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Vol. 11 (2019)

Charge Engineering of Mo2C@Defect-Rich N-Doped Carbon Nanosheets for Efficient Electrocatalytic H2 Evolution

https://doi.org/10.1007/s40820-019-0279-8
Chunsheng Lei
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Wen Zhou
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Qingguo Feng
Key Laboratory of Advanced Technologies of Materials, Ministry of Education, and Institute of Materials Dynamics, Southwest Jiaotong University, Chengdu 610031, Sichuan, People’s Republic of China
Yongpeng Lei
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, People’s Republic of China
Yi Zhang
Hunan Provincial Key Laboratory of Chemical Power Sources, College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, People’s Republic of China
Yin Chen
Hunan Provincial Key Laboratory of Chemical Power Sources, College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, People’s Republic of China
Jiaqian Qin
Metallurgy and Materials Science Research Institute, Chulalongkorn University, Bangkok 10330, Thailand

Corresponding Author: Yongpeng Lei

lypkd@163.com

Nano-Micro Letters, Vol. 11 (2019), Article Number: 45

Abstract

Charge engineering of carbon materials with many defects shows great potential in electrocatalysis, and molybdenum carbide (Mo2C) is one of the noble-metal-free electrocatalysts with the most potential. Herein, we study the Mo2C on pyridinic nitrogen-doped defective carbon sheets (MoNCs) as catalysts for the hydrogen evolution reaction. Theoretical calculations imply that the introduction of Mo2C produces a graphene wave structure, which in some senses behaves like N doping to form localized charges. Being an active electrocatalyst, MoNCs demonstrate a Tafel slope as low as 60.6 mV dec−1 and high durability of up to 10 h in acidic media. Besides charge engineering, plentiful defects and hierarchical morphology also contribute to good performance. This work underlines the importance of charge engineering to boost catalytic performance.


Highlights:


1 The Mo2C modified carbon nanosheets produce a graphene wave structure to form localized charges and further enhance the N-doping effect.
2 The optimal sample shows a Tafel slope as low as 60.6 mV dec−1 and high durability up to 10 h in acidic media.








