Issue

Vol. 18 (2026)

Engineering Fe–Ni Dual-Atom Sites Via Ru Nanoclusters on 3D Carbon Aerogel for Enhanced Bifunctional Oxygen Electrocatalysis

https://doi.org/10.1007/s40820-026-02211-x
Yifan Zhang
College of Textile and Clothing Engineering, National Engineering Laboratory for Modern Silk, Soochow University, Suzhou 215123, People’s Republic of China
Kexin Kong
College of Textile and Clothing Engineering, National Engineering Laboratory for Modern Silk, Soochow University, Suzhou 215123, People’s Republic of China
Hongyuan Jie
State Key Laboratory of Marine Resource Utilization in South China Sea, School of Materials Science and Engineering, Hainan University, Haikou 570228, People’s Republic of China
Xiaoyan Jin
Department of Applied Chemistry, University of Seoul, Seoul 02504, Republic of Korea
Long Tian
Newtech Textile Technology Development (Shanghai) Co., Ltd., Shanghai 201506, People’s Republic of China
Yipu Liu
State Key Laboratory of Marine Resource Utilization in South China Sea, School of Materials Science and Engineering, Hainan University, Haikou 570228, People’s Republic of China
Zhijuan Pan
College of Textile and Clothing Engineering, National Engineering Laboratory for Modern Silk, Soochow University, Suzhou 215123, People’s Republic of China
Seong‑Ju Hwang
Department of Materials Science and Engineering, Yonsei University, Seoul 03722, Republic of Korea
Liang Li
School of Physical Science and Technology, Jiangsu Key Laboratory of Frontier Material Physics and Devices, Suzhou Key Laboratory of Intelligent Photoelectric Perception, Jiangsu Key Laboratory of Advanced Negative Carbon Technologies, Center for Energy Conversion Materials & Physics (CECMP), Soochow University, Suzhou 215006, People’s Republic of China
Zhe Wang
College of Textile and Clothing Engineering, National Engineering Laboratory for Modern Silk, Soochow University, Suzhou 215123, People’s Republic of China

Corresponding Author: Zhe Wang

zhewang1119@suda.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 404

Abstract

Dual-atom catalysts (DACs) show great promise in catalyzing oxygen reduction/evolution reactions (ORR/OER), yet facing significant challenges in achieving simultaneous high catalytic activity and stability in zinc–air batteries (ZABs). In this study, we synthesized a porous three-dimensional carbon aerogel anchored with atomically isolated FeN4/NiN4 dual sites and Ru6 nanoclusters (FeN4–Ru6–NiN4@PCA) to address these challenges. The adjacent Ru6 nanoclusters effectively regulate the geometric structures of FeN4 and NiN4 sites and catalyze the formation of a highly graphitic carbon matrix. These structural features endow FeN4–Ru6–NiN4@PCA with remarkable ORR/OER activity and stability, outperforming counterparts with only FeN4/NiN4 dual species and benchmark Pt/C and RuO2 catalysts. Density functional theory calculations reveal that Ru6 clusters induce obvious electron redistribution of FeN4/NiN4 sites and optimize their electron transfer to the key oxygen intermediates (OH*) at the rate-determining steps, thereby accelerating the ORR and OER kinetics. When employed FeN4–Ru6–NiN4@PCA as the cathode catalyst in ZABs, the resulting ZAB delivers a peak power density of 197.76 mW cm–2 and demonstrates outstanding cycling stability over 2000 h, highlighting its great potential for use in applications of energy storage device.


Highlights:
1 A heterogeneous catalyst consisting of atomically dispersed FeN4 and NiN4 sites along with Ru6 nanoclusters anchored on a 3D carbon aerogel was synthesized.
2 The Ru6 nanoclusters optimize the electron transfer from the Fe/Ni centers to the key intermediate (*OH) at the rate-determining steps.
3 Zin–air battery employed FeN4–Ru6–NiN4@PCA as the air cathode catalysts achieves an exceptional long-term cycling stability for over 2000 h.

