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Vol. 9 No. 4 (2017)

2D MOF Nanoflake-Assembled Spherical Microstructures for Enhanced Supercapacitor and Electrocatalysis Performances

https://doi.org/10.1007/s40820-017-0144-6
Huicong Xia
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Jianan Zhang
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Zhao Yang
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Shiyu Guo
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Shihui Guo
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, People’s Republic of China
Qun Xu
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, People’s Republic of China

Corresponding Author: Qun Xu

qunxu@zzu.edu.cn

Nano-Micro Letters, Vol. 9 No. 4 (2017), Article Number: 43

Abstract

Metal–organic frameworks (MOFs) are of great interest as potential electrochemically active materials. However, few studies have been conducted into understanding whether control of the shape and components of MOFs can optimize their electrochemical performances due to the rational realization of their shapes. Component control of MOFs remains a significant challenge. Herein, we demonstrate a solvothermal method to realize nanostructure engineering of 2D nanoflake MOFs. The hollow structures with Ni/Co- and Ni-MOF (denoted as Ni/Co-MOF nanoflakes and Ni-MOF nanoflakes) were assembled for their electrochemical performance optimizations in supercapacitors and in the oxygen reduction reaction (ORR). As a result, the Ni/Co-MOF nanoflakes exhibited remarkably enhanced performance with a specific capacitance of 530.4 F g−1 at 0.5 A g−1 in 1 M LiOH aqueous solution, much higher than that of Ni-MOF (306.8 F g−1) and ZIF-67 (168.3 F g−1), a good rate capability, and a robust cycling performance with no capacity fading after 2000 cycles. Ni/Co-MOF nanoflakes also showed improved electrocatalytic performance for the ORR compared to Ni-MOF and ZIF-67. The present work highlights the significant role of tuning 2D nanoflake ensembles of Ni/Co-MOF in accelerating electron and charge transportation for optimizing energy storage and conversion devices.


Highlights:


1 A solvothermal method was used to improve the conductivity and electrochemical activity of metal–organic framework (MOF) materials by tuning their morphology and components.
2 Ni/Co-MOF nanoflakes exhibit remarkably enhanced performances including enhanced electrocatalytic performance for the oxygen reduction reaction.
3 The synthetic strategy driven by rational design gives the first example of exploring MOF-derived nanomaterials to achieve improved efficiency energy storage and conversion devices.