Keywords

Molybdenum carbide Nitrogen-doped carbon nanosheets Charge engineering Graphene wave Hydrogen evolution reaction
Lei, Chunsheng, Wen Zhou, Qingguo Feng, Yongpeng Lei, Yi Zhang, Yin Chen, and Jiaqian Qin. 2019. “Charge Engineering of Mo2C@Defect-Rich N-Doped Carbon Nanosheets for Efficient Electrocatalytic H2 Evolution”. Nano-Micro Letters 11 (June):45. https://doi.org/10.1007/s40820-019-0279-8.
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References
  1. Z. Shi, K. Nie, Z.J. Shao, B. Gao, H. Lin et al., Phosphorus-Mo2C@carbon nanowires toward efficient electrochemical hydrogen evolution: composition, structural and electronic regulation. Energy Environ. Sci. 10, 1262–1271 (2017). https://doi.org/10.1039/C7EE00388A
  2. C. Tang, N. Cheng, Z. Pu, W. Xing, X. Sun, NiSe nanowire film supported on nickel foam: An efficient and stable 3D bifunctional electrode for full water splitting. Angew. Chem. Int. Ed. 54, 9351–9355 (2015). https://doi.org/10.1002/anie.201503407
  3. Y. Fang, H. Zhou, Y. Huang, J. Sun, F. Qin, J. Bao, W.A. Goddardlll, S. Chen, Z. Ren, High-performance bifunctional porous non-noble metal phosphide catalyst for overall water splitting. Nat. Commun. 9, 2551 (2018). https://doi.org/10.1038/s41467-018-04746-z
  4. Z.L. Chen, H. Yuan, Y. Liu, H. Wang, H.Y. Yang, H.B. Xu, Y.J. Li, R.B. Wu, In situ formation of cobalt nitrides/graphitic carbon composites as efficient bifunctional electrocatalysts for overall water splitting. ACS Appl. Mater. Interfaces. 10, 7134–7144 (2018). https://doi.org/10.1021/acsami.7b18858
  5. W. Ma, R. Ma, J. Wu, P. Sun, X. Liu, K. Zhou, T. Sasaki, Development of efficient electrocatalysts via molecular hybridization of NiMn layered double hydroxide nanosheets and graphene. Nanoscale 8, 10425–10432 (2016). https://doi.org/10.1039/C6NR00988C
  6. G. Fang, Q. Wang, J. Zhou, Y. Lei, Z. Chen, B. Wu, A. Pan, S. Liang, Metal organic framework-templated synthesis of bimetallic selenides with rich phase boundaries for sodium-ion storage and oxygen evolution reaction. ACS Nano 9b00816 (2019). https://doi.org/10.1021/acsnano.9b00816
  7. T. He, H. Xue, X. Wang, S. He, Y. Lei et al., Architecture of CoNx single clusters on nanocarbon as excellent oxygen reduction catalysts with high-efficient atomic utilization. Nanoscale 9, 8341–8348 (2017). https://doi.org/10.1039/C7NR02165H
  8. H. Zhang, H. Qiao, H. Wang, N. Zhou, J. Chen, Y. Tang, J. Li, C. Huang, Nickel cobalt oxide/carbon nanotubes hybrid as a high-performance electrocatalyst for metal/air battery. Nanoscale 6, 10235–10242 (2014). https://doi.org/10.1039/C4NR02125H
  9. M. Wang, Z. Fang, K. Zhang, J. Fang, F. Qin, Z. Zhang, J. Li, Y. Liu, Y. Lai, Synergistically enhanced activity of graphene quantum dots/graphene hydrogel composites: A novel all-carbon hybrid electrocatalyst for metal/air batteries. Nanoscale 8, 11398–11402 (2016). https://doi.org/10.1039/C6NR02622B
  10. T. Sun, L. Xu, D. Wang, Y. Li, Metal organic frameworks derived single atom catalysts for electrocatalytic energy conversion. Nano Res. (2019). https://doi.org/10.1007/s12274-019-2345-4
  11. F. Yu, L. Yu, I.K. Mishra, Y. Yu, Z. Ren, H. Zhou, Recent developments in earth-abundant and non-noble electrocatalysts for water electrolysis. Mater. Today Phys. 7, 121–138 (2018). https://doi.org/10.1016/j.mtphys.2018.11.007
  12. R.B. Levy, M. Boudart, Platinum-like behavior of tungsten carbide in surface catalysis. Science 181, 547–549 (1973). https://doi.org/10.1126/science.181.4099.547
