Advertisement

Ionics

, Volume 25, Issue 2, pp 785–796 | Cite as

MOF-derived Co nanoparticles embedded in N,S-codoped carbon layer/MWCNTs for efficient oxygen reduction in alkaline media

  • Shasha Li
  • Zhongqing JiangEmail author
  • Xunwen XiaoEmail author
  • Weiheng Chen
  • Xiaoning Tian
  • Xiaogang HaoEmail author
  • Zhong-Jie Jiang
Original Paper
  • 64 Downloads

Abstract

The hydrothermal reaction of cobalt salt in the presence of 4-pyridyl-tetrathiafulvalene-4-pyridyl (4-py-TTF-4-py) and terephthalic acid (PTA) has been employed for the preparation of a novel metal–organic framework (MOF), i.e., (4-py-TTF-4-py)2M2(PTA)4 (M = Co2+). The obtained MOF is then used as a starting material for the synthesis of Co nanoparticles embedded in N,S-codoped carbon layer and supported on multi-walled carbon nanotubes (Co@NSC/MWCNTs) through the high-temperature calcination. Specifically, the calcination leads to the formation of N,S-codoped carbon-coated Co nanoparticles with simultaneous growth on the MWCNTs due to decomposition of the MOF. When used as the electrocatalyst, the Co@NSC/MWCNTs are found to have a higher activity for the oxygen reduction reaction (ORR) and follow a four-electron pathway. The catalytic activity of the Co@NSC/MWCNTs is much higher than that of the pure MWCNTs and the MOFs/MWCNTs. Although the Co@NSC/MWCNTs still exhibit slightly higher overpotential for the ORR, it is indeed more kinetically facile than the commercial Pt/C catalyst, as demonstrated by its higher limiting current density and lower Tafel slope. Additionally, the Co@NSC/MWCNTs also show superior stability and better tolerance to methanol crossover and CO poisoning, compared with those of the commercial Pt/C catalyst. These results strongly suggest that the Co@NSC/MWCNTs could be used as one of the most promising ORR electrocatalysts for the ORR with great potential to replace the Pt/C. The work present here opens up a new route for the design of carbon-integrated ORR electrocatalysts with high performance from a great number of available and yet rapidly growing MOFs.

Keywords

Metal–organic framework N,S-codoped carbon Multi-walled carbon nanotube Oxygen reduction reaction Nonprecious metal electrocatalyst 

Notes

Funding information

This work is supported by the Chinese National Natural Science Foundation (Nos. U1532139 and 21476156), the Ningbo Natural Science Foundation (No. 2017A610059), Fundamental Research Funds for the Central Universities of SCUT (No.2018ZD25), the Guangdong Provincial Natural Science Foundation (No. 2017A030313092), and the Guangdong Innovative and Entepreneurial Research Team Program (No. 2014ZT05N200).

Supplementary material

11581_2018_2775_MOESM1_ESM.docx (172 kb)
ESM 1 (DOCX 171 kb)

