logo

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

More info
  • ReceivedJul 28, 2018
  • AcceptedOct 8, 2018
  • PublishedNov 14, 2018

Abstract


Funded by

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 Nature Science Foundation of China(21671188,21871263,21521061,21331006)

Youth Innovation Promotion Association

Chinese Academy of Sciences(2014265)


Acknowledgment

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).


Interest statement

The authors declare no conflict of interest.


Contributions statement

Huang YB and Wu Q designed and engineered the samples; Wu Q, Liang J, Yi JD, Shi PC performed the experiments and the characterizations. Wu Q wrote the paper with support from Huang YB and Cao R. All authors contributed to the general discussion.


Author information

Qiao Wu received her bachelor’s degree from the School of Chemistry and Chemical Engineering, Henan Normal University in 2016. She is currently a master candidate in the College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, China. Her current research interest focuses on designing high-performance electrode materials for energy storage systems.


Yuan-Biao Huang obtained his PhD in 2009 under the supervision of Prof. GX Jin from Fudan University. In the same year, he joined Prof. Rong Cao’s group at Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS). In 2014, he joined Prof. Qiang Xu’s group at the National Institute of Advanced Industrial Science and Technology as a JSPS (Japan Society for the Promotion of Science) fellow. In 2015, he moved back to Prof. Cao’s research group at FJIRSM. His research interest focuses on porous MOF and COF based materials for catalysis.


Rong Cao was born in Fujian province, China. He obtained his PhD from FJIRSM, CAS, in 1993. Following post-doctoral experience in the Hong Kong Polytechnic University and JSPS Fellowship in Nagoya University, he became a professor at FJIRSM in 1998. Now, he is the director of FJIRSM. His main research interest includes supramolecular chemistry, inorganic–organic hybrid materials and nanocatalysis.


Supplement

Supplementary information

Supplementary data are available in the online version of the paper.


References

[1] Steele BCH, Heinzel A. Materials for fuel-cell technologies. Nature, 2001, 414: 345-352 CrossRef PubMed Google Scholar

[2] Dai L, Xue Y, Qu L, et al. Metal-free catalysts for oxygen reduction reaction. Chem Rev, 2015, 115: 4823-4892 CrossRef PubMed Google Scholar

[3] Stamenkovic VR, Fowler B, Mun BS, et al. Improved oxygen reduction activity on Pt3Ni (111) via increased surface site availability. Science, 2007, 315: 493-497 CrossRef PubMed ADS Google Scholar

[4] Borup R, Meyers J, Pivovar B, et al. Scientific aspects of polymer electrolyte fuel cell durability and degradation. Chem Rev, 2007, 107: 3904-3951 CrossRef PubMed Google Scholar

[5] Zhang J, Sasaki K, Sutter E, et al. Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters. Science, 2007, 315: 220-222 CrossRef PubMed ADS Google Scholar

[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: 2296-2300 CrossRef Google Scholar

[7] Huang X, Zhao Z, Cao L, et al. High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction. Science, 2015, 348: 1230-1234 CrossRef PubMed ADS Google Scholar

[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: 324-330 CrossRef Google Scholar

[9] Wu G, More KL, Johnston CM, et al. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science, 2011, 332: 443-447 CrossRef PubMed ADS Google Scholar

[10] Byon HR, Suntivich J, Shao-Horn Y. Graphene-based non-noble-metal catalysts for oxygen reduction reaction in acid. Chem Mater, 2011, 23: 3421-3428 CrossRef Google Scholar

[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: 71-74 CrossRef PubMed ADS Google Scholar

[12] Wang DW, Su D. Heterogeneous nanocarbon materials for oxygen reduction reaction. Energy Environ Sci, 2014, 7: 576-591 CrossRef Google Scholar

[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: 780-786 CrossRef PubMed ADS arXiv Google Scholar

[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: 1980-1984 CrossRef Google Scholar

[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: 1557-1566 CrossRef Google Scholar

[16] Tan H, Li Y, Jiang X, et al. Perfectly ordered mesoporous iron-nitrogen doped carbon as highly efficient catalyst for oxygen reduction reaction in both alkaline and acidic electrolytes. Nano Energy, 2017, 36: 286-294 CrossRef Google Scholar

