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N, S-codoped porous carbon as metal-free electrocatalyst for oxygen reduction reaction

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Abstract

Preparing low-cost and metal-free catalysts with outstanding catalytic activity and high stability to replace noble metal catalysts is the current development trend. Herein, a facile and low-cost two-step carbonization is proposed for the preparation of N, S-codoped oxygen reduction reaction (ORR) electrocatalysts, PP350KOH800-S, from the biomass waste pomelo peel by introducing KOH and thiourea as activator. The prepared electrocatalysts have the high specific surface area and the hierarchical porous structure and exhibit excellent ORR catalytic activity with the half-wave potential of 0.87 V and the limiting diffusion current density of −7.2 mA cm−2 in alkaline media. The excellent ORR electrocatalytic activity largely depends on the large specific surface area, the porous structure, the high degree of defects, and the synergistic effect of nitrogen and sulfur atoms. The present work provides a reliable method for the preparation of cheap and effective electrocatalysts using biomass waste.

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References

  1. 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

    Article  CAS  Google Scholar 

  2. Debe MK (2012) Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486(7401):43–51

    Article  CAS  Google Scholar 

  3. Zhang Z, Deng Y-P, Xing Z, Luo D, Sy S, Can ZP, Liu G, Jiang Y, Chen Z (2019) “Ship in a bottle” design of highly efficient bifunctional electrocatalysts for long-lasting rechargeable Zn–Air batteries. ACS Nano 13(6):7062–7072

  4. Kwon NH, Conder J, Srout M, Fromm KM (2019) Surface modifications of positive-electrode materials for lithium ion batteries. Chimia 73(11):880–893

    Article  CAS  Google Scholar 

  5. Huang Z-F, Wang J, Peng Y, Jung C-Y, Fisher A, Wang X (2017) Design of efficient bifunctional oxygen reduction/evolution electrocatalyst: recent advances and perspectives. Adv Energy Mater 7(23):1700544

  6. Dai L, Xue Y, Qu L, Choi H-J, Baek J-B (2015) Metal-free catalysts for oxygen reduction reaction. Chem Rev 115(11):4823–4892

    Article  CAS  Google Scholar 

  7. Yu Z-Y, Duan Y, Liu J-D, Chen Y, Liu X-K, Liu W, Ma T, Li Y, Zheng X-S, Yao T, Gao M-R, Zhu J-F, Ye B-J, Yu S-H (2019) Unconventional CN vacancies suppress iron-leaching in Prussian blue analogue pre-catalyst for boosted oxygen evolution catalysis. Nat Commun 10(1):2799

  8. Dutta A, Bizzotto F, Quinson J, Zana A, Morstein CE, Rahaman MA, López AC, Arenz M, Broekmann P (2019) Catalyst development for water/CO2 co-electrolysis. Chimia 73(9):707–713

  9. Zhou M, Wang H-L, Guo S (2016) Towards high-efficiency nanoelectrocatalysts for oxygen reduction through engineering advanced carbon nanomaterials. Chem Soc Rev 45(5):1273–1307

    Article  CAS  Google Scholar 

  10. Zhou T, Xu W, Zhang N, Du Z, Zhong C, Yan W, Ju H, Chu W, Jiang H, Wu C, Xie Y (2019) Ultrathin cobalt oxide layers as electrocatalysts for high-performance flexible Zn–Air batteries. Adv Mater 31(15):1807468

    Article  Google Scholar 

  11. Wood KN, O’Hayre R, Pylypenko S (2014) Recent progress on nitrogen/carbon structures designed for use in energy and sustainability applications. Energy Environ Sci 7(4):1212–1249

  12. Yang Z, Nie H, Chen XA, Chen X, Huang S (2013) Recent progress in doped carbon nanomaterials as effective cathode catalysts for fuel cell oxygen reduction reaction. J Power Sources 236(16):238–249

    Article  CAS  Google Scholar 

  13. Ge H, Li G, Shen J, Ma W, Meng X, Xu L (2020) Co4N nanoparticles encapsulated in N-doped carbon box as tri-functional catalyst for Zn-air battery and overall water splitting. Appl Catal B 275:119104

  14. Silva R, Voiry D, Chhowalla M, Asefa T (2013) Efficient metal-free electrocatalysts for oxygen reduction: polyaniline-derived N- and O-Doped mesoporous carbons. J Am Chem Soc 135(21):7823–7782

    Article  CAS  Google Scholar 

  15. Ma Z, Dou S, Shen A, Tao L, Dai L, Wang S (2015) Sulfur-doped graphene derived from cycled lithium-sulfur batteries as a metal-free electrocatalyst for the oxygen reduction reaction. Angew Chem Int Ed 54(6):1888–1892

