石墨烯量子点-TiO<sub>2</sub>/聚丙烯酰胺荧光水凝胶的制备与性能

杜娟; 田洪莉; 何雨璇; 张超; 佘小红; 朱雯莉; 杨巧玲

doi:10.13801/j.cnki.fhclxb.20230831.001

石墨烯量子点-TiO₂/聚丙烯酰胺荧光水凝胶的制备与性能

doi: 10.13801/j.cnki.fhclxb.20230831.001

四川轻化工大学　材料科学与工程学院，自贡 643000

基金项目: 四川省科技计划项目(2022JDRC0090)

详细信息

通讯作者:
杜娟，博士，讲师，硕士生导师，研究方向为高强度水凝胶的设计合成及性能、有机无机纳米复合材料的制备及功能化　E-mail: dujuan@suse.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2023-06-21
- 修回日期: 2023-08-16
- 录用日期: 2023-08-18
- 网络出版日期: 2023-08-31
- 刊出日期: 2024-04-15

Preparation and properties of GQDs-TiO₂/polyacrylamide fluorescent hydrogel

College of Materials Science and Engineering, Sichuan University of Science and Engineering, Zigong 643000, China

Funds: Sichuan Science and Technology Program (2022JDRC0090)

摘要

摘要: 通过将原位溶胶-凝胶法和自由基聚合法巧妙相结合制备了一种坚固、荧光的杂化水凝胶石墨烯量子点-TiO₂/聚丙烯酰胺(GQDs-TiO₂/PAM)。在该杂化水凝胶中，同时充当多功能交联剂和纳米填料的TiO₂和GQDs粒子与水凝胶网络中的亲水基团通过氢键等非共价键牢固地结合。PAM、TiO₂和GQDs之间的强非共价键作用赋予该凝胶优异的力学性能。GQDs-TiO₂/PAM (0.5wt%GQDs)水凝胶的断裂伸长率和抗拉强度分别高达2412%和181 kPa，为TiO₂/PAM水凝胶的1.78和1.13倍。另外，GQDs的引入还赋予该复合水凝胶特殊的荧光性能，它能够在365 nm紫外光照射下发出明显的蓝色荧光。因此，该水凝胶在生物医药、重金属离子检测、荧光探针等领域有很大发展潜力。
- GQDs /
- TiO₂ /
- 杂化水凝胶 /
- 力学性能 /
- 荧光性能
Abstract: A kind of strong and fluorescent hybrid hydrogel graphene quantum dots (GQDs)-TiO₂/polyacrylamide (PAM) hydrogel was prepared via a simultaneous in-situ sol-gel method and free radical polymerization. In the hybrid hydrogel, TiO₂ and GQDs particles, which served as multifunctional crosslinkers and nano-fillers, were firmly bound to hydrophilic groups in the hydrogel network through noncovalent bonds such as hydrogen bonds. The strong non-covalent interactions among PAM, TiO₂ and GQDs endowed the gel with excellent mechanical properties. The elongation at break and tensile strength of GQDs-TiO₂/PAM (0.5wt%GQDs) hybrid hydrogels are 2412% and 181 kPa, respectively, which are 1.78 and 1.13 times that of TiO₂/PAM hydrogels. In addition, the introduction of GQDs also endowed the hybrid hydrogels with special fluorescence properties, which could emit obvious blue fluorescence under 365 nm ultraviolet light. Therefore, the hydrogel has great development potential in biomedicine, heavy metal ion detection, fluorescence probes, and other fields.
- GQDs /
- TiO₂ /
- hybrid hydrogel /
- mechanical properties /
- fluorescence

HTML全文

图 1 (a) GQDs-TiO₂/聚丙烯酰胺(PAM)杂化水凝胶的形成过程示意图；TiO₂溶胶(b)、AM-TiO₂分散液(c)、AM-GQDs-TiO₂分散液(d)及水凝胶(e)的照片