Keywords

Dual-atom catalysts Nanoclusters Porous carbon aerogels ORR/OER Zinc–air batteries
Zhang, Yifan, Kexin Kong, Hongyuan Jie, Xiaoyan Jin, Long Tian, Yipu Liu, Zhijuan Pan, Seong‑Ju Hwang, Liang Li, and Zhe Wang. 2026. “Engineering Fe–Ni Dual-Atom Sites Via Ru Nanoclusters on 3D Carbon Aerogel for Enhanced Bifunctional Oxygen Electrocatalysis”. Nano-Micro Letters 18 (June):404. https://doi.org/10.1007/s40820-026-02211-x.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. G. Nazir, A. Rehman, J.-H. Lee, C.-H. Kim, J. Gautam et al., A review of rechargeable zinc-air batteries: recent progress and future perspectives. Nano-Micro Lett. 16(1), 138 (2024). https://doi.org/10.1007/s40820-024-01328-1
  2. S. Qiao, H. Shou, W. Xu, Y. Cao, Y. Zhou et al., Regulating and identifying the structures of PdAu alloys with splendid oxygen reduction activity for rechargeable zinc–air batteries. Energy Environ. Sci. 16(12), 5842–5851 (2023). https://doi.org/10.1039/D3EE02719H
  3. S. Chandrasekaran, R. Hu, L. Yao, L. Sui, Y. Liu et al., Mutual self-regulation of d-electrons of single atoms and adjacent nanops for bifunctional oxygen electrocatalysis and rechargeable zinc-air batteries. Nano-Micro Lett. 15(1), 48 (2023). https://doi.org/10.1007/s40820-023-01022-8
  4. J. Zhang, Y. Yu, C. Zhu, D. Zhu, J. Li et al., Recent progress of carbon-based heterojunction electrocatalysts for zinc-air batteries. Coord. Chem. Rev. 549, 217344 (2026). https://doi.org/10.1016/j.ccr.2025.217344
  5. R. Liu, C. Jiang, J. Guo, Y. Zheng, L. Zhang et al., Activating Ru nanoclusters for robust oxygen reduction in aqueous wide-temperature zinc-air batteries. Matter 7(11), 4031–4045 (2024). https://doi.org/10.1016/j.matt.2024.08.005
  6. L. Lyu, X. Hu, S. Lee, W. Fan, G. Kim et al., Oxygen reduction kinetics of Fe–N–C single atom catalysts boosted by pyridinic N vacancy for temperature-adaptive Zn–air batteries. J. Am. Chem. Soc. 146(7), 4803–4813 (2024). https://doi.org/10.1021/jacs.3c13111
  7. Q. Kang, M. Su, Y. Luo, T. Wang, F. Gao et al., Chemical fermentation porecreation on multilevel bio-carbon structure with in situ Ni–Fe alloy loading for superior oxygen evolution reaction electrocatalysis. Nano-Micro Lett. 17(1), 269 (2025). https://doi.org/10.1007/s40820-025-01777-2
  8. Y. Chen, T. He, Q. Liu, Y. Hu, H. Gu et al., Highly durable iron single-atom catalysts for low-temperature zinc-air batteries by electronic regulation of adjacent iron nanoclusters. Appl. Catal. B Environ. 323, 122163 (2023). https://doi.org/10.1016/j.apcatb.2022.122163
  9. Z. Wang, Z. Lu, Q. Ye, Z. Yang, R. Xu et al., Construction of Fe nanoclusters/nanops to engineer FeN4 sites on multichannel porous carbon fibers for boosting oxygen reduction reaction. Adv. Funct. Mater. 34(23), 2315150 (2024). https://doi.org/10.1002/adfm.202315150
  10. Q. Ye, X. Yi, C.-Z. Wang, T. Zhang, Y. Liu et al., Data-driven screening of pivotal subunits in edge-anchored single atom catalysts for oxygen reactions. Adv. Funct. Mater. 34(28), 2400107 (2024). https://doi.org/10.1002/adfm.202400107
  11. P. Rao, Y. Yu, S. Wang, Y. Zhou, X. Wu et al., Understanding the improvement mechanism of plasma etching treatment on oxygen reduction reaction catalysts. Exploration 4, 20230034 (2024). https://doi.org/10.1002/exp.20230034
  12. Q. Chang, F. He, Z. Zhang, X. Fu, Y. Wang et al., Self-organized integrated electrocatalyst on oxygen conversion for highly durable zinc-air batteries. Angew. Chem. Int. Ed. 64(4), e202416664 (2025). https://doi.org/10.1002/anie.202416664
  13. B. Tang, Y. Zhou, Q. Ji, Z. Zhuang, L. Zhang et al., A Janus dual-atom catalyst for electrocatalytic oxygen reduction and evolution. Nat. Synth. 3(7), 878–890 (2024). https://doi.org/10.1038/s44160-024-00545-1
