei X , Wang H . . Secondary-atom-doping enables robust Fe-N-C single-atom catalysts with enhanced oxygen reduction reaction. Nano-Micro Letters, 2020, 12(1): 163

[41] Wu G , Chen Y S , Xu B Q . Remarkable support effect of SWNTs in Pt catalyst for methanol electrooxidation. Electrochemistry Communications, 2005, 7(12): 1237–1243

[42] Soo L T , Loh K S , Mohamad A B . . Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction. Journal of Alloys and Compounds, 2016, 677: 112–120

[43] Yang H , Liu Y , Liu X . . Large-scale synthesis of N-doped carbon capsules supporting atomically dispersed iron for efficient oxygen reduction reaction electrocatalysis. eScience, 2022, 2(2): 227–234

[44] Chen J , Huang B , Cao R . . Steering local electronic configuration of Fe-N-C-based coupling catalysts via ligand engineering for efficient oxygen electroreduction. Advanced Functional Materials, 2023, 33(4): 2209315

[45] Wei J , Xia D , Wei Y . . Probing the oxygen reduction reaction intermediates and dynamic active site structures of molecular and pyrolyzed Fe-N-C electrocatalysts by in situ raman spectroscopy. ACS Catalysis, 2022, 12(13): 7811–7820

[46] Ni L , Gallenkamp C , Wagner S . . Identification of the catalytically dominant iron environment in iron-and nitrogen-doped carbon catalysts for the oxygen reduction reaction. Journal of the American Chemical Society, 2022, 144(37): 16827–16840

[47] Zhang G , Liu X , Yu P . . Fe₃C coupled with Fe-N_x supported on N-doped carbon as oxygen reduction catalyst for assembling Zn-air battery to drive water splitting. Chinese Chemical Letters, 2022, 33(8): 3903–3908

[48] Li J , Xiao D , Wang P . . Highly strong interaction between Fe/Fe₃C nanoparticles and N-doped carbon toward enhanced oxygen reduction reaction performance. Particle & Particle Systems Characterization, 2023, 40(1): 2200141

Acknowledgements

This work was supported by the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (Grant No. 23KJD430007), Qinglan Project of Jiangsu Province, Innovative Research Group Project of the National Natural Science Foundation of China (Grant No. 51902145), Nanjing Technology Innovation Team of Optometric Materials and Application and Doctoral Start-up Fund Research supported by Jinling Institute of Technology (jit-b-202026), and the European Union (ERDF) and Région Nouvelle Aquitaine.

Competing Interests

The authors declare that they have no competing interests.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11708-024-0956-2 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2024 Higher Education Press 2024