[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: 654-663 CrossRef Google Scholar

[18] Bu L, Zhang N, Guo S, et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science, 2016, 354: 1410-1414 CrossRef PubMed ADS Google Scholar

[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: 9576-9582 CrossRef PubMed Google Scholar

[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: 4569-4575 CrossRef Google Scholar

[21] Gong K, Du F, Xia Z, et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science, 2009, 323: 760-764 CrossRef PubMed ADS Google Scholar

[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: 2619-2623 CrossRef Google Scholar

[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: 4350-4358 CrossRef PubMed Google Scholar

[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: 7270-7273 CrossRef Google Scholar

[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: 390-395 CrossRef Google Scholar

[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: 3315-3319 CrossRef Google Scholar

[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: 205-211 CrossRef PubMed Google Scholar

[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: 1027-1029 CrossRef PubMed Google Scholar

[29] Jeon IY, Choi HJ, Choi M, et al. Facile, scalable synthesis of edge-halogenated graphene nanoplatelets as efficient metal-free eletrocatalysts for oxygen reduction reaction. Sci Rep, 2013, 3: 1810 CrossRef PubMed ADS Google Scholar

[30] Zhang M, Dai L. Carbon nanomaterials as metal-free catalysts in next generation fuel cells. Nano Energy, 2012, 1: 514-517 CrossRef Google Scholar

[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: 161-166 CrossRef Google Scholar

[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: 11496-11500 CrossRef PubMed Google Scholar

[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: 21454-21460 CrossRef PubMed Google Scholar

[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: 6316-6319 CrossRef Google Scholar

[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: 679-685 CrossRef Google Scholar

[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: 10584-10589 CrossRef PubMed ADS Google Scholar

[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: 130-142 CrossRef Google Scholar

[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: 2839-2855 CrossRef Google Scholar

[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: 238-249 CrossRef Google Scholar

[40] Ranjbar Sahraie N, Paraknowitsch JP, Göbel C, et al. Noble-metal-free electrocatalysts with enhanced ORR performance by task-specific functionalization of carbon using ionic liquid precursor systems. J Am Chem Soc, 2014, 136: 14486-14497 CrossRef PubMed Google Scholar

[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: 23996-24005 CrossRef Google Scholar

[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: 13486-13491 CrossRef PubMed ADS Google Scholar

[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: 4596-4597 CrossRef PubMed Google Scholar

[44] Mahmood A, Guo W, Tabassum H, et al. Metal-organic framework-based nanomaterials for electrocatalysis. Adv Energy Mater, 2016, 6: 1600423 CrossRef Google Scholar

[45] Dang S, Zhu QL, Xu Q. Nanomaterials derived from metal–organic frameworks. Nat Rev Mater, 2017, 3: 17075 CrossRef ADS Google Scholar

[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: 5390-5391 CrossRef PubMed Google Scholar

[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: 11854-11857 CrossRef PubMed Google Scholar

[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: 6498-6501 CrossRef PubMed Google Scholar

[49] Jiang HL, Xu Q. Porous metal–organic frameworks as platforms for functional applications. Chem Commun, 2011, 47: 3351-3370 CrossRef PubMed Google Scholar

[50] Hu M, Reboul J, Furukawa S, et al. Direct carbonization of Al-based porous coordination polymer for synthesis of nanoporous carbon. J Am Chem Soc, 2012, 134: 2864-2867 CrossRef PubMed Google Scholar

[51] Yi FY, Zhang R, Wang H, et al. Metal-organic frameworks and their composites: synthesis and electrochemical applications. Small Methods, 2017, 1: 1700187 CrossRef Google Scholar

[52] Lin T, Chen IW, Liu F, et al. Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage. Science, 2015, 350: 1508-1513 CrossRef PubMed ADS Google Scholar

[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: 8212-8221 CrossRef PubMed Google Scholar

[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: 12660-12668 CrossRef PubMed Google Scholar