  14. J. Kundu, T. Kwon, K. Lee, S.-I. Choi, Exploration of metal-free 2D electrocatalysts toward the oxygen electroreduction. Exploration 4(4), 20220174 (2024). https://doi.org/10.1002/EXP.20220174
  15. Y. Li, Y. Li, H. Sun, L. Gao, X. Jin et al., Current status and perspectives of dual-atom catalysts towards sustainable energy utilization. Nano-Micro Lett. 16(1), 139 (2024). https://doi.org/10.1007/s40820-024-01347-y
  16. R. Xu, Z. Wang, X. Jin, T. Li, Z. Lu et al., NiN4/FeN4 dual sites engineered by Fe5 clusters on porous flexible carbon fibers for promoting oxygen reduction and evolution. J. Colloid Interface Sci. 693, 137620 (2025). https://doi.org/10.1016/j.jcis.2025.137620
  17. N. Liu, Y. Li, W. Liu, Z. Liang, B. Liao et al., Engineering bipolar doping in a Janus dual-atom catalyst for photo-enhanced rechargeable Zn-air battery. Nano-Micro Lett. 17(1), 203 (2025). https://doi.org/10.1007/s40820-025-01707-2
  18. L. Zhang, Y. Dong, L. Li, Y. Shi, Y. Zhang et al., Concurrently boosting activity and stability of oxygen reduction reaction catalysts via judiciously crafting Fe–Mn dual atoms for fuel cells. Nano-Micro Lett. 17(1), 88 (2024). https://doi.org/10.1007/s40820-024-01580-5
  19. Y. Li, H. Wang, C. Chen, X. Xie, Y. Yang et al., Ten thousand hour stable zinc air batteries via Fe and W dual atom sites. Nat. Commun. 16, 8085 (2025). https://doi.org/10.1038/s41467-025-63540-w
  20. H. Liu, J. Huang, K. Feng, R. Xiong, S. Ma et al., Reconstructing the coordination environment of Fe/co dual-atom sites towards efficient oxygen electrocatalysis for Zn-air batteries. Angew. Chem. Int. Ed. 64(7), e202419595 (2025). https://doi.org/10.1002/anie.202419595
  21. J. Qiao, Y. You, L. Kong, W. Feng, H. Zhang et al., Precisely constructing orbital-coupled Fe─Co dual-atom sites for high-energy-efficiency Zn–air/iodide hybrid batteries. Adv. Mater. 36(32), 2405533 (2024). https://doi.org/10.1002/adma.202405533
  22. W. Deng, Z. Song, M. Jing, T. Wu, W. Li et al., Highly active air electrode catalysts for Zn-air batteries: catalytic mechanism and active center from obfuscation to clearness. Carbon Neutralization 3(4), 501–532 (2024). https://doi.org/10.1002/cnl2.133
  23. J. Zhu, X.F. Lu, D. Luan, X.W.D. Lou, Metal–organic frameworks derived carbon-supported metal electrocatalysts for energy-related reduction reactions. Angew. Chem. Int. Ed. 63(38), e202408846 (2024). https://doi.org/10.1002/anie.202408846
  24. Z. Lu, Z. Wang, Z. Yang, X. Jin, L. Tong et al., Engineering CoN4 and FeN4 dual sites with adjacent nanoclusters on flexible porous carbon fibers for enhanced electrocatalytic oxygen reduction and evolution. Adv. Funct. Mater. 35(16), 2418489 (2025). https://doi.org/10.1002/adfm.202418489
  25. C. Zhao, B. Chu, H. Nian, B. Shao, Y. Lu et al., Sulfur-mediated microenvironment modulation of high-density Fe-N4 sites for high-efficiency oxygen reduction and cryotolerant quasi-solid-state zinc-air batteries. Adv. Mater. 37(47), e10621 (2025). https://doi.org/10.1002/adma.202510621
  26. K. Yu, J. Qin, H. Zhang, S. Zhang, Y. Cao et al., Tailoring the first/second coordination layer of FeNi single atoms with nucleophile atoms to boost oxygen electrocatalysis for zinc-air batteries. Adv. Energy Mater. 15(29), 2501091 (2025). https://doi.org/10.1002/aenm.202501091
  27. T. Li, D. Zhang, Y. Zhang, D. Yang, R. Li et al., A pH-dependent microkinetic modeling guided synthesis of porous dual-atom catalysts for efficient oxygen reduction in Zn–air batteries. Energy Environ. Sci. 18(10), 4949–4961 (2025). https://doi.org/10.1039/d5ee00215j
