Citation: Ning Feng, Hongguang Li, Jingcheng Hao. Toward the Neutralization of Carbon Dots Prepared by Mixed Acid Reflux[J]. Acta Physico-Chimica Sinica, ;2021, 37(10): 200500. doi: 10.3866/PKU.WHXB202005004 shu

Toward the Neutralization of Carbon Dots Prepared by Mixed Acid Reflux

Ning Feng ^{1, 2} ,
Hongguang Li ^1,, ,
Jingcheng Hao ^1,,

1.
Key Laboratory of Colloid and Interface Chemistry, School of Chemistry and Engineering, Shandong University, Jinan 250100, China
2.
China Research Institute of Daily Chemical Industry, Taiyuan 030000, China

Corresponding author: Hongguang Li, hgli@sdu.edu.cn Jingcheng Hao, jhao@sdu.edu.cn
Received Date: 5 May 2020
Revised Date: 5 June 2020
Accepted Date: 5 June 2020
Available Online: 11 June 2020
Fund Project: the National Natural Science Foundation of China 21875129

Carbon dots (C dots) are relatively novel carbon nanomaterials that have attracted significant interest due to their unique photoluminescence, good biocompatibility, and stability. The preparation methods of C dots was usually summarized into "top-down" and "bottom-up", and mixed acid reflux is a top-down strategy that can be used to synthesize C dots, during which neutralization is a necessary step that can significantly influence the properties and potential applications of the final product. Previously, this research area mainly focused on tuning the properties of C dots by changing the starting materials and/or varying the reaction conditions; the influence of the reagents used during neutralization has been largely ignored. As the previously reported C dots prepared by mixed acid reflux were obtained from different starting materials under varied conditions, a meaningful comparison is difficult. Herein, yellow-emitting C dots were prepared by mixed acid-refluxing a carbon-rich material derived from fullerene carbon soot. For the same batch of as-prepared C dots, the influences of four reagents, i.e., NaOH, Na₂CO₃, K₂CO₃, and NH₃·H₂O, during neutralization on the structures and photoluminescence of the resulting C dots were investigated in detail. The results of thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy clearly showed that the reagent used during neutralization can affect the degree of dissociation of the acidic functional groups on the C dots. This is further supported by examination of the C dot/surfactant mixtures where subtle changes in the phase behavior were observed. Structural changes of the C dots cause variations in their surface states, ultimately altering the optical characteristics, including UV-vis absorption and fluorescence. Among the treated C dots, the sample prepared with Na₂CO₃ showed the strongest emission under the same excitation wavelength, while that prepared with NH₃·H₂O exhibited a distinct red shift (~8 nm) in the emission curve. The results presented herein provide clear evidence that neutralization reagent selection is important for optimizing the properties of the resulting C dots obtained by mixed acid reflux. In addition, the photoluminescence of the C dots can be influenced by their counterions, providing a novel method for tuning the properties of C dots while explaining their behavior in saline solutions. In short, the basicity of the neutralizing reagent and the type of counterions affect the structure of the C dots surface, which brings different performances. This work reminds researchers that it is necessary to use the type of neutralizing reagent as an experimental condition when preparing C dots in the future.
