Volume 40 Issue 2
Feb.  2023
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WAN Zeyuan, LI Guilin, WU Jiao. Transition metal and phosphorus co-doped porous carbon as electrocatalyst for oxygen reduction[J]. Acta Materiae Compositae Sinica, 2023, 40(2): 844-851. doi: 10.13801/j.cnki.fhclxb.20220228.002
Citation: WAN Zeyuan, LI Guilin, WU Jiao. Transition metal and phosphorus co-doped porous carbon as electrocatalyst for oxygen reduction[J]. Acta Materiae Compositae Sinica, 2023, 40(2): 844-851. doi: 10.13801/j.cnki.fhclxb.20220228.002

Transition metal and phosphorus co-doped porous carbon as electrocatalyst for oxygen reduction

doi: 10.13801/j.cnki.fhclxb.20220228.002
  • Received Date: 2022-01-06
  • Accepted Date: 2022-02-12
  • Rev Recd Date: 2022-02-08
  • Available Online: 2022-03-01
  • Publish Date: 2023-02-01
  • Carbon-based materials, as non-noble catalysts, have attracted extensive attention in the field of cathode catalysts for fuel cells due to their high conductivity, long-term stability, low-cost and environmental friendliness. Especially, the oxygen reduction reaction (ORR) activity of carbon materials can be significantly improved after co-doping with transition metal and heteroatoms. In this work, transition metal (Co, Fe, Ni, Mn) and phosphorus (P) co-doped porous carbon (TM-P-C) was prepared via self-assembly method combined with a carbonization process, in which polyether (F127) was introduced as soft template, phenol and formaldehyde as carbon precursor, tetraphenylphosphine bromide as phosphorus source, and nitrate as transition metal source. The electrocatalytic activity of TM-P-C for ORR in alkaline electrolyte was studied by using the rotating ring-disk electrode (RRDE) technique. The results reveal that TM-P-C exhibits high electrocatalytic performance for ORR in 0.1 mol/L KOH, and the activity follows P-Co-C>P-Ni-C>P-Fe-C>P-Mn-C. Moreover, the ORR performance of P-Co-C is compared to that of commercial 20wt%Pt/C catalyst. The diffusion limiting current density of P-Co-C reaches that of 20wt%Pt/C and a negative shift of about 66 mV exists in the half-wave potential of P-Co-C as compared to 20wt%Pt/C, indicating the four-electron pathway during the ORR. The enhancement in the activity for ORR is mainly attributed to the synergistic effect of P and transition metal doping in carbon of TM-P-C. Moreover, TM-P-C shows excellent long-term stability and methanol toxicity resistance, superior to that of commercial 20wt%Pt/C.