  28. T. Qin, L. Zheng, Z. Pei, W. Wang, X. Ouyang et al., Electron redistribution via LDH-to-DACs coupling enhances d-band regulation and stability for zinc-air battery electrocatalysis. ACS Nano 19(36), 32231–32245 (2025). https://doi.org/10.1021/acsnano.5c06786
  29. Z. Qiu, T. Yang, P. Liu, Y. Zhang, X. Liang et al., Multi-dimensional interphase modulation by plasma for construction of advanced lithium metal batteries. Adv. Funct. Mater. 35(42), 2501761 (2025). https://doi.org/10.1002/adfm.202501761
  30. M. Shen, L. Xie, Y. Zhang, J. Sun, Y. Jia et al., Molecular engineering and channel structure modulation for single-atom iron-embedded high-porosity carbon fibers with enhanced oxygen reduction reaction and zinc-air battery performance. J. Colloid Interface Sci. 699, 138230 (2025). https://doi.org/10.1016/j.jcis.2025.138230
  31. L. Zhang, L. Zong, F. Lu, C. Wang, Z. Liu et al., Metal-saloph complexes pre-coordination for Fe single atom catalyst towards oxygen reduction reaction in rechargeable quasi-solid-state Zn-air battery. Appl. Catal. B Environ. Energy 370, 125189 (2025). https://doi.org/10.1016/j.apcatb.2025.125189
  32. H. Yu, C. Li, Y. Lei, Z. Xiang, Strategic secondary coordination implantation towards efficient and stable Fe─N─C electrocatalysts for the oxygen reduction reaction in PEMFCs. Angew. Chem. Int. Ed. 64(33), e202508141 (2025). https://doi.org/10.1002/anie.202508141
  33. M. Li, H. Chen, C. Guo, S. Qian, H. Li et al., Interfacial engineering on cathode and anode with iminated polyaniline@rGO-CNTs for robust and high-rate full lithium–sulfur batteries. Adv. Energy Mater. 13(25), 2300646 (2023). https://doi.org/10.1002/aenm.202300646
  34. J. Sun, M. Shen, A.J. Chang, J. Huang, P. Wang et al., Asymmetric Fe-N3Se single atoms coupled with Fe atomic clusters on alveolar-inspired hierarchically porous carbon submicronspheres for enhanced oxygen reduction. Appl. Catal. B Environ. Energy 383, 126102 (2026). https://doi.org/10.1016/j.apcatb.2025.126102
  35. J. Xu, Y. Meng, X. Qiu, H. Zhong, S. Liu et al., Honeycomb-like single-atom catalysts with FeN3Cl sites for high-performance oxygen reduction. Adv. Powder Mater. 4(4), 100298 (2025). https://doi.org/10.1016/j.apmate.2025.100298
  36. Y. Wu, S. Tang, W. Shi, Z. Ning, X. Du et al., Graphene-based phthalocyanine-assembled synergistic Fe-co-Ni trimetallic single-atomic bifunctional electrocatalysts by rational design for boosting oxygen reduction/evolution reactions. Carbon Energy 7(9), e70062 (2025). https://doi.org/10.1002/cey2.70062
  37. S. Xie, S. Tian, J. Yang, N. Wang, Q. Wan et al., Synergizing Mg single atoms and Ru nanoclusters for boosting the ammonia borane hydrolysis to produce hydrogen. Angew. Chem. Int. Ed. 64(15), e202424316 (2025). https://doi.org/10.1002/anie.202424316
  38. G. Qin, H.-G. Lu, G. Han, Y. Li, Ultrafast activity tuning and kilogram-scale synthesis of Fe–N–C catalysts via confinement-engineered joule heating. ACS Nano 20(7), 6352–6363 (2026). https://doi.org/10.1021/acsnano.6c00048
  39. L. Wu, M. Ning, X. Xing, Y. Wang, F. Zhang et al., Boosting oxygen evolution reaction of (Fe, Ni)OOH via defect engineering for anion exchange membrane water electrolysis under industrial conditions. Adv. Mater. 35(44), 2306097 (2023). https://doi.org/10.1002/adma.202306097
  40. J.-X. An, Y. Meng, L. Fang, Z. Lyu, S. Tang et al., Surface engineering strategy to synthesize bicomponent carbons for rechargeable zinc-air batteries. Energy Storage Mater. 70, 103520 (2024). https://doi.org/10.1016/j.ensm.2024.103520