- Carbon nanomaterial,
- Carbon dot,
- Mixed Acid reflux,
- Photoluminescence,
- Top-down,
- Neutralization,
- Phase behavior
1. [1]
  Lim, S. Y.; Shen, W.; Gao, Z. Q. Chem. Soc. Rev. 2015, 44, 362. doi: 10.1039/c4cs00269e doi: 10.1039/c4cs00269e
2. [2]
  Zhu, S. J.; Song, Y. B.; Zhao, X. H.; Shao, J. R.; Zhang, J. H.; Yang, B. Nano Res. 2015, 8 (2), 355. doi: 10.1007/s12274-014-0644-3 doi: 10.1007/s12274-014-0644-3
3. [3]
  Shen, L. M.; Liu, J. Talanta 2016, 156-157, 245. doi: 10.1016/j.talanta.2016.05.028 doi: 10.1016/j.talanta.2016.05.028
4. [4]
  He, P.; Yuan, F. L.; Wang, Z. F.; Tan, Z. A.; Fan, L. Z. Acta Phys. -Chim. Sin. 2018, 34 (11), 1250. doi: 10.3866/PKU.WHXB201804041
5. [5]
  Chen, B. B.; Liu, M. L.; Li, C. M.; Huang, C. Z. Adv. Colloid Interface Sci. 2019, 270, 165. doi: 10.1016/j.cis.2019.06.008 doi: 10.1016/j.cis.2019.06.008
6. [6]
  Hu, C.; Mu, Y.; Li, M.; Qiu, J. Acta Phys. -Chim. Sin. 2019, 35 (6), 572. doi: 10.3866/PKU.WHXB201806060
7. [7]
  Xu, X. Y.; Ray, R.; Gu, Y. L.; Ploehn, H. J.; Gearheart, L.; Raker, K.; Scrivens, W. A. J. Am. Chem. Soc. 2004, 126 (40), 12736. doi: 10.1021/ja040082h doi: 10.1021/ja040082h
8. [8]
  Sun, Y. P.; Zhou, B.; Lin, Y.; Wang, W.; Fernando, K. A. S.; Pathak, P.; Meziani, M. J.; Harruff, B. A.; Wang, X.; Wang, H. F.; et al. J. Am. Chem. Soc. 2006, 128 (24), 7756. doi: 10.1021/ja062677d doi: 10.1021/ja062677d
9. [9]
  Bourlinos, A. B.; Stassinopoulos, A.; Anglos, D.; Zboril, R.; Karakassides, M.; Giannelis, E. P. Small 2008, 4 (4), 455. doi: 10.1002/smll.200700578 doi: 10.1002/smll.200700578
10. [10]
  Bourlinos, A. B.; Stassinopoulos, A.; Anglos, D.; Zboril, R.; Georgakilas, V.; Giannelis, E. P. Chem. Mater. 2008, 20 (14), 4539. doi: 10.1021/cm800506r doi: 10.1021/cm800506r
11. [11]
  Li, H. T.; He, X. D.; Kang, Z. H.; Huang, H.; Liu, Y.; Liu, J. L.; Lian, S. Y.; Tsang, C. H. A.; Yang, X. B.; Lee, S. T. Angew. Chem. Int. Ed. 2010, 49 (26), 4430. doi: 10.1002/anie.200906154 doi: 10.1002/anie.200906154
12. [12]
  Tao, H. Q.; Yang, K.; Ma, Z.; Wan, J. M.; Zhang, Y. J.; Kang, Z. H.; Liu, Z. Small 2012, 8 (2), 281. doi: 10.1002/smll.201101706 doi: 10.1002/smll.201101706
13. [13]
  Wu, M. B.; Wang, Y.; Wu, W. T.; Hu, C.; Wang, X. N.; Zheng, J. T.; Li, Z. T.; Jiang, B.; Qiu, J. S. Carbon 2014, 78, 480. doi: 10.1016/j.carbon.2014.07.029 doi: 10.1016/j.carbon.2014.07.029
14. [14]
  Wang, Y.; Wu, W. T.; Wu, M. B.; Sun, H. D.; Xie, H.; Hu, C.; Wu, X. Y.; Qiu, J. S. New Carbon Mater. 2015, 30 (6), 550. doi: 10.1016/S1872-5805(15)60204-9 doi: 10.1016/S1872-5805(15)60204-9
15. [15]
  Shao, X.; Wu, W.; Wang, R.; Zhang, J.; Li, Z.; Wang, Y.; Zheng, J.; Xia, W.; Wu, M. J. Catal. 2016, 344, 236. doi: 10.1016/j.jcat.2016.09.006 doi: 10.1016/j.jcat.2016.09.006
16. [16]
  Ye, R. Q.; Xiang, C. S.; Lin, J.; Peng, Z. W.; Huang, K. W.; Yan, Z.; Cook, N. P.; Samuel, E. L. G.; Hwang, C.; Ruan, G.; et al. Nat. Commun. 2013, 4, 2943. doi: 10.1038/ncomms3943 doi: 10.1038/ncomms3943
17. [17]
  Hu, C.; Yu, C.; Li, M. Y.; Wang, X. N.; Yang, J. Y.; Zhao, Z. B.; Eychmüller, A.; Sun, Y. P.; Qiu, J. S. Small 2014, 10 (23), 4926. doi: 10.1002/smll.201401328 doi: 10.1002/smll.201401328
18. [18]
  Li, M. Y.; Hu, C.; Yu, C.; Wang, S.; Zhang, P.; Qiu, J. S. Carbon 2015, 91, 291. doi: 10.1016/j.carbon.2015.04.083 doi: 10.1016/j.carbon.2015.04.083
19. [19]
  Dong, Y. Q.; Lin, J. P.; Chen, Y. M.; Fu, F. F.; Chi, Y. W.; Chen, G. N. Nanoscale 2014, 6, 7410. doi: 10.1039/c4nr01482k doi: 10.1039/c4nr01482k