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  • [1]
    CHIU Y S P, LIAN J H, CHIU V, et al. Mathematical modeling for a multiproduct manufacturing system featuring postponement, external suppliers, overtime, and scrap[J]. International Journal of Industrial Engineering Computations,2020,13:1-12.
    MA M J, YANG X X, QIAO J S, et al. Progress and challenges of carbon-fueled solid oxide fuel cells anode[J]. Journal of Energy Chemistry,2021,56:209-222. doi: 10.1016/j.jechem.2020.08.013
    LYU D, YAO S X, BAHARI Y, et al. In situ molecular-level synthesis of N, S co-doped carbon as efficient metal-free oxygen redox electrocatalysts for rechargeable Zn-air batteries[J]. Applied Materials Today,2020,20:100737-100747. doi: 10.1016/j.apmt.2020.100737
    LIU T, ZHANG L M, TIAN Y. Earthworm-like N, S-doped carbon tube-encapsulated Co9S8 nanocomposites derived from nanoscaled metal-organic frameworks for highly efficient bifunctional oxygen catalysis[J]. Journal of Materials Chemistry A,2018,6:5935-5943. doi: 10.1039/C7TA11122C
    AMIJNU I S, PU Z H, LIU X B, et al. Multifunctional Mo-N/C@MoS2 electro-catalysts for HER, OER, ORR, and Zn-air batteries[J]. Advanced Functional Material,2017,27:1702300-1702311. doi: 10.1002/adfm.201702300
    WEI J, HU Y X, LIANG Y, et al. Nitrogen-doped nanoporous carbon/graphene nano-sandwiches: Synthesis and application for efficient oxygen reduction[J]. Advanced Functional Material,2015,25:5768-5777. doi: 10.1002/adfm.201502311
    LI J, QIN X P, HOU P X, et al. Identification of active sites in nitrogen and sulfur co-doped carbon-based oxygen reduction catalysts[J]. Carbon,2019,147:303-311. doi: 10.1016/j.carbon.2019.01.018
    ZHAO Y, KAMYIYA K, HASHIMOTO K, et al. Efficient bifunctional Fe/C/N electrocatalysts for oxygen reduction and evolution reaction[J]. Journal of Physical Chemistry C,2015,119:2583-2588. doi: 10.1021/jp511515q
    QIAN Y H, HU Z G, GE X M. A metal-free ORR/OER bifunctional electrocatalyst derived from metal-organic frameworks for rechargeable Zn-air batteries[J]. Carbon,2017,111:641-650. doi: 10.1016/j.carbon.2016.10.046
    ZENG K, SU J M, CAO X C, et al. B, N co-doped ordered mesoporous carbon with enhanced electrocatalytic activity for the oxygen reduction reaction[J]. Journal of Alloys and Compounds,2020,824:153908-153914. doi: 10.1016/j.jallcom.2020.153908
    ZHANG D, SUN P P, ZUO Z, et al. N, P-co-doped carbon nanotubes coupled with Co2p nanoparticles as bifunctional oxygen electrocatalyst[J]. Journal of Electroanalytical Chemistry,2020,871:114327-114335. doi: 10.1016/j.jelechem.2020.114327
    HUANG N, YANG L, ZHANG M Y, et al. Cobalt-embedded N-doped carbon arrays derived in situ as trifunctional catalyst toward hydrogen and oxygen evolution, and oxygen reduction[J]. ChemElectroChem,2019,6:4522-4532. doi: 10.1002/celc.201901106
    QUÍLEZ-BERMEJ J, GONZALEZ-GAITAN C, EMILIA M, et al. Effect of carbonization conditions of polyaniline on its catalytic activity towards ORR-Some insights about the nature of the active sites[J]. Carbon,2017,119:62-71. doi: 10.1016/j.carbon.2017.04.015
    SON S, LIM D, NAM D, et al. N, S-doped nanocarbon derived from ZIF-8 as a highly efficient and durable electro-catalyst for oxygen reduction reaction[J]. Journal of Solid State Chemistry,2019,274:237-242. doi: 10.1016/j.jssc.2019.03.036
    ZHANG W M, YAO X Y, ZHOU S N, et al. ZIF-8/ZIF-67-derived co-Nx-embedded 1D porous carbon nanofibers with graphitic carbon-encased Co nanoparticles as an efficient bifunctional electrocatalyst[J]. Small,2018,14:1800423-1800430. doi: 10.1002/smll.201800423
    YUAN H L, WANG Y Q, ZHOU S M. Low-temperature preparation of superparamagnetic CoFe2O4 microspheres with high saturation magnetization[J]. Nanoscale Research Letters,2010,5:1817-1821. doi: 10.1007/s11671-010-9718-7
    LI J S, LI S L, TANG Y J, et al. Nitrogen-doped Fe/Fe3C@graphitic layer/carbon nanotube hybrids derived from MOFs: Efficient bifunctional electrocatalysts for ORR and OER[J]. Chemical Communications,2015,51:2710-2713. doi: 10.1039/C4CC09062D
    SHARMA Y, SHARMA N, RAO G V S, et al. Studies on spinel cobaltites, FeCo2O4 and MgCo2O4 as anodes for Li-ion batteries[J]. Solid State Ionics,2008,179:587-597. doi: 10.1016/j.ssi.2008.04.007
    OKU M, HIROKAWA K. X-ray photoelectron spectra of inequivalent atoms in inorganic compounds[J]. Journal of Solid State Chemistry,1979,30:45-53. doi: 10.1016/0022-4596(79)90128-2
    XIAO J W, YANG S. Bio-inspired synthesis of NaCl-type CoxNi1-xO (0 ≤ x < 1) nanorods on reduced graphene oxide sheets and screening for asymmetric electrochemical capacitors[J]. Journal of Material Chemistry,2012,22:12253-12262. doi: 10.1039/c2jm31057k
    FU Y Y, XU L, ZHAO W K, et al. Spinel CoMn2O4 nanosheet arrays grown on nickel foam for high-performance supercapacitor electrode[J]. Applied Surface Science,2015,357:2013-2021. doi: 10.1016/j.apsusc.2015.09.176
    MA S C, SUN L Q, CONG L N. Multiporous MnCo2O4 microspheres as an efficient bifunctional catalyst for nonaqueous Li-O2 batteries[J]. Journal of Physical Chemistry C,2013,117:25890-25897. doi: 10.1021/jp407576q
    WU J, YANG Z R, SUN Q J, et al. Synthesis and electrocatalytic activity of phosphorus-doped carbon xerogel for oxygen reduction[J]. Electrochimica Acta,2014,127:53-60. doi: 10.1016/j.electacta.2014.02.016
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