[55] Tang H, Yin H, Wang J, et al. Molecular architecture of cobalt porphyrin multilayers on reduced graphene oxide sheets for high-performance oxygen reduction reaction. Angew Chem, 2013, 125: 5695-5699 CrossRef Google Scholar

[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: 568-576 CrossRef Google Scholar

[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: 1604437 CrossRef PubMed Google Scholar

[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: 1570-1575 CrossRef PubMed Google Scholar

[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: 11399-11408 CrossRef PubMed Google Scholar

[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: 417-421 CrossRef Google Scholar

[61] Zhu Y, Murali S, Cai W, et al. Graphene and graphene oxide: synthesis, properties, and applications. Adv Mater, 2010, 22: 3906-3924 CrossRef PubMed Google Scholar

[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: 7610-7618 CrossRef Google Scholar

[63] Zheng J, Ekström TC, Gordeev SK, et al. Carbon with an onion-like structure obtained by chlorinating titanium carbide. J Mater Chem, 2000, 10: 1039-1041 CrossRef Google Scholar

[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: 14302-14310 CrossRef Google Scholar

[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: 361-365 CrossRef PubMed ADS Google Scholar

[66] Guan BY, Yu L, (David) Lou XW. A dual-metal–organic-framework derived electrocatalyst for oxygen reduction. Energy Environ Sci, 2016, 9: 3092-3096 CrossRef Google Scholar

[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: 369-376 CrossRef Google Scholar

[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: 241-247 CrossRef Google Scholar

[69] Chang H, Joo SH, Pak C. Synthesis and characterization of mesoporous carbon for fuel cell applications. J Mater Chem, 2007, 17: 3078-3088 CrossRef Google Scholar

[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: 6226-6231 CrossRef PubMed Google Scholar

[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: 12322-12329 CrossRef Google Scholar

[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: 6590-6602 CrossRef PubMed ADS Google Scholar

[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: 7936-7942 CrossRef Google Scholar

[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: 3612-3641 CrossRef Google Scholar

[75] Zheng F, Yang Y, Chen Q. High lithium anodic performance of highly nitrogen-doped porous carbon prepared from a metal-organic framework. Nat Commun, 2014, 5: 5261 CrossRef PubMed ADS Google Scholar

  • Figure 1

    (a) PXRD patterns and (b) Raman spectra of NC-800, INC-800 and BrNC-800.

  • Scheme 1

    Preparation of nanoscale Im-UiO-66, (I)Meim-UiO-66 and (Br)Etim-UiO-66 via post-synthetic ionization (PSI) strategy and their conversion to heteroatoms doped nanocarbons, which are denoted as NC-800, INC-800 and BrNC-800 via carbonization at 800°C and acid etching treatment. Lavender sphere represents the pore cavity.

  • Figure 2

    TEM images of (a) NC-800; (b) INC-800 and (c) BrNC-800; (d) HRTEM image of BrNC-800.

  • Figure 3

    N 1s spectra of (a) NC-800, (b) INC-800 and (c) BrNC-800. (d) Bar diagrams representing the variation of the four kinds of nitrogen species (pyridinic-N, pyrrolic-N, graphitic-N, and pyridine-N-oxide, respectively) in the various nanocarbons.

  • Figure 4

    (a) N2 sorption isotherms and (b) pore size distributions for NC-800, INC-800 and BrNC-800. Solid symbols denote adsorption, open symbols denote desorption (P/P0=partial pressure).

  • Figure 5

    (a) LSV curves for NC-800, INC-800, BrNC-800 and 20 wt% Pt/C at RDE rotation rate of 1,600 rpm with a scan rate of 5 mV s−1 in O2-saturated 0.1 mol L−1 KOH solution; (b) LSV curves of BrNC-800 at different rotation rates (inset: K-L plots); (c) corresponding Tafel plots obtained from the RDE polarization curves; (d) electron transfer number (n; top) and H2O2 yield (bottom) by RRDE at 1,600 rpm; (e) current-time chronoamperometry for BrNC-800 and Pt/C in an O2-saturated 0.1 mol L−1 KOH solution; (f) methanol-crossover effects test of BrNC-800 and Pt/C.

qqqq

Contact and support