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Science China Materials

, Volume 62, Issue 5, pp 671–680 | Cite as

Porous nitrogen/halogen dual-doped nanocarbons derived from imidazolium functionalized cationic metal-organic frameworks for highly efficient oxygen reduction reaction

  • Qiao Wu (伍巧)
  • Jun Liang (梁均)
  • Jun-Dong Yi (伊俊东)
  • Peng-Chao Shi (石鹏超)
  • Yuan-Biao Huang (黄远标)Email author
  • Rong Cao (曹荣)Email author
Articles

Abstract

Heteroatom-doped carbon materials as alternative catalysts for oxygen reduction reaction (ORR) have drawn increasing attention due to their tunable chemical and electronic structures for achieving high activity and stability. However, there still remains a great challenge to fabricate porous heteroatoms dual-doped carbons with uniformly doping in a facile and controllable way. Herein, imidazole/imidazolium-functionalized metal-organic frameworks (MOFs) are employed as precursors and templates to achieve porous nitrogen and halogen dual-doped nanocarbons. Among these carbon materials, the as-prepared nitrogen/bromine dual-doped catalyst BrNC-800 exhibits the best ORR performance with a positive half-wave potential at 0.80 V (vs. RHE) in 0.1 mol L−1 KOH, which is comparable to the benchmark commercial 20 wt% Pt/C catalyst. BrNC-800 shows excellent long term stability and methanol tolerance. This work provides a facile approach to fabricate highly efficient heteroatoms dual-doped carbon catalysts for energy conversion.

Keywords

cationic metal-organic framework imidazolium nitrogen/halogen dual-doped nanocarbon catalysts oxygen reduction reaction 

咪唑鎓盐官能化阳离子型金属-有机框架衍生的多孔氮/卤素双掺杂纳米碳高效氧还原催化剂

摘要

低成本、高效稳定的非金属材料作为氧还原反应(ORR)的电催化剂对于燃料电池的规模化应用至关重要. 杂原子掺杂的多孔碳材料具有可调的化学组成和电子结构, 能显著提升氧还原催化活性. 基于此, 我们采用咪唑鎓盐功能化的金属-有机框架(MOFs)作为前驱体 和自牺牲模板, 制备了氮和卤素双掺杂多孔纳米碳催化剂. 其中氮/溴双掺杂催化剂BrNC-800在碱性条件下具有优异的电催化性能、稳定 性和抗甲醇毒化能力. 其优异的电催化活性归因于: (1) 大量吡啶氮和石墨氮的掺杂产生丰富的碳活性位点, 同时高的石墨化程度有助于 提高导电性, 促进氧还原活性; (2) 溴的存在改变了催化剂的化学组分和结构特征, 并活化相邻碳产生额外活性位点; (3) 高比表面和多级 孔结构有助于传质与增加暴露的氧还原活性位的数量, 而提高催化效率. 这项工作为以MOFs为前驱体制备高效的杂原子双掺杂碳材料提供了一种简便的方法.

Notes

Acknowledgements

We acknowledge the financial support from the National Key Research and Development Program of China (2018YFA0208600), National Basic Research Program of China (973 Program, 2014CB845605), Key Research Program of Frontier Science, Chinese Academy of Sciences (QYZDJ-SSW-SLH045), Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), National Natural Science Foundation of China (21671188, 21871263, 21521061 and 21331006) and Youth Innovation Promotion Association, Chinese Academy of Sciences (2014265).

Supplementary material

40843_2018_9364_MOESM1_ESM.pdf (2.7 mb)
Porous nitrogen/halogen dual-doped nanocarbons derived from imidazolium functionalized cationic metal-organic frameworks for highly efficient oxygen reduction reaction