References

  1. 1.
    Chen Z, Higgins D, Chen Z (2010) Nitrogen doped carbon nanotubes and their impact on the oxygen reduction reaction in fuel cells. Carbon 48(11):3057–3065CrossRefGoogle Scholar
  2. 2.
    Hu C, Dai L (2016) Carbon-based metal-free catalysts for electrocatalysis beyond the ORR. Angew Chem Int Ed 55(39):11736–11758CrossRefGoogle Scholar
  3. 3.
    Jiang Z, Jiang Z-J, Maiyalagan T, Manthiram A (2016) Cobalt oxide-coated N- and B-doped graphene hollow spheres as bifunctional electrocatalysts for oxygen reduction and oxygen evolution reactions. J Mater Chem A 4(16):5877–5889CrossRefGoogle Scholar
  4. 4.
    Li Q, Cao R, Cho J, Wu G (2014) Nanocarbon electrocatalysts for oxygen reduction in alkaline media for advanced energy conversion and storage. Adv Energy Mater 4(6):1301415–1301433Google Scholar
  5. 5.
    Paraknowitsch JP, Thomas A (2013) Doping carbons beyond nitrogen: an overview of advanced heteroatom doped carbons with boron, sulphur and phosphorus for energy applications. Energy Environ Sci 6(10):2839–2855Google Scholar
  6. 6.
    Jiang Z, Zhao X, Tian X, Luo L, Fang J, Gao H, Jiang ZJ (2015) Hydrothermal synthesis of boron and nitrogen codoped hollow graphene microspheres with enhanced electrocatalytic activity for oxygen reduction reaction. ACS Appl Mater Interfaces 7(34):19398–19407CrossRefGoogle Scholar
  7. 7.
    Li J, Chen Y, Tang Y, Li S, Dong H, Li K, Han M, Lan Y-Q, Bao J, Dai Z (2014) Metal–organic framework templated nitrogen and sulfur co-doped porous carbons as highly efficient metal-free electrocatalysts for oxygen reduction reactions. J Mater Chem A 2(18):6316–6319CrossRefGoogle Scholar
  8. 8.
    Kim J, Lee SW, Carlton C, Shao-Horn Y (2011) Pt-covered multiwall carbon nanotubes for oxygen reduction in fuel cell applications. J Phys Chem Lett 2(11):1332–1336CrossRefGoogle Scholar
  9. 9.
    Yu X, Ye S (2007) Recent advances in activity and durability enhancement of Pt/C catalytic cathode in PEMFC. J Power Sources 172(1):145–154CrossRefGoogle Scholar
  10. 10.
    Ma R, Zhou Y, Chen Y, Li P, Liu Q, Wang J (2015) Ultrafine molybdenum carbide nanoparticles composited with carbon as a highly active hydrogen-evolution electrocatalyst. Angew Chem Int Ed 54(49):14723–14727CrossRefGoogle Scholar
  11. 11.
    Ge L, Lin R, Zhu Z, Wang H (2017) A nitrogen-doped electrocatalyst from metal–organic framework-carbon nanotube composite. J Mater Res 33(05):538–545CrossRefGoogle Scholar
  12. 12.
    Hou Y, Wen Z, Cui S, Ci S, Mao S, Chen J (2015) An advanced nitrogen-doped graphene/cobalt-embedded porous carbon polyhedron hybrid for efficient catalysis of oxygen reduction and water splitting. Adv Funct Mater 25(6):872–882CrossRefGoogle Scholar
  13. 13.
    Zhang L, Wang A, Wang W, Huang Y, Liu X, Miao S, Liu J, Zhang T (2015) Co–N–C catalyst for C–C coupling reactions: on the catalytic performance and active sites. ACS Catal 5(11):6563–6572CrossRefGoogle Scholar
  14. 14.
    Aijaz A, Masa J, Rosler C, Xia W, Weide P, Botz AJ, Fischer RA, Schuhmann W, Muhler M (2016) Co@Co3O4 encapsulated in carbon nanotube-grafted nitrogen-doped carbon polyhedra as an advanced bifunctional oxygen electrode. Angew Chem Int Ed 55(12):4087–4091CrossRefGoogle Scholar
  15. 15.
    Jiang ZJ, Jiang Z (2016) Interaction induced high catalytic activities of CoO nanoparticles grown on nitrogen-doped hollow graphene microspheres for oxygen reduction and evolution reactions. Sci Rep 6:27081-27094Google Scholar
  16. 16.
    Feng Y, Alonso-Vante N (2012) Carbon-supported cubic CoSe2 catalysts for oxygen reduction reaction in alkaline medium. Electrochim Acta 72:129–133CrossRefGoogle Scholar
  17. 17.
    Feng Y, He T, Alonso-Vante N (2007) In situ free-surfactant synthesis and ORR-electrochemistry of carbon-supported Co3S4 and CoSe2 nanoparticles. Chem Mater 20(1):26–28CrossRefGoogle Scholar
  18. 18.
    Xia W, Mahmood A, Liang Z, Zou R, Guo S (2016) Earth-abundant nanomaterials for oxygen reduction. Angew Chem Int Ed 55(8):2650–2676CrossRefGoogle Scholar