Keywords

Metal–organic frameworks Nanoflakes Spherical microstructure Supercapacitor Oxygen reduction reaction
Xia, Huicong, Jianan Zhang, Zhao Yang, Shiyu Guo, Shihui Guo, and Qun Xu. 2017. “2D MOF Nanoflake-Assembled Spherical Microstructures for Enhanced Supercapacitor and Electrocatalysis Performances”. Nano-Micro Letters 9 (4):43. https://doi.org/10.1007/s40820-017-0144-6.
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References
  1. R. Banerjee, H. Furukawa, D. Britt, C. Knobler, M. O’Keeffe, O.M. Yaghi, Control of pore size and functionality in isoreticular zeolitic imidazolate frameworks and their carbon dioxide selective capture properties. J. Am. Chem. Soc. 131(11), 3875–3877 (2009). doi:10.1021/ja809459e
  2. A.U. Czaja, N. Trukhan, U. Muller, Industrial applications of metal–organic frameworks. Chem. Soc. Rev. 38(5), 1284–1293 (2009). doi:10.1039/b804680h
  3. E. Jeong, W.R. Lee, D.W. Ryu, Y. Kim, W.J. Phang, E.K. Koh, C.S. Hong, Reversible structural transformation and selective gas adsorption in a unique aqua-bridged Mn(II) metal–organic framework. Chem. Commun. 49(23), 2329–2331 (2013). doi:10.1039/c3cc00093a
  4. T. Rodenas, I. Luz, G. Prieto, B. Seoane, H. Miro et al., Metal–organic framework nanosheets in polymer composite materials for gas separation. Nat. Mater. 14(1), 48–55 (2015). doi:10.1038/nmat4113
  5. N.L. Rosi, J. Eckert, M. Eddaoudi, D.T. Vodak, J. Kim, M. O’Keeffe, O.M. Yaghi, Hydrogen storage in microporous metal–organic frameworks. Science 300(5622), 1127–1129 (2003). doi:10.1126/science.1083440
  6. H. Wu, W. Zhou, T. Yildirim, Hydrogen storage in a prototypical zeolitic imidazolate framework-8. J. Am. Chem. Soc. 129(17), 5314–5315 (2007). doi:10.1021/ja0691932
  7. A. Morozan, F. Jaouen, Metal organic frameworks for electrochemical applications. Energy Environ. Sci. 5(11), 9269–9290 (2012). doi:10.1039/c2ee22989g
  8. D. Wu, Z. Guo, X. Yin, Q. Pang, B. Tu, L. Zhang, Y.G. Wang, Q. Li, Metal–organic frameworks as cathode materials for Li–O2 batteries. Adv. Mater. 26(20), 3258–3262 (2014). doi:10.1002/adma.201305492
  9. S. Bai, X. Liu, K. Zhu, S. Wu, H. Zhou, Metal–organic framework-based separator for lithium–sulfur batteries. Nat. Energy 1(7), 16094 (2016). doi:10.1038/nenergy.2016.94
  10. A. Mahmood, R. Zou, Q. Wang, W. Xia, H. Tabassum, B. Qiu, R. Zhao, Nanostructured electrode materials derived from metal–organic framework xerogels for high-energy-density asymmetric supercapacitor. ACS Appl. Mater. Interfaces 8(3), 2148–2157 (2016). doi:10.1021/acsami.5b10725
  11. R.Q. Zou, H. Sakurai, Q. Xu, Preparation, adsorption properties, and catalytic activity of 3D porous metal–organic frameworks composed of cubic building blocks and alkali-metal ions. Angew. Chem. Int. Ed. 45(16), 2542–2546 (2006). doi:10.1002/anie.200503923
  12. R.Q. Zou, H. Sakurai, S. Han, R.Q. Zhong, Q. Xu, Probing the Lewis acid sites and CO catalytic oxidation activity of the porous metal–organic polymer [Cu(5-methylisophthalate)]. J. Am. Chem. Soc. 129(27), 8402–8403 (2007). doi:10.1021/ja071662s
  13. A. Corma, H. Garcia, F.X. Llabres, I. Xamena, Engineering metal organic frameworks for heterogeneous catalysis. Chem. Rev. 110(8), 4606–4655 (2010). doi:10.1021/cr9003924
  14. M.A. Nasalevich, R. Becker, E.V. Ramos-Fernandez, S. Castellanos, S.L. Veber et al., Co@NH2-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H2 production. Energy Environ. Sci. 8(1), 364–375 (2015). doi:10.1039/c4ee02853h
  15. P.Z. Li, X.J. Wang, J. Liu, J.S. Lim, R. Zou, Y. Zhao, A triazole-containing metal–organic framework as a highly effective and substrate size-dependent catalyst for CO2 conversion. J. Am. Chem. Soc. 138(7), 2142–2145 (2016). doi:10.1021/jacs.5b13335
  16. R. Zou, P.Z. Li, Y.F. Zeng, J. Liu, R. Zhao et al., Bimetallic metal–organic frameworks: probing the lewis acid site for CO2 conversion. Small 12(17), 2334–2343 (2016). doi:10.1002/smll.201503741
