Citation: LEE Jordan, LI Yong, TANG Jianing, CUI Xiaoli. Synthesis of Hydrogen Substituted Graphyne through Mechanochemistry and Its Electrocatalytic Properties[J]. Acta Physico-Chimica Sinica, ;2018, 34(9): 1080-1087. doi: 10.3866/PKU.WHXB201802262 shu

Synthesis of Hydrogen Substituted Graphyne through Mechanochemistry and Its Electrocatalytic Properties

LEE Jordan ¹ ,
LI Yong ² ,
TANG Jianing ^1,3 ,
CUI Xiaoli ^1,,

1.
Department of Materials Science, Fudan University, Shanghai 200433, P.R.China
2.
Shanghai Institute of Space Power Sources, Shanghai 200245, P.R.China
3.
Department of Advanced Materials Science and Engineering, Imperial College London, London SW72AZ, Britain

Corresponding author: CUI Xiaoli, xiaolicui@fudan.edu.cn
Received Date: 3 February 2018
Revised Date: 20 February 2018
Accepted Date: 22 February 2018
Available Online: 26 September 2018
Fund Project: The project was supported by National Natural Science Foundation of China (21273047) and the Aerospace Science and Technology Innovation Fund of SAST, China (YF07050117F4051)the Aerospace Science and Technology Innovation Fund of SAST, China YF07050117F4051National Natural Science Foundation of China 21273047