20. [20]
  Sun, D.; Ban, R.; Zhang, P. H.; Wu, G. H.; Zhang, J. R.; Zhu, J. J. Carbon 2013, 64, 424. doi: 10.1016/j.carbon.2013.07.095 doi: 10.1016/j.carbon.2013.07.095
21. [21]
  Peng, J.; Gao, W.; Gupta, B. K.; Liu, Z.; Romero-Aburto, R.; Ge, L. H.; Song, L.; Alemany, L. B.; Zhan, X. B.; Gao, G. H.; et al. Nano Lett. 2012, 12 (2), 844. doi: 10.1021/nl2038979 doi: 10.1021/nl2038979
22. [22]
  Qiao, Z. A.; Wang, Y. F.; Gao, Y.; Li, H. W.; Dai, T. Y.; Liu, Y. L.; Huo, Q. S. Chem. Commun. 2009, 46 (46), 8812. doi: 10.1039/c0cc02724c doi: 10.1039/c0cc02724c
23. [23]
  Liu, H. P.; Ye, T.; Mao, C. D. Angew. Chem. Int. Ed. 2007, 46 (34), 6473. doi: 10.1002/anie.200701271 doi: 10.1002/anie.200701271
24. [24]
  Tian, L.; Ghosh, D.; Chen, W.; Pradhan, S.; Chang, X. J.; Chen, S. W. Chem. Mater. 2009, 21 (13), 2803. doi: 10.1021/cm900709w doi: 10.1021/cm900709w
25. [25]
  Ray, S. C.; Saha, A.; Jana, N. R.; Sarkar, R. J. Phys. Chem. C 2009, 113 (43), 18546. doi: 10.1021/jp905912n doi: 10.1021/jp905912n
26. [26]
  Zhang, Q. H.; Sun, X. F.; Ruan, H.; Yin, K. Y.; Li, H. G. Sci. China Mater. 2017, 60 (2): 141. doi: 10.1007/s40843-016-5160-9 doi: 10.1007/s40843-016-5160-9
27. [27]
  Sun, X. F.; Chen, M. J.; Zhang, Y. Q.; Yin, Y. J.; Zhang, L. W.; Li, H. G.; Hao, J. C. J. Mater. Chem. B 2018, 6 (43), 7021. doi: 10.1039/c8tb00630j doi: 10.1039/c8tb00630j
28. [28]
  Zhou, S. J.; Zhang, L. W.; Feng, Y. Q.; Li, H. G.; Chen, M. J.; Pan, W.; Hao, J. C. Chem. -Eur. J. 2018, 24 (62), 16609. doi: 10.1002/chem.201803612 doi: 10.1002/chem.201803612
29. [29]
  Sun, X. F.; Zhang, Q. H.; Yin, K. Y. Zhou, S. J.; Li, H. G. Chem. Commun. 2016, 52, 12024. doi: 10.1039/c6cc05783g doi: 10.1039/c6cc05783g
30. [30]
  Tang, S. H.; Huang, J. B.; Dai, L. R.; Wang, C. Z.; Fu, H. L. Acta Chim. Sin. 2002, 60 (1), 1. doi: 10.3321/j.issn:0567-7351.2002.01.001
31. [31]
  Zhu, B. Y.; Zhang, P.; Huang, J. B.; Zhao, G. X. Acta Phys. -Chim. Sin. 1999, 15 (2): 110. doi: 10.3866/PKU.WHXB19990204
32. [32]
  Lu, T.; Li, Z. H.; Huang, J. B.; Fu, H. L. Langmuir 2008, 24 (19), 10723. doi: 10.1021/la801301v doi: 10.1021/la801301v
33. [33]
  Li, H. G.; Hao, J. C. J. Phys. Chem. B 2008, 112 (34), 10497. doi: 10.1021/jp802235g doi: 10.1021/jp802235g
34. [34]
  Xu, X. Y.; Bao, Z. J.; Tang, W. S.; Wu, H. Y.; Pan, J.; Hu, J. G.; Zeng, H. B. Carbon 2017, 121, 201. doi: 10.1016/j.carbon.2017.05.095 doi: 10.1016/j.carbon.2017.05.095
35. [35]
  Ding, H.; Yu, S. B.; Wei, J. S.; Xiong, H. M. ACS Nano 2016, 10, 484. doi: 10.1021/acsnano.5b05406 doi: 10.1021/acsnano.5b05406
36. [36]
  Chen, D. Q.; Gao, H. B.; Chen, X.; Fang, G. L.; Yuan, S.; Yuan, Y. J. ACS Photonics 2017, 4, 2352. doi: 10.1021/acsphotonics.7b00675 doi: 10.1021/acsphotonics.7b00675
37. [37]
  Bao, L.; Liu, C.; Zhang, Z. L.; Pang, D. W. Adv. Mater. 2015, 27, 1663. doi: 10.1002/adma.201405070 doi: 10.1002/adma.201405070
38. [38]
  Yuan, Y. H.; Liu, Z. X.; Li, R. S.; Zou, H. Y.; Lin, M.; Liu, H.; Huang, C. Z. Nanoscale 2016, 8, 6770. doi: 10.1039/C6NR00402D doi: 10.1039/C6NR00402D
39. [39]
  Han, L.; Liu, S. G.; Dong, J. X.; Liang, J. Y.; Li, L. J.; Li, N. B.; Luo, H. Q. J. Mater. Chem. C 2017, 5, 10785. doi: 10.1039/C7TC03314A doi: 10.1039/C7TC03314A
40. [40]
  Yuan, K.; Zhang, X. H.; Qin, R. H.; Ji, X. F.; Cheng, Y. H.; Li, L. L.; Yang, X. J.; Lu, Z. M.; Liu, H. J. Mater. Chem. C 2018, 6, 12631. doi: 10.1039/C8TC04468F doi: 10.1039/C8TC04468F
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