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Phosphorescent carbon dots: Microstructure design, synthesis and applications

KANG Hai-xin ZHENG Jing-xia LIU Xu-guang YANG Yong-zhen

康海鑫, 郑静霞, 刘旭光, 杨永珍. 磷光碳点的结构设计、合成及其应用. 新型炭材料, 2021, 36(4): 649-664. doi: 10.1016/S1872-5805(21)60083-5
引用本文: 康海鑫, 郑静霞, 刘旭光, 杨永珍. 磷光碳点的结构设计、合成及其应用. 新型炭材料, 2021, 36(4): 649-664. doi: 10.1016/S1872-5805(21)60083-5
KANG Hai-xin, ZHENG Jing-xia, LIU Xu-guang, YANG Yong-zhen. Phosphorescent carbon dots: Microstructure design, synthesis and applications. New Carbon Mater., 2021, 36(4): 649-664. doi: 10.1016/S1872-5805(21)60083-5
Citation: KANG Hai-xin, ZHENG Jing-xia, LIU Xu-guang, YANG Yong-zhen. Phosphorescent carbon dots: Microstructure design, synthesis and applications. New Carbon Mater., 2021, 36(4): 649-664. doi: 10.1016/S1872-5805(21)60083-5

磷光碳点的结构设计、合成及其应用

doi: 10.1016/S1872-5805(21)60083-5
基金项目: 国家自然科学基金(51972221);山西省回国留学人员科研资助项目(HGKY2019027,2020-051)
详细信息
    通讯作者:

    刘旭光,教授. E-mail:liuxuguang@tyut.edu.cn

    杨永珍,教授. E-mail:yyztyut@126.com

  • 中图分类号: TQ127.1+1

Phosphorescent carbon dots: Microstructure design, synthesis and applications

Funds: National Natural Science Foundation of China (51972221), Shanxi Scholarship Council of China (HGKY2019027, 2020-051)
More Information
  • 摘要: 磷光碳点(CDs)因其具有长寿命、长波长发射、低背景干扰等优点,在能源、信息和生物医学等领域具有较大的潜力。但是,磷光CDs的制备及其发光机理依然面临一些挑战,如:其三重态极易受到外界环境的影响,从而导致磷光猝灭。因此,针对存在的问题,本文首先分析和总结了磷光CDs的起源以及杂元素掺杂、刚性结构和共轭结构等对磷光CDs结构和性能的影响;其次,从一步和两步法两方面综述了其合成方法;再次,归纳了磷光CDs在信息防伪、发光二极管、离子检测和生物成像等方面的应用研究;最后,提出目前仍然存在的问题,并展望了其研究和应用发展方向。
  • FIG. 776.  FIG. 776.

    FIG. 776.. 

    Figure  1.  Diagram of phosphorescence and fluorescence emission process of CDs (Abs: absorption; FL: fluorescence; Phos: phosphorescence).

    Figure  2.  The microstructure design synthesis methods, and applications of RTP CDs.

    Figure  3.  (a) Digital photographs of RTP CDs, (b) phosphorescence excitation spectrum (olive dots) and absorption spectrum of RTP CDs dispersed in water (blue dots)[42], (c) high resolution XPS spectra of RTP CDs, (d) representation of the tunable phosphorescence emission from RTP CDs[44], (e) FTIR spectrum of RTP CDs, (f) high-resolution N1s XPS spectrum of RTP CDs and (g) the UV-Vis diffuse reflectance (red line), PL excitation (PLE) and emission (PL) spectra of RTP CD powder (inset: RTP CDs powder under daylight and UV lamp (365 nm) irradiation)[32]. Reprinted with permission.

    Figure  4.  High resolution XPS spectra of O1s and P2p for RTP CDs[49]. Reprinted with permission.

    Figure  5.  RTP emission spectra of URTP-CDs, EG-CDs and S-CDs powders under excitation of 340 nm[37]. Reprinted with permission.

    Figure  6.  (a) TEM images , (b) HRTEM images of RTP CDs[59], (c) schematic illustration of the possible structural formation of CDs@SiO2[60], (d) schematic of the design strategy of the multi-confined (rigid network, stable covalent bonds, and three-dimensional nano-space) phosphorescence[61], (e) TEM image of CDs@MP dispersion, (f) CDs@MP without matrices[51]and (g) N-doped CDs are embedded into recrystallized molten urea and biuret matrices[47]. Reprinted with permission.