References

  1. 1.
    Steele BCH, Heinzel A. Materials for fuel-cell technologies. Nature, 2001, 414: 345–352CrossRefGoogle Scholar
  2. 2.
    Dai L, Xue Y, Qu L, et al. Metal-free catalysts for oxygen reduction reaction. Chem Rev, 2015, 115: 4823–4892CrossRefGoogle Scholar
  3. 3.
    Stamenkovic VR, Fowler B, Mun BS, et al. Improved oxygen reduction activity on Pt3Ni (111) via increased surface site availability. Science, 2007, 315: 493–497CrossRefGoogle Scholar
  4. 4.
    Borup R, Meyers J, Pivovar B, et al. Scientific aspects of polymer electrolyte fuel cell durability and degradation. Chem Rev, 2007, 107: 3904–3951CrossRefGoogle Scholar
  5. 5.
    Zhang J, Sasaki K, Sutter E, et al. Stabilization of platinum oxygenreduction electrocatalysts using gold clusters. Science, 2007, 315: 220–222CrossRefGoogle Scholar
  6. 6.
    Zhang C, Sandorf W, Peng Z. Octahedral Pt2CuNi uniform alloy nanoparticle catalyst with high activity and promising stability for oxygen reduction reaction. ACS Catal, 2015, 5: 2296–2300CrossRefGoogle Scholar
  7. 7.
    Huang X, Zhao Z, Cao L, et al. High-performance transition metaldoped Pt3Ni octahedra for oxygen reduction reaction. Science, 2015, 348: 1230–1234CrossRefGoogle Scholar
  8. 8.
    Kuroki H, Tamaki T, Matsumoto M, et al. Refined structural analysis of connected platinum–iron nanoparticle catalysts with enhanced oxygen reduction activity. ACS Appl Energy Mater, 2018, 1: 324–330CrossRefGoogle Scholar
  9. 9.
    Wu G, More KL, Johnston CM, et al. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science, 2011, 332: 443–447CrossRefGoogle Scholar
  10. 10.
    Byon HR, Suntivich J, Shao-Horn Y. Graphene-based non-noblemetal catalysts for oxygen reduction reaction in acid. Chem Mater, 2011, 23: 3421–3428CrossRefGoogle Scholar
  11. 11.
    Lefèvre M, Proietti E, Jaouen F, et al. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science, 2009, 324: 71–74CrossRefGoogle Scholar
  12. 12.
    Wang DW, Su D. Heterogeneous nanocarbon materials for oxygen reduction reaction. Energy Environ Sci, 2014, 7: 576–591CrossRefGoogle Scholar
  13. 13.
    Liang Y, Li Y, Wang H, et al. Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat Mater, 2011, 10: 780–786CrossRefGoogle Scholar
  14. 14.
    Zhang H, Zhou W, Chen T, et al. A modular strategy for decorating isolated cobalt atoms into multichannel carbon matrix for electrocatalytic oxygen reduction. Energy Environ Sci, 2018, 11: 1980–1984CrossRefGoogle Scholar
  15. 15.
    Zeng L, Cui X, Shi J. A facile strategy for ultrasmall Pt NPs being partially-embedded in N-doped carbon nanosheet structure for efficient electrocatalysis. Sci China Mater, 2018, 61: 1557–1566CrossRefGoogle Scholar
  16. 16.
    Tan H, Li Y, Jiang X, et al. Perfectly ordered mesoporous ironnitrogen doped carbon as highly efficient catalyst for oxygen reduction reaction in both alkaline and acidic electrolytes. Nano Energy, 2017, 36: 286–294CrossRefGoogle Scholar
  17. 17.
    Wu S, Zhu Y, Huo Y, et al. Bimetallic organic frameworks derived CuNi/carbon nanocomposites as efficient electrocatalysts for oxygen reduction reaction. Sci China Mater, 2017, 60: 654–663CrossRefGoogle Scholar
  18. 18.
    Bu L, Zhang N, Guo S, et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science, 2016, 354: 1410–1414CrossRefGoogle Scholar
  19. 19.
    Bu L, Shao Q, E B, et al. PtPb/PtNi intermetallic core/atomic layer shell octahedra for efficient oxygen reduction electrocatalysis. J Am Chem Soc, 2017, 139: 9576–9582CrossRefGoogle Scholar
  20. 20.
    Bu L, Tang C, Shao Q, et al. Three-dimensional Pd3Pb nanosheet assemblies: high-performance non-Pt electrocatalysts for bifunctional fuel cell reactions. ACS Catal, 2018, 8: 4569–4575CrossRefGoogle Scholar
  21. 21.
    Gong K, Du F, Xia Z, et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science, 2009, 323: 760–764CrossRefGoogle Scholar