Figure 1. (a) Schematic diagram for the preparation of GQDs-TiO₂/polyacrylamide (PAM) hybrid hydrogel; Photographs of TiO₂ hydrosol (b), AM-TiO₂ dispersion (c), AM-GQDs-TiO₂ dispersion (d) and hydrogel (e)

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图 2 GQDs-TiO₂/PAM杂化水凝胶(1wt%GQDs)的SEM图像

Figure 2. SEM image of the GQDs-TiO₂/PAM hybrid hydrogels (1wt%GQDs)

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图 3 GQDs和TiO₂/PAM、GQDs/PAM、GQDs-TiO₂/PAM(1wt%GQDs) 水凝胶的FTIR图谱

Figure 3. FTIR spectra of GQDs, TiO₂/PAM, GQDs/PAM, andGQDs-TiO₂/PAM hydrogels (1wt%GQDs)

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图 4 GQDs-TiO₂/PAM杂化水凝胶(1wt%GQDs)力学性能图片：(a) 交叉和拉伸；(b) 打结和拉伸；(c) 压缩和释放

Figure 4. Photographs of GQDs-TiO₂/PAM hybrid hydrogels (1wt%GQDs) under external forces: (a) Cross-bended and stretched; (b) Knotted and stretched; (c) Compressed and released

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图 5 PAM、TiO₂/PAM和GQDs-TiO₂/PAM水凝胶拉伸应力-应变曲线 (GQDs含量为0wt%、0.5wt%、1wt%、3wt%)

Figure 5. Tensile stress-strain curves of PAM, TiO₂/PAM and GQDs-TiO₂/PAM hydrogels (GQDs contents are 0wt%, 0.5wt%, 1wt%, 3wt%)

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图 6 GQDs/PAM、TiO₂/PAM及GQDs-TiO₂/PAM (1wt%GQDs) 水凝胶的TG (a)和DTG (b)曲线

Figure 6. TG (a) and DTG (b) curves of GQDs/PAM, TiO₂/PAM, and GQDs-TiO₂/PAM (1wt%GQDs) hydrogels

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图 7 GQDs-TiO₂/PAM杂化水凝胶(1wt%GQDs)在365 nm紫外光下的光致发光照片(a)和荧光图谱(b)

Figure 7. Photoluminescence photos (a) and fluorescence spectrum (b) of GQDs-TiO₂/PAM (1wt%GQDs) hybrid hydrogels under 365 nm UV light

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图 8 TiO₂/PAM、GQDs/PAM和GQDs-TiO₂/PAM水凝胶薄膜覆盖的不同浓度亚甲基蓝溶液 (0.01wt‰和0.004wt‰)紫外光照前后的吸收光谱

Figure 8. Absorption spectra of methylene blue solutions (0.01wt‰ and 0.004wt‰) with different concentrations covered by TiO₂/PAM, GQDs/PAM and GQDs-TiO₂/PAM hydrogel films before and after ultraviolet irradiation, respectively

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表 1 不同石墨烯量子点(GQDs)含量水凝胶的配方

Table 1. Formula of hydrogels with different contents of graphene quantum dot (GQDs)

Hydrogel	TEOA/g	TBOT/µL	AM/g	GQDs/wt%	BIS (0.1wt%, mL)	APS/g
PAM	—	—	2.5	—	2	0.08
GQDs/PAM	—	—	2.5	1	2	0.08
TiO₂/PAM	0.1756	200	2.5	—	2	0.08
GQDs-TiO₂/PAM	0.1756	200	2.5	0.5	2	0.08
GQDs-TiO₂/PAM	0.1756	200	2.5	1	2	0.08
GQDs-TiO₂/PAM	0.1756	200	2.5	3	2	0.08
GQDs-TiO₂/PAM	0.1756	200	2.5	5	2	0.08
Notes: TEOA—Triethanolamine; TBOT—Tetrabutyl titanate; AM—Acrylamide; BIS—N, N'-methylenebis(2-propenamide); APS—Ammo-nium persulphate; PAM—Polyacrylamide.

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