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Hydrogel derived N, P co-doped 3D honeycomb-like nano porous carbon: CAMN6P-3 and its electrochemical properties

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Abstract

The cost-effective and green preparation of electrocatalysts that are highly effective for both the cathode (reduction of oxygen) and anode (methanal oxidation) reactions is crucial for boosting the development of Direct Methanol fuel cells (DMFCs). This article describes a novel designed nitrogen and phosphorous co-doped honeycomb-like electrocatalyst (CAMN6P-3), which is derived from a hydrogel network formed with silk protein, polyaniline, and polyacrylamide. Notably, the CAMN6P-3 material has a surprisingly high nitrogen content (6.82%) and a high specific surface area (2494.55 m2 g−1). A high onset potential (1.11 V) was observed for the CAMN6P-3 catalyst, as well as a high limiting current density (5.4 mA.cm−2) during ORR. Furthermore, Pt/CAMN6P-3 demonstrates considerable catalytic activity as well as electrochemical stability for MOR as a catalyst carrier for Pt nanoparticles (Pt NPs). After long-term stability tests, the current density in the MOR was equivalent to a factor of twenty times that of the catalyst made from Pt/C. This superior performance can be attributed to the special nanostructure, where the honeycomb nanostructure not only provides an efficient channel for electron transfer and exposes more active sites, but also facilitates a high degree of dispersion of the Pt nanoparticles. From the perspective of sustainable development, combined with low-cost materials and the green preparation process, this work has a certain reference value for the development of highly efficient catalysts in the field of clean fuel cells.

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References

  1. Wang Y, Luo S, Pan W, Leung DYC (2021) Microfluidic fuel cells with different types of fuels: A prospective review. Renew Sust Energ Rev 141:110806

    Article  CAS  Google Scholar 

  2. Stamenkovic VR, Strmcnik D, Lopes PP (2016) Energy and fuels from electrochemical interfaces. Nat Mater 16:57–69

    Article  Google Scholar 

  3. Neaţu S, Neaţu F, Chirica IM (2021) Recent progress in electrocatalysts and electrodesfor portable fuel cells. Mater Chem A 9:17065–17128

    Article  Google Scholar 

  4. Pan ZF, An I, Zhao TS (2018) Advances and challenges in alkaline anion exchange membrane fuel cells. Prog Energy Combust Sci 66:141–175

    Article  Google Scholar 

  5. Ioroi T, Siroma Z, Yamazaki SI (2018) Electrocatalysts for PEM Fuel Cells. Adv Energy Mater 9:1801284

    Article  Google Scholar 

  6. Liu X, Zhai S, Zhang X (2021) Efficient and durable composite membranes based on polydopamine-mediated sulfonated graphene oxide for direct methanol fuel cells. J Mater Chem A 9:24044

    Article  CAS  Google Scholar 

  7. Xiao F, Wang YC, Wu ZP (2021) Recent Advances in Electrocatalysts for Proton Exchange Membrane Fuel Cells and Alkaline Membrane Fuel Cells. Adv Mater 33:2006292

    Article  CAS  Google Scholar 

  8. Zuo Y, Sheng W, Tao W (2022) Direct methanol fuel cells system-A review of dual-role electrocatalysts for oxygen reduction and methanol oxidation. J Mater Sci Technol 114:29–41

    Article  CAS  Google Scholar 

  9. Li S, Tang X, Jia H (2020) Nanoporous high-entropy alloys with low Pt loadings for high performance electrochemical oxygen reduction. J Catal 383:164–171

    Article  CAS  Google Scholar 

  10. Shao MH, Chang QW, Dodelet JP (2016) Recent advances in electrocatalysts for oxygen reduction reaction. Chem Rev 116:3594–3657

    Article  CAS  Google Scholar 

  11. Huang L, Zaman S, Tian X (2021) Advanced Platinum-Based Oxygen Reduction Electrocatalysts for Fuel Cells. Acc Chem Res 54:311–322

    Article  CAS  Google Scholar 

  12. Wang P, Shao Q, Huang X (2018) Updating Pt-Based Electrocatalysts for Practical Fuel Cells. Joule 2:2514–2516

    Article  Google Scholar 

  13. Zhang C, Li J, Li C (2021) Surface and interface engineering of hollow carbon sphere-based electrocatalysts for the oxygen reduction reaction. J Mater Chem A 9:25706