  19. 19.
    Wang Z, Xiao S, Zhu Z, Long X, Zheng X, Lu X, Yang S (2015) Cobalt-embedded nitrogen doped carbon nanotubes: a bifunctional catalyst for oxygen electrode reactions in a wide pH range. ACS Appl Mater Interfaces 7(7):4048–4055CrossRefGoogle Scholar
  20. 20.
    Zhou M, Wang HL, Guo S (2016) Towards high-efficiency nanoelectrocatalysts for oxygen reduction through engineering advanced carbon nanomaterials. Chem Soc Rev 45(5):1273–1307CrossRefGoogle Scholar
  21. 21.
    Sohrabi S, Dehghanpour S, Ghalkhani M (2017) A cobalt porphyrin-based metal organic framework/multi-walled carbon nanotube composite electrocatalyst for oxygen reduction and evolution reactions. J Mater Sci 53(5):3624–3639CrossRefGoogle Scholar
  22. 22.
    Chen B, Ma G, Zhu Y, Xia Y (2017) Metal-organic-frameworks derived cobalt embedded in various carbon structures as bifunctional electrocatalysts for oxygen reduction and evolution reactions. Sci Rep 7(1):5266–5274Google Scholar
  23. 23.
    Ma L, Chen S, Pei Z, Huang Y, Liang G, Mo F, Yang Q, Su J, Gao Y, Zapien JA, Zhi C (2018) Single-site active iron-based bifunctional oxygen catalyst for a compressible and rechargeable zinc-air battery. ACS Nano 12(2):1949–1958CrossRefGoogle Scholar
  24. 24.
    Zhu H, Sun Z, Chen N, Cao H, Chen M, Li K, Cai Y, Wang F (2017) A non-precious-metal catalyst derived from a Cp2-Co+-PBI composite for cathodic oxygen reduction under both acidic and alkaline conditions. ChemElectroChem 4(5):1117–1123CrossRefGoogle Scholar
  25. 25.
    Zuo Z, Wang D, Zhang J, Lu F, Li Y (2018) Synthesis and applications of graphdiyne-based metal-free catalysts. Adv Mater 1803762–1803774Google Scholar
  26. 26.
    Huang C, Li Y, Wang N, Xue Y, Zuo Z, Liu H, Li Y (2018) Progress in research into 2D graphdiyne-based materials. Chem Rev 118(16):7744–7803CrossRefGoogle Scholar
  27. 27.
    Song Z, Cheng N, Lushington A, Sun X (2016) Recent progress on MOF-derived nanomaterials as advanced electrocatalysts in fuel cells. Catalysts 6(12):116–134Google Scholar
  28. 28.
    Yap MH, Fow KL, Chen GZ (2017) Synthesis and applications of MOF-derived porous nanostructures. Green Energy Environ 2(3):218–245CrossRefGoogle Scholar
  29. 29.
    Zhang W, Liu Y, Lu G, Wang Y, Li S, Cui C, Wu J, Xu Z, Tian D, Huang W, DuCheneu JS, Wei WD, Chen H, Yang Y, Huo F (2015) Mesoporous metal-organic frameworks with size-, shape-, and space-distribution-controlled pore structure. Adv Mater 27(18):2923–2929CrossRefGoogle Scholar
  30. 30.
    Xiao X, Pan W, Wang Z, Shen L, Fang J, Gao H, Li X, Fujiwara H (2014) Self-ordering of organic-metal hybrid microstructures based on tetrathiafulvalene derivatives. Synth Met 189:42–46CrossRefGoogle Scholar
  31. 31.
    Yadav RM, Wu J, Kochandra R, Ma L, Tiwary CS, Ge L, Ye G, Vajtai R, Lou J, Ajayan PM (2015) Carbon nitrogen nanotubes as efficient bifunctional electrocatalysts for oxygen reduction and evolution reactions. ACS Appl Mater Interfaces 7(22):11991–12000CrossRefGoogle Scholar
  32. 32.
    Wang S, Yu D, Dai L (2011) Polyelectrolyte functionalized carbon nanotubes as efficient metal-free electrocatalysts for oxygen reduction. J Am Chem Soc 133(14):5182–5185CrossRefGoogle Scholar
  33. 33.
    Shi Q, Wang Y, Wang Z, Lei Y, Wang B, Wu N, Han C, Xie S, Gou Y (2015) Three-dimensional (3D) interconnected networks fabricated via in-situ growth of N-doped graphene/carbon nanotubes on Co-containing carbon nanofibers for enhanced oxygen reduction. Nano Res 9(2):317–328CrossRefGoogle Scholar
  34. 34.
    Tendeloo G, Nagy J (1998) Purification of catalytically produced multi-wall nanotubes. J Chem Soc Faraday Trans 94(24):3753–3758CrossRefGoogle Scholar
  35. 35.
    Zhang L, Wang X, Wang R, Hong M (2015) Structural evolution from metal–organic framework to hybrids of nitrogen-doped porous carbon and carbon nanotubes for enhanced oxygen reduction activity. Chem Mater 27(22):7610–7618CrossRefGoogle Scholar
  36. 36.
