有机硅烷功能化碳点的制备及应用进展

曹文兵; 孙争光; 武钰涵; 张玉红; 詹园

doi:10.13801/j.cnki.fhclxb.20210816.001

有机硅烷功能化碳点的制备及应用进展

doi: 10.13801/j.cnki.fhclxb.20210816.001

1.
湖北大学　材料科学与工程学院功能材料绿色制备与应用教育部重点实验室，武汉 430062
2.
湖北大学　化学化工学院，武汉 430062

基金项目: 湖北大学功能材料绿色制备与应用教育部重点实验室2020年开放课题项目

详细信息

通讯作者:
詹园，博士，硕士生导师，研究方向为纳米碳功能材料　E-mail：zy@hubu.edu.cn

中图分类号: O613.71；O613.72；TB383
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- 被引次数: 0
出版历程
- 收稿日期: 2021-06-22
- 修回日期: 2021-07-23
- 录用日期: 2021-07-31
- 网络出版日期: 2021-08-17
- 刊出日期: 2021-03-01

Progresses in preparation and application of organosilane functionalized carbon dots

1.
Key Laboratory for the Green Preparation and Application of Functional Materials, Ministry of Education, School of Materials Science and Engineering, Hubei University, Wuhan 430062, China
2.
School of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, China

摘要

摘要: 碳点(Carbon dots，CDs)因其合成方法简单、原料来源广泛、光致发光性能优异、生物相容性好等优点，在生物成像、荧光探针等方面引起了广泛的研究兴趣。然而，CDs仍存在荧光量子产率低、聚集诱导荧光猝灭等不足，限制了其在光电器件领域中的应用。有机硅烷功能化CDs (SiCDs)不仅具有良好的液态荧光，而且能够保持其固态荧光性能，对拓展CDs的应用领域具有重要意义。综述了近年来国内外 SiCDs 的制备方法、性能调控与应用，总结了 SiCDs 在发展中存在的问题，并对 SiCDs 的发展方向进行了展望。
- 有机硅烷功能化CDs /
- 制备方法 /
- 固态荧光 /
- 生物应用 /
- 光电器件
Abstract: Carbon dots (CDs) have attracted extensive attention in biological imaging, fluorescent probe and so on owing to their simple synthesis methods, wide range of raw materials, excellent photoluminescence properties and good biocompatibility. However, CDs still undergo some limitations such as low quantum yield, aggregation induced fluorescence quenching and so on, which will limit their application on photoelectric devices. Organosilane functionalized CDs (SiCDs) exhibit bright emission in solution, and their fluorescence properties could be maintained in solid state, which is an effective strategy to exploit the application field of CDs. The preparation methods of SiCDs are reported, including direct synthesis method and post-processing method, and the fluorescence properties of SiCDs prepared by different methods were compared. We also reviewed the applications of SiCDs in different fields, and further summarized the problems of SiCDs in the preparations and applications, which need to be solved in future. Finally, the preparation method, performance regulation and application of SiCDs are prospected.
- organosilane functionalized carbon dots /
- preparation methods /
- solid state fluorescence /
- biological applications /
- photoelectric devices

HTML全文

图 1 一系列高发光有机硅烷功能化碳点 (SiCDs)的制备示意图^[31]

Figure 1. Schematic diagram for the preparation of a series of highly luminescent organosilane functionalized CDs (SiCDs)^[31]

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图 2 SiCDs的合成原理图及其在白光LED中的应用^[32]

Figure 2. A schematic of synthesizing SiCDs with their application in white LED ^[32]

CA—Citric acid; KH-792—N-[3-(Trimethoxysilyl)propyl]ethylenediamine

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图 3 水热法制备红色荧光SiCDs的示意图^[44]

Figure 3. A schematic for the preparation of red emission SiCDs^[44]

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图 4 CDs、SiCDs以及SiCDs凝胶玻璃的制备^[54](a)和CDs 杂化硅球的制备示意图^[55](b)

Figure 4. Schematic diagrams for the preparations of CDs, SiCDs and SiCDs gel glasses ^[54](a) and carbon nanodots-hybridized silica nanospheres^[55](b)

TEOS–Tetraethyl orthosilicate; CSNs–Carbon dots-hybridized silica nanospheres

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图 5 (a) SiCDs表面与Hg²⁺络合示意图；(b) SiCDs在添加0~5 µmol/L的Hg²⁺后的PL光谱^[46]

Figure 5. (a) Schematic illustration of the Hg²⁺complexation on SiCDs surface; (b) PL spectra of SiCDs in water with different Hg²⁺ concentrations of 0-5 µmol/L^[46]

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图 6 (a) SiCDs作为荧光探针对槲皮素的检测；(b) SiCDs(5×10⁻⁵ g/mL)水溶液在添加不同浓度的槲皮素(0~40 μmol/L)后的荧光光谱图^[63]

Figure 6. (a) Schematic illustration for quercetin sensing based on the SiCDs fluorescence system; (b) Fluorescence spectra of SiCDs (5×10⁻⁵ g/mL) in aqueous solution upon addition of different amounts of quercetin (0–40 μmol/L) ^[63]