  13. Y. Zhu, G. Chen, X. Xu, G. Yang, M. Liu, Z. Shao, Enhancing electrocatalytic activity for hydrogen evolution by strongly coupled molybdenum nitride@nitrogen-doped carbon porous nano-octahedrons. ACS Catal. 7, 3540–3547 (2017). https://doi.org/10.1021/acscatal.7b00120
  14. J. Wang, W. Chen, T. Wang, N. Bate, C. Wang, E. Wang, A strategy for highly dispersed Mo2C/MoN hybrid nitrogen-doped graphene via ion-exchange resin synthesis for efficient electrocatalytic hydrogen reduction. Nano Res. 11, 4535–4548 (2018). https://doi.org/10.1007/s12274-018-2034-8
  15. L. Chen, H. Jiang, H. Jiang, H. Zhang, S. Guo, Y. Hu, C. Li, Mo-based ultrasmall nanoparticles on hierarchical carbon nanosheets for superior lithium ion storage and hydrogen generation catalysis. Adv. Energy Mater. 7, 1602782 (2017). https://doi.org/10.1002/aenm.201602782
  16. L. Zhao, Q. Wang, X. Zhang, C. Deng, Z. Li, Y. Lei, M. Zhu, Combined electron and structure manipulation on Fe containing N-doped CNTs to boost bifunctional oxygen electrocatalysis. ACS Appl. Mater. Interfaces 10, 35888–35895 (2018). https://doi.org/10.1021/acsami.8b09197
  17. Y. Dong, B. Zeng, J. Xiao, X. Zhang, D. Li, M. Li, J. He, M. Long, Effect of sulphur vacancy and interlayer interaction on the electronic structure and spin splitting of bilayer MoS2. J. Phys. Condens. Mat. 30, 125302 (2018). https://doi.org/10.1088/1361-648X/aaad3b
  18. Y.Y. Chen, Y. Zhang, W.J. Jiang, X. Zhang, Z. Dai, L.J. Wan, J.S. Hu, Pomegranate-like N, P-doped Mo2C@C nanospheres as highly active electrocatalysts for alkaline hydrogen evolution. ACS Nano 10, 8851–8860 (2016). https://doi.org/10.1021/acsnano.6b04725
  19. N. Han, K.R. Yang, Z. Lu, W. Xu, T. Gao et al., Nitrogen-doped tungsten carbide nanoarray as an efficient bifunctional electrocatalyst for water splitting. Nat. Commun. 9, 924 (2018). https://doi.org/10.1038/s41467-018-03429-z
  20. Y. Bai, H. Huang, C. Wang, R. Long, Y. Xiong, Engineering the surface charge states of nanostructures for enhanced catalytic performance. Mater. Chem. Front. 1, 1951–1964 (2017). https://doi.org/10.1039/C7QM00020K
  21. W.F. Chen, C.H. Wang, K. Sasaki, N. Marinkovic, W. Xu, J.T. Muckerman, Y. Zhu, R.R. Adzic, Highly active and durable nanostructured molybdenum carbide electrocatalysts for hydrogen production. Energy Environ. Sci. 6, 943–951 (2013). https://doi.org/10.1039/c2ee23891h
  22. Y. Lei, Q. Shi, C. Han, B. Wang, N. Wu, H. Wang, Y. Wang, N-doped graphene grown on silk cocoon-derived interconnected carbon fibers for oxygen reduction reaction and photocatalytic hydrogen production. Nano Res. 9, 2498–2509 (2016). https://doi.org/10.1007/s12274-016-1136-4
  23. Q. Wang, Y. Lei, D. Wang, Y. Li, Defect engineering in earth-abundant electrocatalysts for CO2 and N2 reduction. Energy Environ. Sci. (Advance Article, 2019). https://doi.org/10.1039/C8EE03781G
  24. L. Zhang, Y. Jia, G. Gao, X. Yan, N. Chen et al., Graphene defects trap atomic Ni species for hydrogen and oxygen evolution reactions. Chem 4, 285–297 (2018). https://doi.org/10.1016/j.chempr.2017.12.005
  25. Y. Wei, X. Zhang, Z. Luo, D. Tang, C. Chen, T. Zhang, Z. Xie, Nitrogen-doped carbon nanotube supported Pd catalyst for improved electrocatalytic performance towards ethanol electrooxidation. Nano-Micro Lett. 9, 28 (2017). https://doi.org/10.1007/s40820-017-0129-5