Since the successful synthesis of graphdiyne, graphynes have emerged as an active field in carbon materials research.Hydrogen-substituted graphyne, structurally similar to graphynes, is a kind of two-dimensional (2D) carbon-rich material composed of sp²-hybridized carbon and hydrogen from phenyl groups and sp-hybridized carbon from ethynyl linkages.The large pore size in the molecular structure of hydrogen-substituted graphyne aids the diffusion of ions and molecules.In this work, hydrogen-substituted graphyne was synthesized by a facile mechanochemical route.Calcium carbide (CaC₂) was employed as the precursor of sp-hybridized carbon and 1, 3, 5 tribromobenzene (PhBr₃) as that of sp²-hybridized carbon and hydrogen.Hydrogen-substituted graphyne was directly obtained via the cross-coupling reaction performed by ball milling under vacuum and the impurities were removed by dilute nitric acid and benzene.Mechanochemistry is a mature technology for the simple and high-yield synthesis of nanostructured materials.The composition of the as-prepared hydrogen-substituted graphyne was confirmed by Raman and ¹H solid-state nuclear magnetic spectroscopies.Energy-dispersive X-ray (EDX) spectrum and X-ray diffraction (XRD) patterns indicated that the purity and crystallinity of the prepared samples are high, which was further confirmed by the corresponding selected area electron diffraction (SAED) patterns.Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) images illustrated that samples had nanosheet structure with a layer-to-layer distance of 0.35 nm.However, owing to the lack of a substrate, the nanosheets reunite to form irregular microparticles, as shown in the scanning electron microscopy (SEM) images.Twin structure was found in the as-prepared samples, which might be relevant to the mechanochemical process.The samples were used to prepare electrodes for the photoelectrochemical and electrochemical catalytic analysis.The open circuit potential under chopped irradiation of the electrode showed that the as-prepared hydrogen-substituted graphyne was a p-type semiconductor.The band gap was calculated to be 2.30 eV by UV-Vis diffused reﬂectance (UV-Vis DRS) spectroscopy.The electrocatalytic properties of the sample were determined using a three-electrode cell in a neutral solution (Na₂SO₄, 0.5 mol·L⁻¹).The onset overpotential for hydrogen evolution was −0.17 V; however, the Tafel slope was too large (1088.4 mV·dec⁻¹), which restricted application in electrocatalytic hydrogen evolution.On the other hand, the overpotential for oxygen evolution reaction was only 0.04 V and the Tafel slope was 70.0 mV·dec⁻¹, making applications in electrocatalytic oxygen evolution and photocatalysis possible.This strategy opens a new avenue for preparing graphyne with good electrochemical properties using readily available precursors under mild conditions.
- Hydrogen substituted graphyne,
- Mechanochemistry,
- Semiconductor,
- Oxygen evolution reaction
1. [1]
  Baughman, R. H.; Eckhardt, H.; Kertesz, M. J. Chem. Phys. 1987, 87, 6687. doi:10.1063/1.453405 doi: 10.1063/1.453405
2. [2]
  Malko, D.; Neiss, C.; Vies, F.; Grling, A. Phys. Rev. Lett. 2012, 108, 086804. doi:10.1103/PhysRevLett.108.086804 doi: 10.1103/PhysRevLett.108.086804
3. [3]
  Jia, Z. Y.; Li, Y. J.; Zuo, Z. C.; Liu, H. B. Huang, C. S. Li, Y. L. Acc. Chem. Res. 2017, 50, 2470. doi:10.1021/acs.accounts.7b00205 doi: 10.1021/acs.accounts.7b00205
4. [4]
  Li, Y. J.; Xu, L. Liu, H. B. Li, Y. L. Chem. Soc. Rev. 2014, 43, 2572. doi:10.1039/c3cs60388a doi: 10.1039/c3cs60388a
5. [5]
  Li, G. X.; Li, Y. L.; Liu, H. B.; Guo, Y. B.; Li, Y. J. Zhu, D. B. Chem. Commun. 2010, 46, 3256. doi:10.1039/b922733d doi: 10.1039/b922733d
6. [6]
  Li, Y. J.; Li, Y. L. Acta Polym. Sin. 2015, No. 2, 147. doi: 10.11777/j.issn1000-3304.2015.14409
7. [7]
  Huang, C. S.; Li, Y. L. Acta Phys. -Chim. Sin. 2016, 32, 1314. doi: 10.3866/PKU.WHXB201605035
8. [8]
  Chen, Y. H.; Liu, H. B.; Li, Y. L. Chin. Sci. Bull. 2016, 61, 290. doi: 10.1360/N972016-00483
9. [9]
  Zhou, J. Y.; Gao, X.; Liu, R.; Xie, Z. Q.; Yang, J.; Zhang, S. Q.; Zhang, G. M.; Liu, H. B. Li, Y. L.; Zhang, J.; et al. J. Am. Chem. Soc. 2015, 137, 7596. doi:10.1021/jacs.5b04057 doi: 10.1021/jacs.5b04057
10. [10]
  Matsuoka, R.; Sakamoto, R.; Hoshiko, K.; Sasaki, S.; Masunaga, H.; Nagashio, K.; Nishihara, H. J. Am. Chem. Soc. 2017, 139, 3145. doi:10.1021/jacs.6b12776 doi: 10.1021/jacs.6b12776
11. [11]
  Li, G. X.; Li, Y. L.; Qian, X. M.; Liu, H. B.; Lin, H. W.; Chen, N.; Li, Y. J. J. Phys. Chem. C 2011, 115, 2611. doi:10.1021/jp107996f doi: 10.1021/jp107996f
12. [12]
  Thangavel, S.; Krishnamoorthy, K.; Krishnaswamy, V.; Raju, N.; Kim, S. J.; Venugopal, G. J. Phys. Chem. C 2015, 119, 22057. doi:10.1021/acs.jpcc.5b06138 doi: 10.1021/acs.jpcc.5b06138