  17. Z. Xu, L.L. Han, G.L. Zhuang, J. Bai, D. Sun, In situ construction of three anion-dependent Cu(I) coordination networks as promising heterogeneous catalysts for azide-alkyne “click” reactions. Inorg. Chem. 54(10), 4737–4743 (2015). doi:10.1021/acs.inorgchem.5b00110
  18. P. Horcajada, C. Serre, G. Maurin, N.A. Ramsahye, F. Balas et al., Flexible porous metal–organic frameworks for a controlled drug delivery. J. Am. Chem. Soc. 130(21), 6774–6780 (2008). doi:10.1021/ja710973k
  19. K.M. Taylor-Pashow, J. Della Rocca, Z. Xie, S. Tran, W. Lin, Postsynthetic modifications of iron-carboxylate nanoscale metal–organic frameworks for imaging and drug delivery. J. Am. Chem. Soc. 131(40), 14261–14263 (2009). doi:10.1021/ja906198y
  20. P. Horcajada, T. Chalati, C. Serre, B. Gillet, C. Sebrie et al., Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging. Nat. Mater. 9(2), 172–178 (2010). doi:10.1038/nmat2608
  21. J. Gascon, A. Corma, F. Kapteijn, F.X. Llabrés i Xamena, Metal organic framework catalysis: quo vadis? ACS Catal. 4(2), 361–378 (2014). doi:10.1021/cs400959k
  22. W. Xia, A. Mahmood, Z. Liang, R. Zou, S. Guo, Earth-abundant nanomaterials for oxygen reduction. Angew. Chem. Int. Ed. 55(8), 2650–2676 (2016). doi:10.1002/anie.201504830
  23. H. Yu, D. Xu, Q. Xu, Dual template effect of supercritical CO2 in ionic liquid to fabricate a highly mesoporous cobalt metal–organic framework. Chem. Commun. 51(67), 13197–13200 (2015). doi:10.1039/c5cc04009d
  24. S.L. Li, Q. Xu, Metal–organic frameworks as platforms for clean energy. Energy Environ. Sci. 6(6), 1656–1683 (2013). doi:10.1039/c3ee40507a
  25. Q.L. Zhu, W. Xia, T. Akita, R. Zou, Q. Xu, Metal–organic framework-derived honeycomb-like open porous nanostructures as precious-metal-free catalysts for highly efficient oxygen electroreduction. Adv. Mater. 28(30), 6391–6398 (2016). doi:10.1002/adma.201600979
  26. W. Xia, R.Q. Zou, L. An, D.G. Xia, S.J. Guo, 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. 8(2), 568–576 (2015). doi:10.1039/c4ee02281e
  27. S. Zhao, Y. Wang, J. Dong, C.-T. He, H. Yin et al., Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution. Nat. Energy 1, 16184 (2016). doi:10.1038/nenergy.2016.184
  28. A. Mahmood, W.H. Guo, H. Tabassum, R.Q. Zou, Metal–organic framework-based nanomaterials for electrocatalysis. Adv. Energy Mater. 6(17), 1600423 (2016). doi:10.1002/aenm.201600423
  29. P. Pachfule, D. Shinde, M. Majumder, Q. Xu, Fabrication of carbon nanorods and graphene nanoribbons from a metal–organic framework. Nat. Chem. 8(7), 718–724 (2016). doi:10.1038/nchem.2515
  30. W. Xia, A. Mahmood, R. Zou, Q. Xu, Metal–organic frameworks and their derived nanostructures for electrochemical energy storage and conversion. Energy Environ. Sci. 8(7), 1837–1866 (2015). doi:10.1039/c5ee00762c
  31. J.R. Selman, Materials science. Poison-tolerant fuel cells. Science 326(5949), 52–53 (2009). doi:10.1126/science.1180820
  32. K.M. Choi, H.M. Jeong, J.H. Park, Y.B. Zhang, J.K. Kang, O.M. Yaghi, Supercapacitors of nanocrystalline metal–organic frameworks. ACS Nano 8(7), 7451–7457 (2014). doi:10.1021/nn5027092
  33. P. Zhou, Q. Xu, H. Li, Y. Wang, B. Yan, Y. Zhou, J. Chen, J. Zhang, K. Wang, Fabrication of two-dimensional lateral heterostructures of WS2/WO3 H2O through selective oxidation of monolayer WS2. Angew. Chem. Int. Ed. 54(50), 15226–15230 (2015). doi:10.1002/anie.201508216
  34. B. Zhang, F. Wang, C. Zhu, Q. Li, J. Song, M. Zheng, L. Ma, W. Shen, A facile self-assembly synthesis of hexagonal ZnO nanosheet films and their photoelectrochemical properties. Nano-Micro Lett. 8(2), 137–142 (2016). doi:10.1007/s40820-015-0068-y
  35. X. Yang, K. Xu, R. Zou, J. Hu, A hybrid electrode of Co3O4@PPy core/shell nanosheet arrays for high-performance supercapacitors. Nano-Micro Lett. 8(2), 143–150 (2016). doi:10.1007/s40820-015-0069-x