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图 7 (a) SiCDs@DA的制备示意图；(b) SiCDs@DA和Ag⁺处理HeLa细胞的荧光显微镜图像^[49]

Figure 7. (a) Schematic illustration of the procedure for SiCDs@DA; (b) Fluorescence microscope images of HeLa cell with different treatment with SiCDs@DA and Ag^+[49]

DA—Dopamine

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图 8 基于绿色SiCDs/红色CDs复合纳米材料的白光LEDs的示意图(a)，冷和暖白光LEDs的发光光谱(b)和色坐标(c)^[68]

Figure 8. Schematic diagram showing WLEDs based on the green SiCDs/red-CDs nanohybrids(a), EL spectra (b) and color coordinates (c) of the cold and warm WLEDs ^[68]

CRI—Color rendering index; T_c—Color temperature

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图 9 氨基丙基甲基聚硅氧烷功能化碳点（AMS-CDs）及其交联硅橡胶的制备和应用^[69]

Figure 9. Preparation and application of aminopropylmethylpolysiloxane carbon dots (AMS-CDs) and their cross-linking silicone rubbers^[69]

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图 10 SiCDs用于制备闭孔结构CDs光子晶体及其亲液不浸润行为的示意图^[71]

Figure 10. Schematic diagram of closed-cell CDs photonic crystals prepared by SiCDs and their wetting state of some organic solvents on the surface^[71]

PS—Polystyrene; PC—Photonic crystal

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图 11 高发光和UV屏蔽的SiCDs及其聚合物凝胶玻璃的制备示意图^[52]

Figure 11. Schematic diagram for the preparation of highly luminescent and UV shielding SiCDs and their polymerized ormosil gel glasses ^[52]

RT—Room temperature

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表 1 典型的前驱体直接合成法制备SiCDs的性能参数

Table 1. Typical performance parameters of SiCDs by direct synthesis method

Materials	Synthetic method	Solvent	T/℃	Reaction time	Ex/Em/nm	PLQY /%	Ref.
CA, KH-602	Simple heating	H₂O	230	5-6 h	390/506	35-40	[20]
CA, glucose, KH-792	Solvothermal	EtOH, H₂O	180	12 h	370/460	–	[21]
CA, KH-792	Microwave-assisted Hydrothermal	H₂O	180	5 min	365/454	65.8	[34]
CA, KH-602	Simple heating	Acetone	150	5 min	580/640	9.6	[36]
p-PD, KH-907	Solvothermal	EtOH	180	12 h	500-560/604	5.5	[44]
CA, KH-602	Solvothermal	KH-602	150	4 h	360/465	51	[46]
EDTA-2Na, KH-792	Microwave irradiation	Glycerol	160	10 min	405/440	62	[47]
CA, KH-550	Hydrothermal	H₂O	180	4 h	340/440	–	[48]
Glycerol, KH-550	Microwave-assisted irradiation	–	–	5 min	400/476	12.4	[49]
CA, KH-602	Simple heating	KH-602	80	1 min	340-480/450-530	47	[50]
CA, KH-602	Hydrothermal	H₂O	180	12 h	375/450	39.2	[51]
CA, KH-792	Hydrothermal	H₂O	180	12 h	360/450	82	[52]
CA, KH-602	Hydrothermal	H₂O	200	2 h	360/450	–	[53]
Notes: T—Reation temperature; Ex—Excitation; Em—Emission; EDTA-2Na—Ethylenediaminetetraacetic acid disodium salt; p-PD—p-Phenylenediamine; PLQY—Photoluminescence quantum yield; KH-602—N-β-(Aminoethyl)-γ-aminopropyl methyl dimethoxysilane; KH-907—(3-Isocyanopropyl) triethoxysilane; KH-550—3-Aminopropyl triethoxysilane.

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表 2 典型的后处理法合成SiCDs的性能参数

Table 2. Typical performance parameters of SiCDs by post-treatment method

Materials of CDs	Synthetic method of CDs	Silane	Synthetic method of SiCDs	Solvent	Ex/Em/nm	PLQY /%	Ref.
p-PD, IPT	Solvothermal	KH-560	Polycondensation	EtOH	490/569-626	40	[54]
Carbon fibers	Simple heating	KH-550	Polycondensation	Ace	400/533	1.7	[55]
CA, urea	Hydrothermal	KH-550	Polycondensation	EtOH	350/445	55	[56]
Chitosan, EDA	Hydrothermal	GPDMS	Solvothermal	EtOH	–	10.4	[57]
Starch	Ultrasonic	KH-570	Modified Stöber approach	EtOH	270-370/343-433	–	[58]
PAR, EDA	Ultrasonic	KH-570	Ultrasonic	H₂O	420/510	28.3	[59]
Notes: IPT—n-Propyl isocyanate; Ace—Acetonitrile; EDA—Ethylenediamine; GPDMS—3-Glycidoxypropyldimethoxymethylsilane; KH-560—3-Glycidoxypropyltrimethoxysilane; PAR—Polyamide resin; KH-570—γ-Methacryloxypropyltrimethoxysilane.

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