    Article  CAS  Google Scholar 

  16. El-Sawy AM, Mosa IM, Su D, Guild CJ, Khalid S, Joesten R, Rusling JF, Suib SL (2016) Controlling the active sites of sulfur-doped carbon nanotube-graphene nanolobes for highly efficient oxygen evolution and reduction catalysis. Adv Energy Mater 6(5):1501966

    Article  Google Scholar 

  17. Zhang M, Dai L (2012) Carbon nanomaterials as metal-free catalysts in next generation fuel cells. Nano Energy 1(4):514–517

    Article  CAS  Google Scholar 

  18. Zeng H, Wang W, Li J, Luo J, Chen S (2018) In situ generated dual-template method for Fe/N/S co-doped hierarchically porous honeycomb carbon for high-performance oxygen reduction. ACS Appl Mater Interfaces 10(10):8721–8729

    Article  CAS  Google Scholar 

  19. Li Y, Guo Q, Jiang Y, Shen W, Li M, He R (2020) A novel ball-in-ball hollow oxygen-incorporating cobalt sulfide spheres as high-efficient electrocatalyst for oxygen evolution reaction. Chin Chem Lett. https://doi.org/10.1016/j.cclet.2020.05.012

  20. Li Q, Chen W, Xiao H, Gong Y, Li Z, Zheng L, Zheng X, Yan W, Cheong WC, Shen R (2018) Fe isolated single atoms on S, N codoped carbon by copolymer pyrolysis strategy for highly efficient oxygen reduction reaction. Adv Mater 30(25):1800588

    Article  Google Scholar 

  21. Jeon IY, Zhang S, Zhang L, Choi HJ, Seo JM, Xia Z, Dai L, Baek JB (2013) Edge‐selectively sulfurized graphene nanoplatelets as efficient metal‐free electrocatalysts for oxygen reduction reaction: the electron spin effect. Adv Mater 25(42):6138–6145

    Article  CAS  Google Scholar 

  22. Hao Y, Zhang X, Yang Q, Chen K, Guo J, Zhou D, Feng L, Slanina Z (2018) Highly porous defective carbons derived from seaweed biomass as efficient electrocatalysts for oxygen reduction in both alkaline and acidic media. Carbon 137:93–103

    Article  CAS  Google Scholar 

  23. Xia BY, Yan Y, Li N, Wu HB, Lou XWD, Wang X (2016) A metal–organic framework-derived bifunctional oxygen electrocatalyst. Nat Energy 1(1):15006

    Article  CAS  Google Scholar 

  24. Li J-C, Hou P-X, Zhao S-Y, Liu C, Tang D-M, Cheng M, Zhang F, Cheng H-M (2016) A 3D bi-functional porous N-doped carbon microtube sponge electrocatalyst for oxygen reduction and oxygen evolution reactions. Energy Environ Sci 9(10):3079–3084

    Article  CAS  Google Scholar 

  25. Mai W, Sun B, Chen L, Xu F, Liu H, Liang Y, Fu R, Wu D, Matyjaszewski K (2015) Water-dispersible, responsive, and carbonizable hairy microporous polymeric nanospheres. J Am Chem Soc 137(41):13256–13259

    Article  CAS  Google Scholar 

  26. Ding W, Li L, Xiong K, Wang Y, Li W, Nie Y, Chen S, Qi X, Wei Z (2015) Shape fixing via salt recrystallization: a morphology-controlled approach to convert nanostructured polymer to carbon nanomaterial as a highly active catalyst for oxygen reduction reaction. J Am Chem Soc 137(16):5414–5420

    Article  CAS  Google Scholar 

  27. Zhang P, Bin D, Wei J-S, Niu X-Q, Chen X-B, Xia Y-Y, Xiong H-M (2019) Efficient oxygen electrocatalyst for Zn–air batteries: carbon dots and Co9S8 nanoparticles in a N,S-codoped carbon matrix. ACS Appl Mater Interfaces 11(15):14085–14094

  28. Wang L, Liang K, Deng L, Liu Y-N (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 246:89–99

    Article  CAS  Google Scholar 

  29. Li G, Pei L, Wu Y, Zhu B, Hu Q, Yang H, Zhang Q, Liu J, He C (2019) Facile synthesis of polyacrylonitrile-based N/S-codoped porous carbon as an efficient oxygen reduction electrocatalyst for zinc–air batteries. J Mater Chem A 7(18):11223–11233

    Article  CAS  Google Scholar 

  30. Zhao Y, Wan J, Yao H, Zhang L, Lin K, Wang L, Yang N, Liu D, Song L, Zhu J, Gu L, Liu L, Zhao H, Li Y, Wang D (2018) Few-layer graphdiyne doped with sp-hybridized nitrogen atoms at acetylenic sites for oxygen reduction electrocatalysis. Nat Chem 10(9):924–931

    Article  CAS  Google Scholar 

  31. Shin J, Guo J, Zhao T, Guo Z (2019) Functionalized carbon dots on graphene as outstanding non-metal bifunctional oxygen electrocatalyst. Small 15(16):1900296