  36. A.K. Geim, K.S. Novoselov, The rise of graphene. Nat. Mater. 6(3), 183–191 (2007). doi:10.1038/nmat1849
  37. F. Cao, M. Zhao, Y. Yu, B. Chen, Y. Huang et al., Synthesis of two-dimensional CoS1.097/Nitrogen-doped carbon nanocomposites using metal–organic framework nanosheets as precursors for supercapacitor application. J. Am. Chem. Soc. 138(22), 6924–6927 (2016). doi:10.1021/jacs.6b0254
  38. S. Li, D. Wu, C. Cheng, J. Wang, F. Zhang, Y. Su, X. Feng, Polyaniline-coupled multifunctional 2D metal oxide/hydroxide graphene nanohybrids. Angew. Chem. Int. Ed. 52(46), 12105–12109 (2013). doi:10.1002/anie.201306871
  39. S. Li, D. Wu, H. Liang, J. Wang, X. Zhuang, Y. Mai, Y. Su, X. Feng, Metal-nitrogen doping of mesoporous carbon/graphene nanosheets by self-templating for oxygen reduction electrocatalysts. ChemSusChem 7(11), 3002–3006 (2014). doi:10.1002/cssc.201402680
  40. Q. Wang, R. Zou, W. Xia, J. Ma, B. Qiu et al., Facile synthesis of ultrasmall CoS2 nanoparticles within thin N-doped porous carbon shell for high performance lithium-ion batteries. Small 11(21), 2511–2517 (2015). doi:10.1002/smll.201403579
  41. J. Yang, F. Zhang, H. Lu, X. Hong, H. Jiang, Y. Wu, Y. Li, Hollow Zn/Co ZIF particles derived from core–shell ZIF-67@ZIF-8 as selective catalyst for the semi-hydrogenation of acetylene. Angew. Chem. Int. Ed. 54(37), 10889–10893 (2015). doi:10.1002/anie.201504242
  42. H. Chen, L.F. Hu, M. Chen, Y. Yan, L.M. Wu, Nickel–cobalt layered double hydroxide nanosheets for high-performance supercapacitor electrode materials. Adv. Funct. Mater. 24(7), 934–942 (2014). doi:10.1002/adfm.201301747
  43. R. Ma, J. Liang, K. Takada, T. Sasaki, Topochemical synthesis of Co–Fe layered double hydroxides at varied Fe/Co ratios: unique intercalation of triiodide and its profound effect. J. Am. Chem. Soc. 133(3), 613–620 (2011). doi:10.1021/ja1087216
  44. N.S. McIntyre, M.G. Cook, X-ray photoelectron studies on some oxides and hydroxides of cobalt, nickel, and copper. Anal. Chem. 47(13), 2208–2213 (1975). doi:10.1021/ac60363a034
  45. Y. Liu, J.A. Zhang, S.P. Wang, K.X. Wang, Z.M. Chen, Q. Xu, Facilely constructing 3D porous NiCo2S4 nanonetworks for high-performance supercapacitors. New J. Chem. 38(9), 4045–4048 (2014). doi:10.1039/c4nj00816b
  46. Q. Liu, J. Jin, J. Zhang, NiCo2S4@graphene as a bifunctional electrocatalyst for oxygen reduction and evolution reactions. ACS Appl. Mater. Interfaces 5(11), 5002–5008 (2013). doi:10.1021/am4007897
  47. J. Tang, R.R. Salunkhe, J. Liu, N.L. Torad, M. Imura, S. Furukawa, Y. Yamauchi, Thermal conversion of core–shell metal–organic frameworks: a new method for selectively functionalized nanoporous hybrid carbon. J. Am. Chem. Soc. 137(4), 1572–1580 (2015). doi:10.1021/ja511539a
  48. S. Zhong, C.X. Zhan, D.P. Cao, Zeolitic imidazolate framework-derived nitrogen-doped porous carbons as high performance supercapacitor electrode materials. Carbon 85, 51–59 (2015). doi:10.1016/j.carbon.2014.12.064
  49. N.L. Torad, R.R. Salunkhe, Y. Li, H. Hamoudi, M. Imura, Y. Sakka, C.C. Hu, Y. Yamauchi, Electric double-layer capacitors based on highly graphitized nanoporous carbons derived from ZIF-67. Chem. Eur. J. 20(26), 7895–7900 (2014). doi:10.1002/chem.201400089
  50. X. Deng, J. Li, S. Zhu, F. He, C. He, E. Liu, C. Shi, Q. Li, N. Zhao, Metal–organic frameworks-derived honeycomb-like Co3O4/three-dimensional graphene networks/Ni foam hybrid as a binder-free electrode for supercapacitors. J. Alloys Compd. 693, 16–24 (2017). doi:10.1016/j.jallcom.2016.09.096
  51. M. Hamdani, R.N. Singh, P. Chartier, Co3O4 and Co-based spinel oxides bifunctional oxygen electrodes. Int. J. Electrochem. Sci. 5(4), 556–577 (2010)
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