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The study of the pyrolysis products of Ni (II) and Pd (II) chelate complexes as catalysts for the oxygen electroreduction reaction


Nitrogen-doped carbon materials were prepared by the pyrolysis of carbon black Vulcan XC-72 impregnated with nitrogen-containing Pd (II) and Ni (II) complexes. The composition of materials was studied at different stages of their synthesis. It is shown that nanoparticles of metals and/or their oxides are not the main electroactive component of materials in the oxygen electroreduction reaction (ORR). It is established that the palladium complex provides a much more efficient doping of carbon with nitrogen compared to the nickel complex of a similar composition. This results in the high ORR electrocatalytic activity of the catalyst obtained, palladium complex being used in an alkaline medium. This material is a promising one to be used as an electrocatalyst in fuel cells with an anion-conducting membrane.

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  1. Banham D, Ye S (2017) Current status and future development of catalyst materials and catalyst layers for proton exchange membrane fuel cells: an industrial perspective. ACS Energy Lett 2(3):629–638

    CAS  Article  Google Scholar 

  2. Stamenkovic VR, Mun BS, Arenz M, Mayrhofer KJJ, Lucas CA, Wang G, Ross PN, Markovic NM (2007) Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat Mater 6(3):241–247

    CAS  Article  Google Scholar 

  3. Sui S, Wang X, Zhou X, Su Y, Riffat S, Liu C (2017) A comprehensive review of Pt electrocatalysts for oxygen reduction reaction: nanostructure, activity, mechanism and carbon support in PEM fuel cells. J Mater Chem A 5(5):1808–1825

    CAS  Article  Google Scholar 

  4. Bezerra CWB, Zhang L, Lee K, Liu H, Marques ALB, Marques EP, Wang H, Zhang J (2008) A review of Fe-N/C and Co-N/C catalysts for the oxygen reduction reaction. Electrochim Acta 53(15):4937–4951

    CAS  Article  Google Scholar 

  5. Niu K, Yang B, Cui J, Jin J, Fu X, Zhao Q, Zhang J (2013) Graphene-based non-noble-metal Co/N/C catalyst for oxygen reduction reaction in alkaline solution. J Power Sources 243:65–71

    CAS  Article  Google Scholar 

  6. Daems N, Sheng X, Vankelecom IFJ, Pescarmona PP (2014) Metal-free doped carbon materials as electrocatalysts for the oxygen reduction reaction. J Mater Chem A 2(12):4085–4110

    CAS  Article  Google Scholar 

  7. Gewirth AA, Varnell JA, DiAscro AM (2018) Nonprecious metal catalysts for oxygen reduction in heterogeneous aqueous systems. Chem Rev 118(5):2313–2339

    CAS  Article  Google Scholar 

  8. Sheng Z, Shao L, Chen J, Bao W, Wang F, Xia X (2011) Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. ACS Nano 5(6):4350–4358

    CAS  Article  Google Scholar 

  9. Tarasevich MR, Davydova ES (2016) Nonplatinum cathodic catalysts for fuel cells with alkaline electrolyte (Review). Russ J Electrochem 52(3):193–219

    CAS  Article  Google Scholar 

  10. Lastovina TA, Budnyk AP, Pimonova YA, Bugaev AL, Fedorenko AG, Dmitriev VP (2018) Step-by-step synthesis of a heteroatom-doped carbon-based electrocatalyst for the oxygen reduction reaction. Electrochem Commun 88:83–87

    CAS  Article  Google Scholar 

  11. Varga T, Varga AT, Ballai G, Haspel H, Kukovecz A, Kony Z (2018) One step synthesis of chlorine-free Pt/nitrogen-doped graphene composite for oxygen reduction reaction. Carbon 133:90–100

    CAS  Article  Google Scholar 

  12. Hossen M, Artyushkova K, Atanassov P, Serov A (2018) A synthesis and characterization of high performing Fe-N-C catalyst for oxygen reduction reaction (ORR) in alkaline exchange membrane fuel cells. J Power Sources 375:214–221

    CAS  Article  Google Scholar 

  13. Davydova ES, Tarasevich MR (2015) Investigation of properties of Co porphyrine pyrolysis products and identification of nature of molecular oxygen reduction active centers in basic electrolyte. Prot Met Phys Chem Surf 51(2):240–247

    CAS  Article  Google Scholar 

  14. Zhutaeva GV, Bogdanovskaya VA, Davydova ES, Kazanskii LP, Tarasevich MR (2014) Kinetics and mechanism of oxygen electroreduction on Vulcan XC72R carbon black modified by pyrolysis products of cobalt 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrine in a broad pH interval. J Solid State Electrochem 18(5):1319–1334