    Article  CAS  Google Scholar 

  14. Serov A, Kwak C (2009) Review of non-platinum anode catalysts for DMFC and PEMFC application. Appl Catal B Environ 90:313–320

    Article  CAS  Google Scholar 

  15. Zhao L, Sui XL, Li JZ (2018) Supramolecular assembly promoted synthesis of three-dimensional nitrogen doped graphene frameworks as efficient electrocatalyst for oxygen reduction reaction and methanol electrooxidation. Appl Catal B Environ 231:224–233

    Article  CAS  Google Scholar 

  16. Yang Q, Xiao Z, Kong D (2019) New insight to the role of edges and heteroatoms in nanocarbons for oxygen reduction reaction. Nano Energy 66:104096

    Article  CAS  Google Scholar 

  17. Razmjooei F, Singh KP, Song MY (2014) Enhanced electrocatalytic activity due to additional phosphorous doping in nitrogen and sulfur-doped graphene: A comprehensive study. Carbon 78:257–267

    Article  CAS  Google Scholar 

  18. Yang L, Zeng X, Wang W (2018) Recent Progress in MOF-Derived, Heteroatom-Doped Porous Carbons as Highly Efficient Electrocatalysts for Oxygen Reduction Reaction in Fuel Cells. Adv Funct Mater 28:1704537

    Article  Google Scholar 

  19. Li JC, Hou PX, Liu C (2017) Heteroatom-Doped Carbon Nanotube and Graphene-Based Electrocatalysts for Oxygen Reduction Reaction. Small 13:1702002

    Article  Google Scholar 

  20. Marbaniang P, Ingavale S, Karuppanan P (2021) Rationale approach of nitrogen doping at defect sites of multiwalled carbon nanotubes: A strategy for oxygen reduction electrocatalysis. Int J Hydrogen Energy 46:10268–10280

    Article  CAS  Google Scholar 

  21. Wang W, Zhao X, Shi H (2020) Shape inducer-free Polygonal Angle Platinum Nanoparticles in Graphene Oxide as Oxygen Reduction Catalyst derived from Gamma Irradiation. J Colloid Interf Sci 575:1–15

    Article  CAS  Google Scholar 

  22. Liu H, Cheng J, Lu Z (2019) Significant enhancement of the oxygen reduction activity of self-heteroatom doped coal derived carbon through oxidative pretreatment. Electrochim Acta 12:22–30

    Article  Google Scholar 

  23. Wang L, Liang K, Deng L (2019) Protein hydrogel networks: A unique approach to heteroatom self-doped hierarchically porous carbon structures as an efficient ORR electrocatalyst in both basic and acidic conditions. Appl Catal B: Environ 246:89–99

    Article  CAS  Google Scholar 

  24. Li D, Yang D, Yang X (2016) Double-helix structure in carrageenan-metal hydrogels: a general approach to porous metal sulfides/carbon aerogels with excellent sodium-ion storage. Angew Chem Int Ed 55:15925–15928

    Article  CAS  Google Scholar 

  25. Wang C, Li Z, Wang L (2019) Facile synthesis of 3D Fe/N codoped mesoporous graphene as efficient bi-functional oxygen electrocatalysts for rechargeable Zn-air batteries. ACS Sustain Chem Eng 7:7

    CAS  Google Scholar 

  26. Chen M, Jiang Y, Mei P (2019) Polyacrylamide Microspheres-Derived Fe3C@N-doped Carbon Nanospheres as Efficient Catalyst for Oxygen Reduction Rectiaon. Polymers 11:767

    Article  CAS  Google Scholar 

  27. Wang C, Xie N-H, Zhang Y (2019) Silk-Derived Highly Active Oxygen Electrocatalysts for Flexible and Rechargeable Zn-Air Batteries. Chem Mater 31:1023–1029

    Article  CAS  Google Scholar 

  28. Tian P, Wang Y, Li W (2020) A salt induced gelatin crosslinking strategy to prepare Fe-N doped aligned porous carbon for efficient oxygen reduction reaction catalysts and high-performance supercapacitors. J Catal 382:109–120

    Article  CAS  Google Scholar 

  29. Wang H, Dou S, Wang S (2017) Synthesis of electrocatalytically functional carbon honeycombs through cooking with molecule precursors. In J Hydrogen Energ 42:6472–6481

