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
1. [1]
  Xiaxue Chen , Yuxuan Yang , Ruolin Yang , Yizhu Wang , Hongyun Liu . Adjustable Polychromatic Fluorescence: Investigating the Photoluminescent Properties of Copper Nanoclusters. University Chemistry, 2024, 39(9): 328-337. doi: 10.3866/PKU.DXHX202308019
2. [2]
  Wenli FENG , Lu ZHAO , Yunfeng BAI , Feng FENG . Research progress on ultralong room temperature phosphorescent carbon dots. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 833-846. doi: 10.11862/CJIC.20240308
3. [3]
  Qianli Ma , Tianbing Song , Tianle He , Xirong Zhang , Huanming Xiong . Sulfur-doped carbon dots: a novel bifunctional electrolyte additive for high-performance aqueous zinc-ion batteries. Acta Physico-Chimica Sinica, 2025, 41(9): 100106-0. doi: 10.1016/j.actphy.2025.100106
4. [4]
  Tiejin Chen , Xiaokuang Xue , Jian Li , Minhui Cui , Yongliang Hao , Mianqi Xue , Haihua Xiao , Jiechao Ge , Pengfei Wang . Membrane-anchoring nanoengineered carbon dots as a pyroptosis amplifier for robust tumor photodynamic-immunotherapy. Acta Physico-Chimica Sinica, 2025, 41(10): 100113-0. doi: 10.1016/j.actphy.2025.100113
5. [5]
  Yanting HUANG , Hua XIANG , Mei PAN . Construction and application of multi-component systems based on luminous copper nanoclusters. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2075-2090. doi: 10.11862/CJIC.20240196
6. [6]
  Jianjun Liu , Xue Yang , Chi Zhang , Xueyu Zhao , Zhiwei Zhang , Yongmei Chen , Qinghong Xu , Shao Jin . Preparation and Fluorescence Characterization of CdTe Semiconductor Quantum Dots. University Chemistry, 2024, 39(7): 307-315. doi: 10.3866/PKU.DXHX202311031
7. [7]
  Yue Wu , Jun Li , Bo Zhang , Yan Yang , Haibo Li , Xian-Xi Zhang . Research on Kinetic and Thermodynamic Transformations of Organic-Inorganic Hybrid Materials for Fluorescent Anti-Counterfeiting Application information: Introducing a Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(6): 390-399. doi: 10.3866/PKU.DXHX202403028
8. [8]
  Ming ZHENG , Yixiao ZHANG , Jian YANG , Pengfei GUAN , Xiudong LI . Energy storage and photoluminescence properties of Sm³⁺-doped Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ lead-free multifunctional ferroelectric ceramics. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 686-692. doi: 10.11862/CJIC.20230388
9. [9]
  Xue Wu , Yupeng Liu , Bingzhe Wang , Lingyun Li , Zhenjian Li , Qingcheng Wang , Quansheng Cheng , Guichuan Xing , Songnan Qu . Rationally assembling different surface functionalized carbon dots for enhanced near-infrared tumor photothermal therapy. Acta Physico-Chimica Sinica, 2025, 41(9): 100109-0. doi: 10.1016/j.actphy.2025.100109
10. [10]
  Chunyuan Kang , Xiaoyu Li , Fan Yang , Bai Yang . Ionic-bond crosslinked carbonized polymer dots for tunable and enhanced room temperature phosphorescence. Acta Physico-Chimica Sinica, 2026, 42(1): 100156-0. doi: 10.1016/j.actphy.2025.100156
11. [11]
  Lin Song , Dourong Wang , Biao Zhang . Innovative Experimental Design and Research on Preparing Flexible Perovskite Fluorescent Gels Using 3D Printing. University Chemistry, 2024, 39(7): 337-344. doi: 10.3866/PKU.DXHX202310107
12. [12]
  Xinyuan Shi , Chenyangjiang , Changyu Zhai , Xuemei Lu , Jia Li , Zhu Mao . Preparation and Photoelectric Performance Characterization of Perovskite CsPbBr₃ Thin Films. University Chemistry, 2024, 39(6): 383-389. doi: 10.3866/PKU.DXHX202312019
13. [13]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
14. [14]
  Zhonghan Xu , Yuejia Li , Kin Shing Chan . 碳中和新旅程. University Chemistry, 2025, 40(6): 167-171. doi: 10.12461/PKU.DXHX202407075
15. [15]
  Xue Xiao , Jiachun Li , Xiangtong Meng , Jieshan Qiu . Sulfur-Doped Carbon-Coated Fe_0.95S_1.05 Nanospheres as Anodes for High-Performance Sodium Storage. Acta Physico-Chimica Sinica, 2024, 40(6): 2307006-0. doi: 10.3866/PKU.WHXB202307006
16. [16]
  Huimin Liu , Kezhi Li , Xin Zhang , Xuemin Yin , Qiangang Fu , Hejun Li . SiC Nanomaterials and Their Derived Carbons for High-Performance Supercapacitors. Acta Physico-Chimica Sinica, 2024, 40(2): 2304026-0. doi: 10.3866/PKU.WHXB202304026
17. [17]
  Siyi ZHONG , Xiaowen LIN , Jiaxin LIU , Ruyi WANG , Tao LIANG , Zhengfeng DENG , Ao ZHONG , Cuiping HAN . Targeting imaging and detection of ovarian cancer cells based on fluorescent magnetic carbon dots. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1483-1490. doi: 10.11862/CJIC.20240093
18. [18]
  Kuaibing Wang , Feifei Mao , Weihua Zhang , Bo Lv . Design and Practice of a Comprehensive Teaching Experiment for Preparing Biomass Carbon Dots from Rice Husk. University Chemistry, 2025, 40(5): 342-350. doi: 10.12461/PKU.DXHX202407042
19. [19]
  Lingqi Zhang , Hairong Huang , Jialin Li , Li Ji , Yufan Pan , Meiling Ye , Cuixue Chen , Shunü Peng . 桂花碳量子点的绿色制备及科普应用方案. University Chemistry, 2025, 40(8): 298-306. doi: 10.12461/PKU.DXHX202409138
20. [20]
  Jinyi Sun , Lin Ma , Yanjie Xi , Jing Wang . Preparation and Electrocatalytic Nitrogen Reduction Performance Study of Vanadium Nitride@Nitrogen-Doped Carbon Composite Nanomaterials: A Recommended Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(4): 184-191. doi: 10.3866/PKU.DXHX202310094

Get Citation

PDF

XML

Metrics

PDF Downloads(15)
Abstract views(772)
HTML views(128)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142