  26. J. Liu, T. He, Q. Wang, Z. Zhou, Y. Zhang et al., Confining ultrasmall bimetal alloys in porous N-Carbon as scalable and sustainable electrocatalysts for rechargeable Zn-air batteries. J. Mater. Chem. A (Advance Article, 2019). https://doi.org/10.1039/C9TA02264C
  27. Q. Wang, Y. Lei, Y. Zhu, H. Wang, J. Feng et al., Edge defect engineering of nitrogen-doped carbon for oxygen electrocatalysts in Zn-air batteries. ACS Appl. Mater. Interfaces 10, 29448–29456 (2018). https://doi.org/10.1021/acsami.8b07863
  28. W. Gao, Y. Shi, Y. Zhang, L. Zuo, H. Lu, Y. Huang, W. Fan, T. Liu, Molybdenum carbide anchored on graphene nanoribbons as highly efficient all-pH hydrogen evolution reaction electrocatalyst. ACS Sustain. Chem. Eng. 4, 6313–6321 (2016). https://doi.org/10.1021/acssuschemeng.6b00859
  29. G. Kresse, J. Hafner, Ab initiomolecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993). https://doi.org/10.1103/PhysRevB.47.558
  30. G. Kresse, J. Hafner, Ab initiomolecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994). https://doi.org/10.1103/PhysRevB.49.14251
  31. G. Kresse, J. Furthmüller, Efficiency of Ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996). https://doi.org/10.1016/0927-0256(96)00008-0
  32. S. Grimme, Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 27, 1787–1799 (2006). https://doi.org/10.1002/jcc.20495
  33. J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996). https://doi.org/10.1103/PhysRevLett.77.3865
  34. P.E. Blöchl, Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994). https://doi.org/10.1103/PhysRevB.50.17953
  35. G. Kresse, D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999). https://doi.org/10.1103/PhysRevB.59.1758
  36. J. Jia, W. Zhou, Z. Wei, T. Xiong, G. Li et al., Molybdenum carbide on hierarchical porous carbon synthesized from Cu–MoO2 as efficient electrocatalysts for electrochemical hydrogen generation. Nano Energy 41, 749–757 (2017). https://doi.org/10.1016/j.nanoen.2017.10.030
  37. J.R. Dos Santos Politi, F. Viñes, J.A. Rodriguez, F. Illas, Atomic and electronic structure of molybdenum carbide phases: bulk and low Miller-index surfaces. Phys. Chem. Chem. Phys. 15, 12617–12625 (2013). https://doi.org/10.1039/c3cp51389k
  38. J. Jia, T. Xiong, L. Zhao, F. Wang, H. Liu, R. Hu, J. Zhou, W. Zhou, S. Chen, Ultrathin N-doped Mo2C nanosheets with exposed active sites as efficient electrocatalyst for hydrogen evolution reactions. ACS Nano 11, 12509–12518 (2017). https://doi.org/10.1021/acsnano.7b06607
  39. K. Momma, F. Izumi, VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Cryst. 44, 1272–1276 (2011). https://doi.org/10.1107/S0021889811038970
  40. F.X. Ma, H.B. Wu, B.Y. Xia, C.Y. Xu, X.W.D. Lou, Hierarchical β-Mo2C nanotubes organized by ultrathin nanosheets as a highly efficient electrocatalyst for hydrogen production. Angew. Chem. Int. Ed. 54, 15395–15399 (2015). https://doi.org/10.1002/anie.201508715
  41. S. Zhou, G. Zhou, S. Jiang, P. Fan, H. Hou, Flexible and refractory tantalum carbide-carbon electrospun nanofibers with high modulus and electric conductivity. Mater. Lett. 200, 97–100 (2017). https://doi.org/10.1016/j.matlet.2017.04.115
  42. M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing, Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 87, 1051–1069 (2015). https://doi.org/10.1515/pac-2014-1117
  43. Q. Wang, Y. Ji, Y. Lei, Y. Wang, Y. Wang, Y. Li, S. Wang, Pyridinic-N-dominated doped defective graphene as a superior oxygen electrocatalyst for ultrahigh-energy-density Zn-air batteries. ACS Energy Lett. 3, 1183–1191 (2018). https://doi.org/10.1021/acsenergylett.8b00303