    Article  CAS  Google Scholar 

  30. Zhao Z, Long Y, Chen Y (2022) Phosphorus doped carbon nitride with rich nitrogen vacancy to enhance the electrocatalytic activity for nitrogen reduction reaction. Chem Eng J 430:132682

    Article  CAS  Google Scholar 

  31. Jiang H, Gu J, Zheng X (2019) Defect-rich and ultrathin N doped carbon nanosheets as advanced trifunctional metal-free electrocatalysts for the ORR, OER and HER. Energy Environ Sci 12:322–333

    Article  CAS  Google Scholar 

  32. Wu M, Wang Y, Wei Z (2018) Ternary doped porous carbon nanofibers with excellent ORR and OER performance for zinc-air batteries. J Mater Chem A 6:10918–10925

    Article  CAS  Google Scholar 

  33. Wang H, Zhang W, Bai P (2020) Ultrasound-assisted transformation from waste biomass to efficient carbon-based metal-free pH-universal oxygen reduction reaction electrocatalysts. Ultrason Sonochem 65:05048

    Article  Google Scholar 

  34. Xing Z, Jin R, Chen X (2021) Self-templating construction of N, P-co-doped carbon nanosheets for efficient eletreocatalytic oxygen reduction reaction. Chem Eng J 410:128015

    Article  CAS  Google Scholar 

  35. Liu L, Zeng G, Chen J (2018) N-doped Porous Carbon Nanosheets as pH- universal ORR Electrocatalyst in Various Fuel Cell Devices. Nano Energy 8:393–402

    Article  Google Scholar 

  36. Macchi S, Watanabe F, Viswanathan T (2021) Characterization and Electrocatalytic Performance of Molasses Derived Co-Doped (P, N) and Tri-Doped (Si, P, N) Carbon for the ORR. Electrochem 2:311–322

    Article  CAS  Google Scholar 

  37. Lei W, Deng Y-P, Li G (2018) Two-Dimensional Phosphorus-Doped Carbon Nanosheets with Tunable Porosity for Oxygen Reactions in Zinc-Air Batteries. ACS Catal 8:2464–2472

    Article  CAS  Google Scholar 

  38. Chai GL, Qiu K, Qiao M (2017) Active sites engineering leads to exceptional ORR and OER bifunctionality in P, N Co-doped graphene frameworks. Energ Environ Sci 10:1186–1195

    Article  CAS  Google Scholar 

  39. Liu Q, Zhou Y, Chen S (2015) Cellulose-derived nitrogen and phosphorus dual-doped carbon as high performance oxygen reduction catalyst in microbial fuel cell. J Power Sources 273:1189–1193

    Article  CAS  Google Scholar 

  40. Shi C, Maimaitiyiming X (2021) Three dimensional nitrogen, phosphorus and sulfur doped porous graphene as efficient bifunctional electrocatalysts for direct methanol fuel cell. In J Hydrogen Energ 46:10247–10258

    Article  CAS  Google Scholar 

  41. Siahkalroudi ZM, Aghabarari B, Vaezi M (2021) Effect of secondary heteroatom (S, P) in N-doped reduced graphene oxide catalysts to oxygen reduction reaction. Mol Catal 502:111372

    Article  Google Scholar 

  42. Mao X, Cao Z, Chen S (2019) Facile synthesis of N, P-doped hierarchical porous carbon framework catalysts based on gelatin/phytic acid supermolecules for electrocatalytic oxygen reduction. J Hydrogen Energy 44:5890–5898

    Article  CAS  Google Scholar 

  43. Jian G, He C, Liu J (2018) Polymerizable ionic liquid as precursor for N, P co-doped carbon toward oxygen reduction reaction. Catal Sci Technol 8:1142–1150

    Article  Google Scholar 

  44. Alonso-Lemus IL, Figueroa-Torres MZ, Lardizabal-Gutíerrez D (2019) Converting chicken manure into highly active N-P co-doped metal-free biocarbon electrocatalysts:effect of chemical treatment on their catalytic activity for the ORR. Sustain Energ Sustain Energ Fuels 3:1307–1316

    Article  CAS  Google Scholar 

  45. Quílez-Bermejo J, Morall E, Cazorla-Amor D (2020) Metal-free heteroatom-doped carbon-based catalysts for ORR: A critical assessment about the role of heteroatoms. Carbon 165:434–454