    CAS  Article  Google Scholar 

  15. Davydova ES, Tarasevich MR (2016) Studies of selectivity of oxygen reduction reaction in acidic electrolyte on electrodes modified by products of pyrolysis of polyacrylonitrile and metalloporphyrins. Russ J Electrochem 52(11):1007–1014

    CAS  Article  Google Scholar 

  16. Alekseenko VA, Zhuchenko TA, Kogan VA (1972) Metall-helaty Сo (II) s o-oksi- i o-aminonaftilazobenzolami. Russ J Gen Chem 42:578–581 (in Russian)

    CAS  Google Scholar 

  17. Briggs D, Seah MP (1983) Practical surface analysis by auger and X-ray photoelectron spectroscopy. Wiley, Chichester

    Google Scholar 

  18. Nefedov VI (1984) Rentgenoelektronnaya spektroskopiya khimicheskikh soedinenii (X-ray photoelectron spectroscopy of chemical compounds). Khimiya, Moscow

    Google Scholar 

  19. Guterman VE, Belenov SV, Alekseenko AA, Tabachkova NY, Volochaev VA (2017) The relationship between activity and stability of deposited platinum-carbon electrocatalysts. Russ J Electrochem 53(5):531–539

    CAS  Article  Google Scholar 

  20. Hyde T (2008) Crystallite size analysis of supported platinum catalysts by XRD. Platin Met Rev 52(2):129–130

    Article  Google Scholar 

  21. Artyushkova K, Pylypenko S, Olson TS, Fulghum JE, Atanassov P (2008) Predictive modeling of electrocatalyst structure based on structure-to-property correlations of X-ray photoelectron spectroscopic and electrochemical measurements. Langmuir 24(16):9082–9088

    CAS  Article  Google Scholar 

  22. Artyushkova K, Levendosky S, Atanassov P, Fulghum J (2007) XPS structural studies of nano-composite non-platinum electrocatalysts for polymer electrolyte fuel cells. Top Catal 46(3-4):263–275

    CAS  Article  Google Scholar 

  23. Mahmood N, Zhang C, Yin H, Hou Y (2014) Graphene-based nanocomposites for energy storage and conversion in lithium batteries, supercapacitors and fuel cells. J Mater Chem A 2(1):15–32

    CAS  Article  Google Scholar 

  24. Zhang H, Li H, Li X, Qiu H, Yuan X, Zhao B, Ma Z, Yang J (2014) Pyrolyzing cobalt diethylenetriamine chelate on carbon (CoDETA/C) as a family of non-precious metal oxygen reduction catalyst. Int J Hydrogen Energy 39(1):267–276

    CAS  Article  Google Scholar 

  25. Davis R, Horvath G, Tobias C (1967) The solubility and diffusion coefficient of oxygen in potassium hydroxide solutions. Electrochim Acta 12(3):287–297

    CAS  Article  Google Scholar 

  26. Yang W, Fellinger T, Antonietti M (2011) Efficient metal-free oxygen reduction in alkaline medium on high-surface-area mesoporous nitrogen-doped carbons made from ionic liquids and nucleobases. J Am Chem Soc 133(2):206–209

    CAS  Article  Google Scholar 

  27. Wei W, Liang H, Parvez K, Zhuang X, Feng X, Müllen K (2014) Nitrogen-doped carbon nanosheets with size-defined mesopores as highly efficient metal-free catalyst for the oxygen reduction reaction. Angew Chem Int Ed 53(6):1570–1574

    CAS  Article  Google Scholar 

  28. Sa Y, Park C, Jeong H, Park S-H, Lee Z, Kim K, Park G-G, Joo S (2014) Carbon nanotubes/heteroatom-doped carbon core-sheath nanostructures as highly active, metal-free oxygen reduction electrocatalysts for alkaline fuel cells. Angew Chem Int Ed 53(16):4102–4106

    CAS  Article  Google Scholar 

  29. Liang H, Zhuang X, Brüller S, Feng X, Müllen K (2014) Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction. Nat Commun.

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This research was financially supported by the Ministry of Science and Higher Education of the Russian Federation (state assignment in the field of scientific activity no 0852-2020-0019).

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Correspondence to Sergey V. Belenov.

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Belenov, S.V., Guterman, V.E., Popov, L.D. et al. The study of the pyrolysis products of Ni (II) and Pd (II) chelate complexes as catalysts for the oxygen electroreduction reaction. J Solid State Electrochem 25, 789–796 (2021).

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  • Pt-free electrocatalyst
  • Oxygen reduction reaction
  • Nitrogen-doped carbon
  • Carbon-based electrocatalyst
  • Fuel cells