  22. 22.
    Liu R, Wu D, Feng X, et al. Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction. Angew Chem, 2010, 122: 2619–2623CrossRefGoogle Scholar
  23. 23.
    Sheng ZH, Shao L, Chen JJ, et al. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. ACS Nano, 2011, 5: 4350–4358CrossRefGoogle Scholar
  24. 24.
    Yang L, Jiang S, Zhao Y, et al. Boron-doped carbon nanotubes as metal-free electrocatalysts for the oxygen reduction reaction. Angew Chem, 2011, 123: 7270–7273CrossRefGoogle Scholar
  25. 25.
    Sheng ZH, Gao HL, Bao WJ, et al. Synthesis of boron doped graphene for oxygen reduction reaction in fuel cells. J Mater Chem, 2012, 22: 390–395CrossRefGoogle Scholar
  26. 26.
    Liu ZW, Peng F, Wang HJ, et al. Phosphorus-doped graphite layers with high electrocatalytic activity for the O2 reduction in an alkaline medium. Angew Chem, 2011, 123: 3315–3319CrossRefGoogle Scholar
  27. 27.
    Yang Z, Yao Z, Li G, et al. Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction. ACS Nano, 2012, 6: 205–211CrossRefGoogle Scholar
  28. 28.
    Yao Z, Nie H, Yang Z, et al. Catalyst-free synthesis of iodine-doped graphene via a facile thermal annealing process and its use for electrocatalytic oxygen reduction in an alkaline medium. Chem Commun, 2012, 48: 1027–1029CrossRefGoogle Scholar
  29. 29.
    Jeon IY, Choi HJ, Choi M, et al. Facile, scalable synthesis of edgehalogenated graphene nanoplatelets as efficient metal-free eletrocatalysts for oxygen reduction reaction. Sci Rep, 2013, 3: 1810CrossRefGoogle Scholar
  30. 30.
    Zhang M, Dai L. Carbon nanomaterials as metal-free catalysts in next generation fuel cells. Nano Energy, 2012, 1: 514–517CrossRefGoogle Scholar
  31. 31.
    You C, Jiang X, Wang X, et al. Nitrogen, sulfur co-doped carbon derived from naphthalene-based covalent organic framework as an efficient catalyst for oxygen reduction. ACS Appl Energy Mater, 2018, 1: 161–166CrossRefGoogle Scholar
  32. 32.
    Liang J, Jiao Y, Jaroniec M, et al. Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. Angew Chem Int Ed, 2012, 51: 11496–11500CrossRefGoogle Scholar
  33. 33.
    Guo Z, Jiang C, Teng C, et al. Sulfur, trace nitrogen and iron codoped hierarchically porous carbon foams as synergistic catalysts for oxygen reduction reaction. ACS Appl Mater Interfaces, 2014, 6: 21454–21460CrossRefGoogle Scholar
  34. 34.
    Li J, Chen Y, Tang Y, et al. 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, 2014, 2: 6316–6319CrossRefGoogle Scholar
  35. 35.
    Yan D, Guo L, Xie C, et al. N, P-dual doped carbon with trace Co and rich edge sites as highly efficient electrocatalyst for oxygen reduction reaction. Sci China Mater, 2018, 61: 679–685CrossRefGoogle Scholar
  36. 36.
    Jiang S, Sun Y, Dai H, et al. Nitrogen and fluorine dual-doped mesoporous graphene: a high-performance metal-free ORR electrocatalyst with a super-low HO2 -yield. Nanoscale, 2015, 7: 10584–10589CrossRefGoogle Scholar
  37. 37.
    Peera SG, Sahu AK, Arunchander A, et al. Nitrogen and fluorine co-doped graphite nanofibers as high durable oxygen reduction catalyst in acidic media for polymer electrolyte fuel cells. Carbon, 2015, 93: 130–142CrossRefGoogle Scholar
  38. 38.
    Paraknowitsch JP, Thomas A. Doping carbons beyond nitrogen: an overview of advanced heteroatom doped carbons with boron, sulphur and phosphorus for energy applications. Energy Environ Sci, 2013, 6: 2839–2855CrossRefGoogle Scholar
  39. 39.
    Yang Z, Nie H, Chen X, et al. Recent progress in doped carbon nanomaterials as effective cathode catalysts for fuel cell oxygen reduction reaction. J Power Sources, 2013, 236: 238–249CrossRefGoogle Scholar
  40. 40.
    Ranjbar Sahraie N, Paraknowitsch JP, Göbel C, et al. Noble-metalfree electrocatalysts with enhanced ORR performance by taskspecific functionalization of carbon using ionic liquid precursor systems. J Am Chem Soc, 2014, 136: 14486–14497CrossRefGoogle Scholar