    Article  Google Scholar 

  46. Zhang J, Wang R, Hua X (2020) MOF-derived Co embedded into N-doped nanotube decorated mesoporous carbon as a robust support of Pt catalyst for methanol electrooxidation-ScienceDirect. Appl Surf Sci 533:147319

    Article  CAS  Google Scholar 

  47. Yang C, Jiang Q, Li W (2019) Ultrafine Pt Nanoparticle-Decorated 3D Hybrid Architectures Built from Reduced Graphene Oxide and MXene Nanosheets for Methanol Oxidation. Chem Mater 31:9277–9287

    Article  CAS  Google Scholar 

  48. An M, Du L, Du C (2018) Pt nanoparticles supported by sulfur and phosphorus co-doped graphene as highly active catalyst for acidic methanol electrooxidation. Electrochim Acta 285:202–213

    Article  CAS  Google Scholar 

  49. Pongpichayakul N, Themsirimongkon S, Maturost S (2021) Cerium oxide-modified surfaces of several carbons as supports for a platinum-based anode electrode for methanol electro-oxidation. In J Hydrogen Energ 46:2905–2916

    Article  CAS  Google Scholar 

  50. Zhong J, Wu L, Lan J (2020) Worm-like Pt nanoparticles anchored on graphene with S, N co-doping and Fe3O4 functionalization for boosting the electrooxidation of methanol. In J Hydrogen Energ 45:22929–22937

    Article  CAS  Google Scholar 

  51. Mu X, Xu Z, Ma Y (2017) Graphene-carbon nanofiber hybrid supported Pt nanoparticles with enhanced catalytic performance for methanol oxidation and oxygen reduction. Electrochim Acta 253:171–177

    Article  CAS  Google Scholar 

  52. Guo Q, Lu X, Fei G (2022) Nitrogen-Doped Graphene Aerogel Microspheres Used as Electrocatalyst Supports for Methanol Oxidation. Ind Eng Chem Res 61:1398–1407

    Article  CAS  Google Scholar 

  53. Gorle DB, Kulandainathan MA (2017) One-pot synthesis of highly efficient graphene based three-dimensional hybrids as catalyst supporting materials for electro-oxidation of liquid fuels. J Mater Chem A. 5:15273–15286

    Article  CAS  Google Scholar 

  54. Su Z, Li C, Cheng Y (2018) Enhanced electrocatalytic performance of platinum nanoparticles on thiolated polyaniline multiwalled carbon nanotubes for methanol oxidation. RSC Adv 8:33742

    Article  CAS  Google Scholar 

  55. Liang X, Dong F, Tang Z (2022) The Pt/g-C3N4-CNS catalyst via in situ synthesis process with excellent performance for methanol electrocatalytic oxidation reaction. New J Chem 46:3121

    Article  CAS  Google Scholar 

  56. Choi SM, Min HS, Kim HJ (2011) Synthesis of surface-functionalized graphene nanosheets with high Pt-loadings and their applications to methanol electrooxidation. Carbon 49:904–909

    Article  CAS  Google Scholar 

  57. Ali A, Shen PK (2019) Recent advances in graphene-based platinum and palladium electrocatalysts for the methanol oxidation reaction. J Mater Chem A 7:22189–22217

    Article  CAS  Google Scholar 

  58. An GH, Gi JH, Jin AH (2018) Platinum nanoparticles on nitrogen-doped carbon and nickel composites surfaces: A high electrical conductivity for methanol oxidation reaction. J Alloys Compd 763:250–256

    Article  CAS  Google Scholar 

  59. Chen D, He Z, Pei SE (2019) Pd nanoparticles supported on N and P dual-doped graphene as an excellent composite catalyst for methanol electro-oxidation. J Alloys Compd 785:781–788

    Article  CAS  Google Scholar 

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Acknowledgements

The authors appreciate the support from Key Research and Development Projects of Xinjiang Uygur Autonomous Region:«Research on Key Technologies for Pre-Treatment of Agroforestry Waste»(2022B02013-1) and the Opening Foundation of Key Laboratory of Xinjiang Uygur Autonomous Region (2020D04001).

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Correspondence to Xieraili Maimaitiyiming or Anjie Liu.

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Yisilamu, Z., Zhao, X., Maimaitiyiming, X. et al. Hydrogel derived N, P co-doped 3D honeycomb-like nano porous carbon: CAMN6P-3 and its electrochemical properties. J Nanopart Res 25, 213 (2023). https://doi.org/10.1007/s11051-023-05859-3

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