Carbonaceous Materials in Electrocatalysis: Innovations and Applications towards Sustainable Energy Storage
DICKSON D. Babu, PRAVEEN Naik
The development of efficient and sustainable electrocatalysts is crucial for advancing energy storage and conversion technologies. While noble metals (e.g., Pt, Pd, Ir, Ru) and transition metal-based compounds (e.g., FeO, MoS₂) have been widely explored, their high cost, limited durability, and environmental concerns have driven the search for alternative materials. Carbonaceous materials, especially metal-free and heteroatom-doped structures, have recently appeared as very efficient and cost-effective electrocatalysts with remarkable performance in fuel cells, metal–air batteries, and catalytic water splitting. This chapter offers a review of the latest breakthroughs in carbon-based electrocatalysis, focusing particularly on two-dimensional (2D) materials. This includes exploration into the fine engineering of active sites via thermal condensation, roles of heteroatom doping and defect modulation, and understanding structure-activity relationships which regulate catalytic efficiency. The mechanistic discussion concerning 2D structural growth also encompasses the impact upon electrocatalytic functionality. Finally, the chapter summarizes some of the major challenges and future opportunities in incorporating carbonaceous materials into next-generation energy storage and conversion systems toward sustainable and scalable applications.
Keywords
Carbonaceous Materials, Electrocatalysts, Energy Storage, 2D-Materials
Published online 10/20/2025, 17 pages
Citation: DICKSON D. Babu, PRAVEEN Naik, Carbonaceous Materials in Electrocatalysis: Innovations and Applications towards Sustainable Energy Storage, Materials Research Foundations, Vol. 182, pp 118-134, 2025
DOI: https://doi.org/10.21741/9781644903797-9
Part of the book on Electrocatalysts and Advanced Materials for Sustainable Energy Storage
References
[1] Anandhababu, G., Huang, Y., Babu, D. D., Wu, M., & Wang, Y. (2019). Oriented growth of ZIF-67 to derive 2D porous CoPO nanosheets for electrochemical-/photovoltage-driven overall water splitting. Advanced Functional Materials, 28(9), 1706120.. https://doi.org/10.1002/adfm.201706120
[2] Huang, Y., Liu, Q., Lv, J., Babu, D. D., Wang, W., Wu, M., Yuan, D., & Wang, Y. (2017). Co-intercalation of multiple active units into graphene by pyrolysis of hydrogen-bonded precursors for zinc-air batteries and water splitting. Journal of Materials Chemistry A, 5(39), 20882-20891.. https://doi.org/10.1039/C7TA06677E
[3] Novoselov, K. S., et al. (2004). Electric field effect in atomically thin carbon films. Science, 306(5696), 666-669.. https://doi.org/10.1126/science.1102896
[4] Dai, L., Xue, Y., Qu, L., Choi, H.-J., & Baek, J.-B. (2016). Metal-free catalysts for oxygen reduction reaction. Chemical Reviews, 115(11), 4823-4892.. https://doi.org/10.1021/cr5003563
[5] Li, Y., Li, Y., Zhu, E., & Zhang, H. (2016). Heteroatom-doped carbon materials for advanced electrochemical energy storage. Advanced Energy Materials, 6(9), 1600751.. https://doi.org/10.1002/aenm.201600751
[6] Qu, L., Liu, Y., Baek, J.-B., & Dai, L. (2015). Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano, 4(3), 1321-1326.. https://doi.org/10.1021/nn901850u
[7] Shui, J., Wang, M., Du, F., & Dai, L. (2015). N-doped carbon nanomaterials are durable catalysts for oxygen reduction and oxygen evolution reactions. Nature Communications, 6, 6392.. https://doi.org/10.1126/sciadv.1400129
[8] Gong, K., Du, F., Xia, Z., Durstock, M., & Dai, L. (2009). Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science, 323(5915), 760-764. https://doi.org/10.1126/science.1168049. https://doi.org/10.1126/science.1168049
[9] Zhao, Y., Watanabe, K., & Hashimoto, K. (2015). Self-supporting oxygen reduction electrocatalysts made from a nitrogen-rich network polymer. Journal of the American Chemical Society, 134(48), 19528-19531.. https://doi.org/10.1021/ja3085934
[10] Wang, X., Jia, Y., Mao, X., Zheng, Y., & Qiao, S.-Z. (2017). Graphene-based electrocatalysts for hydrogen evolution reaction. ACS Catalysis, 7(1), 211-229.