  41. 41.
    Fellinger TP, Su DS, Engenhorst M, et al. Thermolytic synthesis of graphitic boron carbon nitride from an ionic liquid precursor: mechanism, structure analysis and electronic properties. J Mater Chem, 2012, 22: 23996–24005CrossRefGoogle Scholar
  42. 42.
    Fulvio PF, Lee JS, Mayes RT, et al. Boron and nitrogen-rich carbons from ionic liquid precursors with tailorable surface properties. Phys Chem Chem Phys, 2011, 13: 13486–13491CrossRefGoogle Scholar
  43. 43.
    Lee JS, Wang X, Luo H, et al. Facile ionothermal synthesis of microporous and mesoporous carbons from task specific ionic liquids. J Am Chem Soc, 2009, 131: 4596–4597CrossRefGoogle Scholar
  44. 44.
    Mahmood A, Guo W, Tabassum H, et al. Metal-organic framework-based nanomaterials for electrocatalysis. Adv Energy Mater, 2016, 6: 1600423CrossRefGoogle Scholar
  45. 45.
    Dang S, Zhu QL, Xu Q. Nanomaterials derived from metal–organic frameworks. Nat Rev Mater, 2017, 3: 17075CrossRefGoogle Scholar
  46. 46.
    Liu B, Shioyama H, Akita T, et al. Metal-organic framework as a template for porous carbon synthesis. J Am Chem Soc, 2008, 130: 5390–5391CrossRefGoogle Scholar
  47. 47.
    Jiang HL, Liu B, Lan YQ, et al. From metal–organic framework to nanoporous carbon: toward a very high surface area and hydrogen uptake. J Am Chem Soc, 2011, 133: 11854–11857CrossRefGoogle Scholar
  48. 48.
    Aijaz A, Akita T, Yang H, et al. From ionic-liquid@metal–organic framework composites to heteroatom-decorated large-surface area carbons: superior CO2 and H2 uptake. Chem Commun, 2014, 50: 6498–6501CrossRefGoogle Scholar
  49. 49.
    Jiang HL, Xu Q. Porous metal–organic frameworks as platforms for functional applications. Chem Commun, 2011, 47: 3351–3370CrossRefGoogle Scholar
  50. 50.
    Hu M, Reboul J, Furukawa S, et al. Direct carbonization of Albased porous coordination polymer for synthesis of nanoporous carbon. J Am Chem Soc, 2012, 134: 2864–2867CrossRefGoogle Scholar
  51. 51.
    Yi FY, Zhang R, Wang H, et al. Metal-organic frameworks and their composites: synthesis and electrochemical applications. Small Methods, 2017, 1: 1700187CrossRefGoogle Scholar
  52. 52.
    Lin T, Chen IW, Liu F, et al. Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage. Science, 2015, 350: 1508–1513CrossRefGoogle Scholar
  53. 53.
    Meng J, Niu C, Xu L, et al. General oriented formation of carbon nanotubes from metal–organic frameworks. J Am Chem Soc, 2017, 139: 8212–8221CrossRefGoogle Scholar
  54. 54.
    Zhao S, Yin H, Du L, et al. Carbonized nanoscale metal–organic frameworks as high performance electrocatalyst for oxygen reduction reaction. ACS Nano, 2014, 8: 12660–12668CrossRefGoogle Scholar
  55. 55.
    Tang H, Yin H, Wang J, et al. Molecular architecture of cobalt porphyrin multilayers on reduced graphene oxide sheets for highperformance oxygen reduction reaction. Angew Chem, 2013, 125: 5695–5699CrossRefGoogle Scholar
  56. 56.
    Xia W, Zou R, An L, et al. A metal–organic framework route to in situ encapsulation of Co@Co3O4@C core@bishell nanoparticles into a highly ordered porous carbon matrix for oxygen reduction. Energy Environ Sci, 2015, 8: 568–576CrossRefGoogle Scholar
  57. 57.
    Lu XF, Gu LF, Wang JW, et al. Bimetal-organic framework derived CoFe2O4/C porous hybrid nanorod arrays as high-performance electrocatalysts for oxygen evolution reaction. Adv Mater, 2017, 29: 1604437CrossRefGoogle Scholar
  58. 58.
    Liang J, Chen RP, Wang XY, et al. Postsynthetic ionization of an imidazole-containing metal–organic framework for the cycloaddition of carbon dioxide and epoxides. Chem Sci, 2017, 8: 1570–1575CrossRefGoogle Scholar
  59. 59.