    Zheng R, Mo Z, Liao S, Song H, Fu Z, Huang P (2014) Heteroatom-doped carbon nanorods with improved electrocatalytic activity toward oxygen reduction in an acidic medium. Carbon 69:132–141CrossRefGoogle Scholar
  37. 37.
    Wang J, Wu Z, Han L, Lin R, Xiao W, Xuan C, Xin HL, Wang D (2016) Nitrogen and sulfur co-doping of partially exfoliated MWCNTs as 3-D structured electrocatalysts for the oxygen reduction reaction. J Mater Chem A 4(15):5678–5684CrossRefGoogle Scholar
  38. 38.
    Duan J, Chen S, Dai S, Qiao SZ (2014) Shape control of Mn3O4 nanoparticles on nitrogen-doped graphene for enhanced oxygen reduction activity. Adv Funct Mater 24(14):2072–2078CrossRefGoogle Scholar
  39. 39.
    Ferrari AC, Basko DM (2013) Raman spectroscopy as a versatile tool for studying the properties of graphene. Nat Nanotechnol 8(4):235–246CrossRefGoogle Scholar
  40. 40.
    Liu Y, Chen N, Wang F, Cai Y, Zhu H (2017) Pt–Co deposited on polyaniline-modified carbon for the electro-reduction of oxygen: the interaction between Pt–Co nanoparticles and polyaniline. New J Chem 41(14):6585–6592CrossRefGoogle Scholar
  41. 41.
    Meng J, Niu C, Xu L, Li J, Liu X, Wang X, Wu Y, Xu X, Chen W, Li Q, Zhu Z, Zhao D, Mai L (2017) General oriented formation of carbon nanotubes from metal-organic frameworks. J Am Chem Soc 139(24):8212–8221CrossRefGoogle Scholar
  42. 42.
    Mousavi-Khoshdel SM, Jahanbakhsh-bonab P, Targholi E (2016) Structural, electronic properties, and quantum capacitance of B, N and P-doped armchair carbon nanotubes. Phys Lett A 380(41):3378–3383CrossRefGoogle Scholar
  43. 43.
    Song J, Liu T, Ali S, Li B, Su D (2017) The synergy effect and reaction pathway in the oxygen reduction reaction on the sulfur and nitrogen dual doped graphene catalyst. Chem Phys Lett 677:65–69CrossRefGoogle Scholar
  44. 44.
    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):924–931CrossRefGoogle Scholar
  45. 45.
    Shang H, Zuo Z, Zheng H, Li K, Tu Z, Yi Y, Liu H, Li Y, Li Y (2018) N-doped graphdiyne for high-performance electrochemical electrodes. Nano Energy 44:144–154CrossRefGoogle Scholar
  46. 46.
    Liu S, Li G, Gao Y, Xiao Z, Zhang J, Wang Q, Zhang X, Wang L (2017) Doping carbon nanotubes with N, S, and B for electrocatalytic oxygen reduction: a systematic investigation on single, double, and triple doped modes. Catal Sci Technol 7(18):4007–4016CrossRefGoogle Scholar
  47. 47.
    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):1501966–1501977Google Scholar
  48. 48.
    Nie Y, Li L, Wei Z (2015) Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction. Chem Soc Rev 44(8):2168–2201CrossRefGoogle Scholar
  49. 49.
    Yu Y, Xin HL, Hovden R, Wang D, Rus ED, Mundy JA, Muller DA, Abruna HD (2012) Three-dimensional tracking and visualization of hundreds of Pt-Co fuel cell nanocatalysts during electrochemical aging. Nano Lett 12(9):4417–4423CrossRefGoogle Scholar
  50. 50.
    Zhu H, Cai Y, Wang F, Gao P, Cao J (2018) Scalable preparation of the chemically ordered Pt-Fe-Au nanocatalysts with high catalytic reactivity and stability for oxygen reduction reactions. ACS Appl Mater Interfaces 10(26):22156–22166CrossRefGoogle Scholar
  51. 51.
    Zhang Y, Huang Q, Zou Z, Yang J, Vogel W, Yang H (2010) Enhanced durability of Au cluster decorated Pt nanoparticles for the oxygen reduction reaction. J Phys Chem C 114(14):6860–6868CrossRefGoogle Scholar
  52. 52.
    Davies J, Tsotridis G (2008) Temperature-dependent kinetic study of CO desorption from Pt PEM fuel cell anodes. J Phys Chem C 112(9):3392–3397CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Chemical EngineeringTaiyuan University of TechnologyTaiyuanChina
  2. 2.Department of Materials and Chemical EngineeringNingbo University of TechnologyNingboChina
  3. 3.Department of Physics, Key Laboratory of ATMMT Ministry of EducationZhejiang Sci-Tech UniversityHangzhouChina
  4. 4.Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, College of Environment and EnergySouth China University of TechnologyGuangzhouChina

Personalised recommendations