    Figure  7.  (a) Phosphorescence mechanism of N-doped CDs[43], (b) schematic illustration for RTP mechanisms of CDs[64], (c) phosphorescence mechanism of RTP CDs, (d) schematic structure of crosslinking sites, (e) energy level diagrams of single luminescence unit and (f) coupled luminescence units[36]. Reprinted with permission.

    Figure  8.  (a) Schematic illustration of polymer/carbon hybrid structure variation in RTP CDs with increasing the carbonization degree[48], (b) normalized PL of RTP CD powders measured under 360 nm excitation, (c) schematic representation of four different CDs[66], (d) schematic illustration for the synthetic procedure of CDs[64], (e) schematic of the procedure used for the preparation of N-doped CDs[32] and (f) synthesis of N-doped CDs[43]. Reprinted with permission.

    Figure  9.  Schematic of the overall process for fabrication of CDs@SiO2 RTP materials with a ultralong lifetime from rice husks (RHs)[69]. Reprinted with permission.

    Figure  10.  (a) Schematic illustration for the synthetic route of CD-based anticounterfeiting inks[33], (b) a representative diagram of the formation process of the CD-LDH composite[44]. Reprinted with permission.

    Figure  11.  (a−c) Photographs of the inks in quartz cells under daylight and under UV light at 365 nm (Photographs of the printed patterns on papers under excitation at 254, 365 and 450 nm (ON) and after closing the excitation (OFF))[33], (d, e) photographs of the RTP CD-based inks and potential applications[38] and (f) schematic illustration of the time division duplexing based on the RTP CDs and RTP CDs@silica[70]. Reprinted with permission.

    Figure  12.  (a) Emission color coordinates of assembled LEDs[47], (b) emission spectra of the CD-based six WLEDs, (c) photographs of six WLEDs with adjustable CCTs, (d) CIE chromaticity diagram showing the color coordinates of the six WLEDs[66], (e) phosphorescence emission spectra of CDs@LDHs under different oxygen concentrations, (f) plots of I0/I1 as a function of the oxygen concentration[44], (g) phosphorescence spectra of RTP CDs at various calculated concentrations of Fe3+and (h) phosphorescence emission intensity ratio depends on the concentration of the added Fe3+[72]. Reprinted with permission.

    Figure  13.  Photographs of fingerprints on different substrates[69]. Reprinted with permission.

    Table  1.   A summary of the preparation methods and properties of RTP-CDs.

    ApplicationPrecursorMethodRTP CDsLife times (ms)PQY RTP Em (nm)Refs.
    Anti-counterfeiting and information encryption2-Methyl-2,4-pentanediolOne-step hydrothermal
    (180 ℃, 12 h)
    N-doped CDs@PVA22608.7%530[59]
    Folic acid, UreaOne-step hydrothermal
    (260 ℃, 2 h)
    N-doped CDs@urea530500[33]
    Folic acid, UreaOne-step hydrothermal
    (260 ℃, 2 h)
    700500
    o-Phenylenediamine, UreaOne-step hydrothermal
    (180 ℃, 2 h)
    120625
    EthylenediamineHeating (180 ℃, 2 h)N, P-doped CDs1390538[38]
    Ethylenediamine, Phosphoric acidMicrowave (750 W, 130 s)N, P-doped CDs127012.6%520[70]
    WLEDUreaHeating (195 ℃, 10 h)N-doped CDs235520[71]
    Folic acidOne-step hydrothermal
    (260 ℃, 2 h)
    N-doped CDs930490[47]
    Urea, seed CDsHydrothermal reaction
    (180 ℃, 4 h)
    N-doped CDs@PVP419596[66]
    DetectionEthylene diamine tetraacetic acidCalcination method
    (300 ℃, 4 h)
    CDs@LDHs386.8525[44]
    Anhydrous citric acid, Folic acidHydrothermal reaction
    (240 ℃, 4 h)
    N-doped CDs@silica70514%470[72]
    TriethanolamineMicrowave (65 W, 3 min)N, P-doped CDs15.85%518[68]
    Rice husk, EthylenediamineMagnetic stirring
    (180 ℃, 6 h)
    CDs@SiO21620507[69]
    Biological imaging applicationEthylenediamine, Phosphoric acidMicrowave (750 W, 130 s)N-doped CDs186011.6%505[73]
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出版历程
  • 收稿日期:  2021-05-20
  • 修回日期:  2021-07-08
  • 网络出版日期:  2021-07-07
  • 刊出日期:  2021-07-30

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