  41. Y. Guo, Y. Xue, Z. Zhou, Revolutionizing Zn-Air batteries with chainmail catalysts: ultrathin carbon-encapsulated FeNi alloys on N-doped graphene for enhanced oxygen electrocatalysis. Chin. J. Catal. 58, 206–215 (2024). https://doi.org/10.1016/S1872-2067(23)64603-0
  42. L. Zhang, D.-H. Wu, M.U. Haq, J.-J. Feng, F. Yang et al., Coordination engineering and electronic structure modulation of FeNi dual-single-atoms encapsulated in N, P-codoped 3D hierarchically porous carbon electrocatalyst for synergistically boosting oxygen reduction reaction. Appl. Catal. B Environ. Energy 351, 123991 (2024). https://doi.org/10.1016/j.apcatb.2024.123991
  43. M.K. Kabiraz, J. Kim, H.J. Lee, S. Park, Y.W. Lee et al., Nickel nanoplates enclosed by (111) facets as durable oxygen evolution catalysts in anion exchange membrane water electrolyzers. Adv. Funct. Mater. 34(46), 2406175 (2024). https://doi.org/10.1002/adfm.202406175
  44. C. Kou, J. Zhou, H. Wang, J. Han, M. Han et al., Boron pretreatment promotes phosphorization of FeNi catalysts for oxygen evolution. Appl. Catal. B Environ. 330, 122598 (2023). https://doi.org/10.1016/j.apcatb.2023.122598
  45. Y. Guo, L. Yan, J. Li, J. Shi, Z. Liu et al., Zeolitic imidazolate framework induced CoFe-PBA/carbides hollow cube toward robust bi-functional electrochemical oxygen reaction. Chem. Eng. J. 472, 144818 (2023). https://doi.org/10.1016/j.cej.2023.144818
  46. W. Peng, S. Li, Y. Li, C.B. Musgrave III., B. Yuan et al., Breaking the limitations of activity and stability in powdered materials for oxygen evolution reaction: The critical role of catalyst-inducing seeds. Appl. Catal. B Environ. Energy 363, 124777 (2025). https://doi.org/10.1016/j.apcatb.2024.124777
  47. R. Xin, H. Zhao, Y. Liu, Y. Yuan, S. Liu et al., Homologous Mott–Schottky electrocatalysts enable record cycling stability in Zn-air battery and water splitting. Adv. Funct. Mater. 36(27), e24205 (2026). https://doi.org/10.1002/adfm.202524205
  48. H. Jiang, J. Xia, L. Jiao, X. Meng, P. Wang et al., Ni single atoms anchored on N-doped carbon nanosheets as bifunctional electrocatalysts for urea-assisted rechargeable Zn-air batteries. Appl. Catal. B Environ. 310, 121352 (2022). https://doi.org/10.1016/j.apcatb.2022.121352
  49. X. Zou, Q. Lu, J. Wu, K. Zhang, M. Tang et al., Screening spinel oxide supports for RuO2 to boost bifunctional electrocatalysts for advanced Zn–air batteries. Adv. Funct. Mater. 34(36), 2401134 (2024). https://doi.org/10.1002/adfm.202401134
  50. S. Liang, L.-N. Song, X.-X. Wang, Y.-F. Wang, J.-Y. Wu et al., Fluid-induced piezoelectric field enhancing photo-assisted Zn–air batteries based on a Fe@P(V-T) microhelical cathode. Adv. Mater. 36(44), 2407718 (2024). https://doi.org/10.1002/adma.202407718
  51. X. Tang, Y. Wang, Z. Zhang, M. Xu, Z. Tao et al., Flexible Zn-air battery for self-powered aptasensing SARS-CoV-2. Nano Energy 127, 109713 (2024). https://doi.org/10.1016/j.nanoen.2024.109713
  52. J. Chen, C. Qiu, L. Zhang, B. Wang, P. Zhao et al., Wood-derived Fe cluster-reinforced asymmetric single-atom catalysts and weather-resistant organohydrogel for wide-temperature flexible Zn–air batteries. Energy Environ. Sci. 17(13), 4746–4757 (2024). https://doi.org/10.1039/D4EE01226G
  53. X. Fan, Y. Xie, Y. Jiao, P. Wu, Monodentate acetate anion enhanced hydrogel electrolyte for long-term lifespan Zn-air batteries. ACS Nano 18(52), 35705–35717 (2024). https://doi.org/10.1021/acsnano.4c15570
  54. J. Wang, S.-Y. Lang, Z.-Z. Shen, Y.-L. Zhang, G.-X. Liu et al., In situ visualization of interfacial processes at nanoscale in non-alkaline Zn-air batteries. Nat. Commun. 15, 10882 (2024). https://doi.org/10.1038/s41467-024-55239-1
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE

Most read articles by the same author(s)