    Article  Google Scholar 

  32. Xing L, Song C, Kong A (2020) N–S-codoped mesoporous carbons from melamine-2-thenaldehyde polymers on carbon nanotubes for oxygen reduction and Zn-air batteries. J Solid State Chem 287:121348

    Article  CAS  Google Scholar 

  33. Ma R, Lin G, Zhou Y, Liu Q, Zhang T, Shan G, Yang M, Wang J (2019) A review of oxygen reduction mechanisms for metal-free carbon-based electrocatalysts. NPJ Comput Mater 5(1):78

  34. Ito Y, Cong W, Fujita T, Tang Z, Chen M (2015) High catalytic activity of nitrogen and sulfur co-doped nanoporous graphene in the hydrogen evolution reaction. Angew Chem Int Ed 54(7):2131–2136

    Article  CAS  Google Scholar 

  35. Kohila Rani K, Karuppiah C, Wang SF, Alaswad SO, Sireesha P, Devasenathipathy R, Jose R, Yang CC (2020) Direct pyrolysis and ultrasound assisted preparation of N, S co-doped graphene/Fe3C nanocomposite as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions. Ultrason Sonochem 66:105111

    Article  CAS  Google Scholar 

  36. Ni B, Chen R, Wu L, Xu X, Shi C, Sun P, Chen T (2020) Optimized enhancement effect of sulfur in Fe–N–S codoped carbon nanosheets for efficient oxygen reduction reaction. ACS Appl Mater Interfaces 12(21):23995–24006

    Article  CAS  Google Scholar 

  37. Fang W, Bai Z, Yu X, Zhang W, Wu M (2020) Pollen-derived porous carbon decorated with cobalt/iron sulfide hybrids as cathode catalysts for flexible all-solid-state rechargeable Zn–air batteries. Nanoscale 12(21):11746–11758

    Article  CAS  Google Scholar 

  38. Ma Y, You S, Jing B, Xing Z, Chen H, Dai Y, Zhang C, Ren N, Zou J (2019) Biomass pectin-derived N, S-enriched carbon with hierarchical porous structure as a metal-free catalyst for enhancing bio-electricity generation. Energy 44(31):16624–16638

    CAS  Google Scholar 

  39. An L, Yan H, Chen X, Li B, Xia Z, Xia D (2016) Catalytic performance and mechanism of N-CoTi@CoTiO3 catalysts for oxygen reduction reaction. Nano Energy 20:134–143

  40. Liang J, Zheng Y, Chen J, Liu J, Hulicova-Jurcakova D, Jaroniec M, Qiao SZ (2012) Facile oxygen reduction on a three-dimensionally ordered macroporous graphitic C3N4/carbon composite electrocatalyst. Angew Chem Int Ed Eng 51(16):3892–3896

  41. Jin J-T, Qiao X-C, Cheng F-L, Fan H-B, Cui L-F (2017) Direct synthesis of interconnected N, S-codoped porous exfoliated carbon nanosheets as advanced electrocatalysts for oxygen reduction reaction. Carbon 122:114–121

    Article  CAS  Google Scholar 

  42. Wang H, Maiyalagan T, Wang X (2012) Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catal 2(5):781–794

    Article  CAS  Google Scholar 

  43. Yasuda S, Yu L, Kim J, Murakoshi K (2013) Selective nitrogen doping in graphene for oxygen reduction reactions. Chem Commun 49(83):9627–9629

    Article  CAS  Google Scholar 

  44. Wu J, Ma L, Yadav RM, Yang Y, Zhang X, Vajtai R, Lou J, Ajayan PM (2015) Nitrogen-doped graphene with pyridinic dominance as a highly active and stable electrocatalyst for oxygen reduction. ACS Appl Mater Interfaces 7(27):14763–14769

    Article  CAS  Google Scholar 

  45. Naveen MH, Shim K, Hossain MSA, Kim JH, Shim Y-B (2017) Template free preparation of heteroatoms doped carbon spheres with trace Fe for efficient oxygen reduction reaction and supercapacitor. Adv Energy Mater 7(5):1602002

    Article  Google Scholar 

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Acknowledgements

The authors acknowledge the generous financial support from Natural Science Foundation of Chongqing (cstc2018jcyjAX0625).

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  1. Qin Gao and Yi Wang contributed equally to this work.

Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, People’s Republic of China

    Qin Gao, Yi Wang, Miao Yang, Wei Shen, Yimin Jiang, Rongxing He & Ming Li

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  1. Qin Gao
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Correspondence to Ming Li.

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Gao, Q., Wang, Y., Yang, M. et al. N, S-codoped porous carbon as metal-free electrocatalyst for oxygen reduction reaction. J Solid State Electrochem 25, 1765–1773 (2021). https://doi.org/10.1007/s10008-021-04947-5

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  • DOI: https://doi.org/10.1007/s10008-021-04947-5

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