  44. C. Liu, F. Wang, J. Zhang, K. Wang, Y. Qiu, Q. Liang, Z. Chen, Efficient photoelectrochemical water splitting by g-C3N4/TiO2 nanotube array heterostructures. Nano-Micro Lett. 10, 37 (2018). https://doi.org/10.1007/s40820-018-0192-6
  45. J. Liang, Y. Zheng, J. Chen, J. Liu, D. Hulicova-Jurcakova, M. Jaroniec, S.Z. Qiao, Facile oxygen reduction on a three-dimensionally ordered macroporous graphitic C3N4/carbon composite electrocatalyst. Angew. Chem. Int. Ed. 51, 3892–3896 (2012). https://doi.org/10.1002/anie.201107981
  46. Q. Wang, Y. Lei, Z. Chen, N. Wu, Y. Wang, B. Wang, Y. Wang, Fe/Fe3C@C nanoparticles encapsulated in N-doped graphene-CNTs framework as an efficient bifunctional oxygen electrocatalyst for robust rechargeable Zn-air batteries. J. Mater. Chem. A 6, 516–526 (2018). https://doi.org/10.1039/C7TA08423D
  47. N. Wang, T. Hang, D. Chu, M. Li, Three dimensional hierarchical nanostructured Cu/Ni-Co coating electrode for hydrogen evolution reaction in alkaline media. Nano-Micro Lett. 7, 347–352 (2015). https://doi.org/10.1007/s40820-015-0049-1
  48. Z. Chen, Q. Wang, X. Zhang, Y. Lei, W. Hu, Y. Luo, Y. Wang, N-doped defective carbon with trace Co for efficient rechargeable liquid electrolyte-/all-solid-state Zn-air batteries. Sci. Bull. 63, 548–555 (2018). https://doi.org/10.1016/j.scib.2018.04.003
  49. G. Duan, H. Fang, C. Huang, S. Jiang, H. Hou, Microstructures and mechanical properties of aligned electrospun carbon nanofibers from binary composites of polyacrylonitrile and polyamic acid. J. Mater. Sci. 53, 15096–15106 (2018). https://doi.org/10.1007/s10853-018-2700-y
  50. P. Xiao, Y. Yan, X. Ge, Z. Liu, J.Y. Wang, X. Wang, Investigation of molybdenum carbide nano-rod as an efficient and durable electrocatalyst for hydrogen evolution in acidic and alkaline media. Appl. Catal. B Environ. 154–155, 232–237 (2014). https://doi.org/10.1016/j.apcatb.2014.02.020
  51. Y.J. Tang, M.R. Gao, C.H. Liu, S.L. Li, H.L. Jiang, Y.Q. Lan, M. Han, S.H. Yu, Porous molybdenum-based hybrid catalysts for highly efficient hydrogen evolution. Angew. Chem. Int. Ed. 54, 12928–12932 (2015). https://doi.org/10.1002/anie.201505691
  52. Y. Zhao, K. Kamiya, K. Hashimoto, S. Nakanishi, In situ CO2-emission assisted synthesis of molybdenum carbonitride nanomaterial as hydrogen evolution electrocatalyst. J. Am. Chem. Soc. 137, 110–113 (2014). https://doi.org/10.1021/ja5114529
  53. Y. Liu, G. Yu, G.D. Li, Y. Sun, T. Asefa, W. Chen, X. Zou, Coupling Mo2C with nitrogen-rich nanocarbon leads to efficient hydrogen-evolution electrocatalytic sites. Angew. Chem. Int. Ed. 54, 10752–10757 (2015). https://doi.org/10.1002/anie.201504376
  54. C. Lu, D. Tranca, J. Zhang, F.N. Rodrı́guez Hernández, Y. Su, X. Zhuang, F. Zhang, G. Seifert, X. Feng, Molybdenum carbide-embedded nitrogen-doped porous carbon nanosheets as electrocatalysts for water splitting in alkaline media. ACS Nano 11, 3933–3942 (2017). https://doi.org/10.1021/acsnano.7b00365
  55. W.F. Chen, J.T. Muckerman, E. Fujita, Recent developments in transition metal carbides and nitrides as hydrogen evolution electrocatalysts. Chem. Commun. 49, 8896–8909 (2013). https://doi.org/10.1039/c3cc44076a
  56. C. Tang, W. Wang, A. Sun, C. Qi, D. Zhang, Z. Wu, D. Wang, Sulfur-decorated molybdenum carbide catalysts for enhanced hydrogen evolution. ACS Catal. 5, 6956–6963 (2015). https://doi.org/10.1021/acscatal.5b01803
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