    Pachfule P, Biswal BP, Banerjee R. Control of porosity by using isoreticular zeolitic imidazolate frameworks (IRZIFs) as a template for porous carbon synthesis. Chem Eur J, 2012, 18: 11399–11408CrossRefGoogle Scholar
  60. 60.
    Zhao X, Zou X, Yan X, et al. Defect-driven oxygen reduction reaction (ORR) of carbon without any element doping. Inorg Chem Front, 2016, 3: 417–421CrossRefGoogle Scholar
  61. 61.
    Zhu Y, Murali S, Cai W, et al. Graphene and graphene oxide: synthesis, properties, and applications. Adv Mater, 2010, 22: 3906–3924CrossRefGoogle Scholar
  62. 62.
    Zhang L, Wang X, Wang R, et al. Structural evolution from metal–organic framework to hybrids of nitrogen-doped porous carbon and carbon nanotubes for enhanced oxygen reduction activity. Chem Mater, 2015, 27: 7610–7618CrossRefGoogle Scholar
  63. 63.
    Zheng J, Ekström TC, Gordeev SK, et al. Carbon with an onionlike structure obtained by chlorinating titanium carbide. J Mater Chem, 2000, 10: 1039–1041CrossRefGoogle Scholar
  64. 64.
    Kundu S, Nagaiah TC, Xia W, et al. Electrocatalytic activity and stability of nitrogen-containing carbon nanotubes in the oxygen reduction reaction. J Phys Chem C, 2009, 113: 14302–14310CrossRefGoogle Scholar
  65. 65.
    Guo D, Shibuya R, Akiba C, et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science, 2016, 351: 361–365CrossRefGoogle Scholar
  66. 66.
    Guan BY, Yu L, (David) Lou XW. A dual-metal–organicframework derived electrocatalyst for oxygen reduction. Energy Environ Sci, 2016, 9: 3092–3096CrossRefGoogle Scholar
  67. 67.
    Vikkisk M, Kruusenberg I, Joost U, et al. Electrocatalytic oxygen reduction on nitrogen-doped graphene in alkaline media. Appl Catal B-Environ, 2014, 147: 369–376CrossRefGoogle Scholar
  68. 68.
    Zhang G, Luo H, Li H, et al. ZnO-promoted dechlorination for hierarchically nanoporous carbon as superior oxygen reduction electrocatalyst. Nano Energy, 2016, 26: 241–247CrossRefGoogle Scholar
  69. 69.
    Chang H, Joo SH, Pak C. Synthesis and characterization of mesoporous carbon for fuel cell applications. J Mater Chem, 2007, 17: 3078–3088CrossRefGoogle Scholar
  70. 70.
    Liang J, Du X, Gibson C, et al. N-doped graphene natively grown on hierarchical ordered porous carbon for enhanced oxygen reduction. Adv Mater, 2013, 25: 6226–6231CrossRefGoogle Scholar
  71. 71.
    Shi PC, Yi JD, Liu TT, et al. Hierarchically porous nitrogen-doped carbon nanotubes derived from core–shell ZnO@zeolitic imidazolate framework nanorods for highly efficient oxygen reduction reactions. J Mater Chem A, 2017, 5: 12322–12329CrossRefGoogle Scholar
  72. 72.
    Zhang L, Su Z, Jiang F, et al. Highly graphitized nitrogen-doped porous carbon nanopolyhedra derived from ZIF-8 nanocrystals as efficient electrocatalysts for oxygen reduction reactions. Nanoscale, 2014, 6: 6590–6602CrossRefGoogle Scholar
  73. 73.
    Lai L, Potts JR, Zhan D, et al. Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy Environ Sci, 2012, 5: 7936–7942CrossRefGoogle Scholar
  74. 74.
    Bao Z, Chang G, Xing H, et al. Potential of microporous metal–organic frameworks for separation of hydrocarbon mixtures. Energy Environ Sci, 2016, 9: 3612–3641CrossRefGoogle Scholar
  75. 75.
    Zheng F, Yang Y, Chen Q. High lithium anodic performance of highly nitrogen-doped porous carbon prepared from a metalorganic framework. Nat Commun, 2014, 5: 5261CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Qiao Wu (伍巧)
    • 1
    • 2
  • Jun Liang (梁均)
    • 1
  • Jun-Dong Yi (伊俊东)
    • 1
  • Peng-Chao Shi (石鹏超)
    • 1
  • Yuan-Biao Huang (黄远标)
    • 1
    Email author
  • Rong Cao (曹荣)
    • 1
    • 3
    Email author
  1. 1.State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouChina
  2. 2.College of Chemistry and Materials ScienceFujian Normal UniversityFuzhouChina
  3. 3.University of Chinese Academy of SciencesBeijingChina

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