[11] Huang, Y., Babu, D. D., Peng, Z., et al. (2020). Atomic modulation, structural design, and systematic optimization for efficient electrochemical nitrogen reduction. Advanced Science, 7(4), 1902390.. https://doi.org/10.1002/advs.201902390
[12] Huang, Y., Babu, D. D., Wu, M., & Wang, Y. (2018). Synergistic supports beyond carbon black for polymer electrolyte fuel cell anodes. ChemCatChem, 10(20), 4495-4513.. https://doi.org/10.1002/cctc.201801094
[13] Yang, S., Feng, X., Wang, X., & Müllen, K. (2013). Graphene-based carbon nitride nanosheets as efficient metal-free electrocatalysts for oxygen reduction reactions. Angewandte Chemie International Edition, 50(22), 5339-5343.. https://doi.org/10.1002/anie.201100170
[14] Liu, X., Dai, L., & Chen, Z. (2019). Functional carbon-based nanomaterials for electrocatalytic energy conversion. Chemical Society Reviews, 48(10), 3072-3101.
[15] Peng, H., et al. (2013). High performance Fe- and N-doped carbon catalyst with graphene structure for oxygen reduction. Applied Catalysis B:Environmental, 130-131, 31-38.. https://doi.org/10.1038/srep01765
[16] Han, X., Ling, X., Yu, D., Xie, D., Li, L., Peng, S., Zhong, C., Zhao, N., Deng, Y., & Hu, W. (2019). Atomically dispersed binary Co-Ni sites in nitrogen-doped hollow carbon nanocubes for reversible oxygen reduction and evolution. Advanced Materials, 31(49), 1905622.. https://doi.org/10.1002/adma.201905622
[17] Liu, X., Dai, L., & Chen, Z. (2016). Metal-free catalysts for electrochemical CO₂ reduction. Nature Communications, 7, 10921.
[18] Wang, H., Jia, J., Song, P., Wang, Q., Li, D., Min, S., Qian, C., Wang, L., Li, Y. F., Ma, C., Wu, T., Yuan, J., Antonietti, M., & Ozin, G. A. (2017). Efficient electrocatalytic reduction of CO₂ by nitrogen-doped nanoporous carbon/carbon nanotube membranes: A step towards the electrochemical CO₂ refinery. Angewandte Chemie International Edition, 56(27), 7847-7852.. https://doi.org/10.1002/anie.201703720
[19] Abbas, S. C., Babu, D. D., Anandhababu, G., Wu, M., & Wang, Y. (2018). Novel N‐Mo₂C active sites for efficient solar‐to‐hydrogen generation. ChemElectroChem, 5(8), 1186-1190.. https://doi.org/10.1002/celc.201701365
[20] Zhu, J., Huang, Y., Mei, W., Zhao, C., Zhang, C., Zhang, J., Amiinu, I. S., & Mu, S. (2019). Effects of intrinsic pentagon defects on electrochemical reactivity of carbon nanomaterials. Angewandte Chemie International Edition, 58(12), 3859-3864.. https://doi.org/10.1002/anie.201813805
[21] Wang, W., Babu, D. D., Huang, Y., Lv, J., Wang, Y., & Wu, M. (2018). Atomic dispersion of Fe/Co/N on graphene by ball‑milling for efficient oxygen evolution reaction. International Journal of Hydrogen Energy, 43(22), 10351-10358.. https://doi.org/10.1016/j.ijhydene.2018.04.108
[22] Anandhababu, G., Manimuthu, V., Baskaran, S., Babu, D. D., Wu, M., & Wang, Y. (2021). Profuse surface activation of Ir‐dispersed titanium nitride bifunctional electrocatalysts. Advanced Energy and Sustainability Research, 2(2), 2000054.. https://doi.org/10.1002/aesr.202000054
[23] Babu, D. D., Huang, Y., Anandhababu, G., Ghausi, M. A., & Wang, Y. (2017). Mixed-metal-organic framework self-template synthesis of porous hybrid oxyphosphides for efficient oxygen evolution reaction. ACS Applied Materials & Interfaces, 9(44), 38621-38628.. https://doi.org/10.1021/acsami.7b13359
[24] Deng, J., Ren, P., Deng, D., & Bao, X. (2015). Enhanced electron penetration through an ultrathin graphene layer for highly efficient catalysis of the hydrogen evolution reaction. Angewandte Chemie International Edition, 54(7), 2100-2104.. https://doi.org/10.1002/anie.201409524
[25] Li, D., Jia, Y., Chang, G., Chen, J., Liu, H., Wang, J., Hu, Y., Xia, Y., Yang, D., & Yao, X. (2018). A defect-driven metal-free electrocatalyst for oxygen reduction in acidic electrolyte. Chem, 4(10), 2345-2356.. https://doi.org/10.1016/j.chempr.2018.07.005