13. [13]
  Zuo, Z. C.; Shang, H.; Chen, Y. H.; Li, J. F.; Liu, H. B.; Li, Y. J.; Li, Y. L. Chem. Commun. 2017, 53, 8074. doi:10.1039/c7cc03200e doi: 10.1039/c7cc03200e
14. [14]
  Zhang, S. L.; He, J. J.; Zheng, J.; Huang, C. S.; Lv, Q.; Wang, K.; Wang, N.; Lan, Z. G. J. Mater. Chem. A 2017, 5, 2045. doi:10.1039/C6TA09822C doi: 10.1039/C6TA09822C
15. [15]
  Lv, Y. L.; Yang, L.; Cao, D. P. ACS Appl. Mater. Inter. 2017, 9, 32859. doi:10.1021/acsami.7b11371 doi: 10.1021/acsami.7b11371
16. [16]
  Krishnamoorthy, K.; Thangavel, S.; Veetil, J. C.; Raju, N.; Venugopal, G.; Kim, S. J. Int. J. Hydrogen Energy 2016, 41, 1672. doi:10.1016/j.ijhydene.2015.10.118 doi: 10.1016/j.ijhydene.2015.10.118
17. [17]
  Li, J.; Gao, X.; Jiang, X.; Li, X. B.; Liu, Z. F.; Zhang, J.; Tung, C. H.; Wu, L. Z. ACS Catal. 2017, 7, 5209. doi:10.1021/acscatal.7b01781 doi: 10.1021/acscatal.7b01781
18. [18]
  Gao, X.; Li, J.; Du, R. Zhou, J. Y.; Huang, M. Y.; Liu, R.; Li, J.; Xie, Z. Q.; Wu, L. Z.; Liu, Z. F.; et al. Adv. Mater. 2017, 29, 1605308. doi:10.1002/adma.201605308 doi: 10.1002/adma.201605308
19. [19]
  Zhu, S. E.; Li, F. Wang, G. W. Chem. Soc. Rev. 2013, 42, 7535. doi:10.1039/c3cs35494 doi: 10.1039/c3cs35494
20. [20]
  Baláž, P.; Achimovi?ová, M.; Baláž, M.; Billik, P.; Cherkezova-Zheleva, Z.; Criado, J. M.; Delogu, F.; Dutková, E.; Gaffet, E.; Gotor, F. J.; et al. Chem. Soc. Rev. 2013, 42, 7571. doi:10.1039/c3cs35468g doi: 10.1039/c3cs35468g
21. [21]
  Wang G. W. Chem. Soc. Rev. 2013, 42, 7668. doi:10.1039/c3cs35526h doi: 10.1039/c3cs35526h
22. [22]
  Do, J. L.; Friščić, T. ACS Central Sci. 2017, 3, 13. doi:10.1021/acscentsci.6b00277 doi: 10.1021/acscentsci.6b00277
23. [23]
  Jones, W.; Eddleston, M. D. Faraday Discuss. 2014, 170, 9. doi:10.1039/C4FD00162A doi: 10.1039/C4FD00162A
24. [24]
  Rowlands, S. A.; Hall, A. K.; Mccormick, P. G.; Street, R.; Hart, R. J.; Ebell, G. F.; Donecker, P. Nature 1994, 367, 223. doi:10.1038/367223a0 doi: 10.1038/367223a0
25. [25]
  Li, Y.; Liu, Q.; Li, W.; Lu, Y.; Meng, H.; Li, C. Chemosphere 2017, 166, 275. doi:10.1016/j.chemosphere.2016.09.135 doi: 10.1016/j.chemosphere.2016.09.135
26. [26]
  Yang, C. F.; Cui, X. L. Scalable synthesis of graphyne with enhanced lithium storage performance. The 19th National Conference on Electrochemistry. Shanghai, 2017, 12. L1859
27. [27]
  Tan, D. Z.; Fan, W. J.; Xiong, W. N.; Sun, H. X.; Cheng, Y. Q.; Liu, X. Y.; Meng, C. G.; Li, A.; Deng, W. Q. Macromol. Chem. Phys. 2012, 213, 1435. doi:10.1002/macp.201200084 doi: 10.1002/macp.201200084
28. [28]
  Wu, B.; Li, M. R.; Xiao, S. N.; Qu, Y. K.; Qiu, X. Y.; Liu T. F; Tian, F. H.; Li, H. X.; Xiao, S. X. Nanoscale 2017, 9, 11939. doi:10.1039/c7nr02247f doi: 10.1039/c7nr02247f
29. [29]
  He, J. J.; Wang, N.; Cui, Z. L.; Du, H. P.; Fu, L.; Huang, C. S.; Yang, Z.; Shen, X. Y.; Yi, Y. P.; Tu, Z. Y.; et al. Nature Commun. 2017, 8, 1172. doi:10.1038/s41467-017-01202-2 doi: 10.1038/s41467-017-01202-2
30. [30]
  Zhang, S.; Wang, J.; Li, Z.; Zhao, R.; Tong, L.; Liu, Z. F.; Zhang, J.; Liu, Z. R. J. Phys. Chem. C 2016, 120, 10605. doi:10.1021/acs.jpcc.5b12388 doi: 10.1021/acs.jpcc.5b12388
31. [31]
  Li, Y.; Liu, Q.; Li, W.; Meng, H.; Lu, Y. Z.; Li, C. ACS Appl. Mater. Inter. 2017, 9, 3895. doi:10.1021/acsami.6b13610 doi: 10.1021/acsami.6b13610
32. [32]
  Chen, Y. Ma, X. Q.; Cui, X. L.; Jiang, Z. Y. J. Power Sources 2016, 302, 233. doi:10.1016/j.jpowsour.2015.10.057 doi: 10.1016/j.jpowsour.2015.10.057
33. [33]
  Qin, H. L.; Yu, D. Q.; Deng, A. J. Handbook of Analytical Chemistry. 7A Nuclear Magnetic Resonance Spectroscopy Analysis, 3rd ed.; Chemical Industry Press:Beijing, 2016; pp. 8–18.
34. [34]
  Hu, X. B.; Wang. K. C. Chemical Engineer, 2015, 243, 48. doi: 10.16247/j.cnki.23-1171/tq.20151248
35. [35]
  Xue, S. Organic Structure Analysis; University of Science and Technology of China Press:Hefei, 2005; pp:84–178.
36. [36]
  Chang, J. H.; Dong, Q. G. Spectral Principle and Analysis, 3rd ed.; Science Press:Beijing, 2012; pp. 112–165
37. [37]
  Zha, Q. X. An Introduction to Electrode Processes, 2nd ed.; Science Press:Beijing, 1987; pp. 487–540.
38. [38]
  Cui, X. L. Chemistry 2017, 80, 1160. doi: 10.14159/j.cnki.0441-3776.2017.12.014
39. [39]
  Butler, M. A. J. Appl. Phys. 1977, 48, 1914. doi:10.1063/1.323948 doi: 10.1063/1.323948
40. [40]
  Lee, J.; Li, Z.; Zhu, L. Z.; Xie, S. H.; Cui, X. L. Appl. Catal. B:Environ. 2018, 224, 715. doi:10.1016/j.apcatb.2017.10.057 doi: 10.1016/j.apcatb.2017.10.057
41. [41]
  Tu, W. Y.; Su, L.; Liu, W. J.; Wu, B. L. J. Electrochem. 2000, 6, 181. doi: 10.3969/j.issn.1006-3471.2000.02.008
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