隧道内壁耐久型CQDs@TiO<sub>2</sub>自洁净光催化涂层的制备与性能

夏慧芸; 燕敏杰; 吕昕; 张文硕; 宋莉芳; 张景怡; 牛艳辉

doi:10.13801/j.cnki.fhclxb.20230117.004

隧道内壁耐久型CQDs@TiO₂自洁净光催化涂层的制备与性能

doi: 10.13801/j.cnki.fhclxb.20230117.004

长安大学　材料科学与工程学院，西安 710064

基金项目: 国家自然科学基金面上项目(52278427)；长安大学中央高校基本科研业务费专项资金(300102310301；300102311404)；浙江省交通厅科技项目(2021012)

详细信息

通讯作者:
夏慧芸，博士，副教授，硕士生导师，主要从事交通功能材料研究　E-mail: xiahy@chd.edu.cn

中图分类号: TB34；O644.1；X511；TB33
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- 被引次数: 0
出版历程
- 收稿日期: 2022-11-03
- 修回日期: 2022-12-31
- 录用日期: 2023-01-08
- 网络出版日期: 2023-01-18
- 刊出日期: 2023-10-15

Preparation and properties of CQDs@TiO₂ based durable self-cleaning photocatalytic coating for tunnel wall

School of Materials Science and Engineering, Chang'an University, Xi'an 710064, China

Funds: National Natural Science Foundation of China (52278427); Basic Research Fund for Central Universities of Chang'an University (300102310301; 300102311404); Science and Technology Project of Transportation Department of Zhejiang Province (2021012)

摘要

摘要: 隧道因其半封闭结构通风不良导致汽车尾气在隧道中大量聚集，从而造成严重的空气污染。本文首先通过一步法将碳量子点(CQDs)负载于一维TiO₂纳米管(TNs)表面得到一种具有可见光响应、可高效降解NO的CQDs@TNs复合光催化剂；其次采用喷涂法以环氧树脂为成膜基质，通过引入低表面能组分，以上述光催化剂作为光活性组分，制备得到一种超疏水自清洁光催化涂层。采用SEM、XRD、XPS、Brunauer-Emmett-Teller计算(BET)、PL和UV-Vis对复合光催化剂的微观结构和化学组成、光学性能进行表征，并研究了其对NO的光催化降解性能；通过SEM、EDS、表面除灰测试、紫外老化测试、耐水冲测试、砂纸打磨测试对涂层的微观形貌、自清洁性及耐久性进行了系统研究，并探究了其对NO的光降解性能和循环降解性能。结果表明：该涂层具有良好的自清洁性、耐久性，对NO降解率可达42.9%，且具有一定的循环稳定性，可以长期适用于隧道等环境下对NO的降解处理。
- CQDs@TiO₂复合材料 /
- 自清洁 /
- 光催化涂层 /
- 超疏水 /
- NO
Abstract: Due to semi-closed tubular structure and poor ventilation, automobile exhaust gas accumulates in the tunnel, resulting in serious air pollution. In this paper, firstly, a kind of CQDs@TNs composite photocatalyst with visible light response and efficient degradation of NO was prepared by loading carbon quantum dots (CQDs) on the surface of unidimensional TiO₂ nanotubes (TNs). Secondly, a super hydrophobic self-cleaning photocatalyst coating was prepared by spraying epoxy resin as the film matrix, introducing low surface energy components and using the above photocatalyst as the photo active component. The microstructure, chemical composition and optical properties of the composite photocatalyst were characterized by SEM, XRD, XPS, Brunauer-Emmett-Teller calculation (BET), PL and UV-Vis, and the NO photodegradation performance was investigated. The microstructure, self-cleaning property and durability of the coating were systematically studied by SEM-EDS, ash adhesion resistance test, UV aging test, water flushing test, sandpaper abrasion test, and the photodegradation property and cyclic degradation performance of NO were also studied. The results show that the coating has good self-cleaning performance and durability, the NO degradation rate reaches 42.9%. Due to its good cycle stability, the coating is expected to be applied to the degradation of NO in tunnels and other semi enclosed environments.
- CQDs@TiO₂ composite /
- self-cleaning /
- photocatalytic coating /
- super-hydrophobic /
- NO

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图 1 涂层制备及光催化降解测试过程示意图

Figure 1. Schematic diagram of coating preparation and photocatalytic degradation test process

TEOS—Tetraacetoxysilane; PFDTES—1H,1H,2H,2H-Perfluorodecyltriethoxysilane; PCD—Photocatalytic degradation

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图 2 TNs、1-1CQDs@TNs、1-2CQDs@TNs、1-4CQDs@TNs的XRD图谱

Figure 2. XRD patterns of TNs, 1-1CQDs@TNs, 1-2CQDs@TNs and 1-4CQDs@TNs

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图 3 TNs和1-2CQDs@TNs的XPS图谱：(a) C1s；(b) O1s；(c) Ti2p

Figure 3. XPS spectra of TNs and 1-2CQDs@TNs: (a) C1s; (b) O1s; (c) Ti2p

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图 4 TNs (a)与1-2CQDs@TNs ((b)~(d))的SEM图像

Figure 4. SEM images of TNs (a) and 1-2CQDs@TNs ((b)-(d))

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图 5 TNs、1-1CQDs@TNs、1-2CQDs@TNs、1-4CQDs@TNs的PL光谱 (a)、UV-Vis光谱 (b) 及对应的Tauc plot图 (c)

Figure 5. PL spectra (a), UV-Vis spectra (b) and the corresponding plot of Tauc plot pattern (c) of TNs, 1-1CQDs@TNs, 1-2CQDs@TNs and 1-4CQDs@TNs

α—Absorption coefficient; hν—Photon energy; E_g—Band gap

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图 6 1-1CQDs@TNs、1-2CQDs@TNs、1-4CQDs@TNs在紫外光(a)和可见光(b)下对NO的光降解效率

Figure 6. Photodegradation efficiency of 1-1CQDs@TNs, 1-2CQDs@TNs, 1-4CQDs@TNs for NO under UV light (a) and visible light (b)

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图 7 FCTE涂层的SEM图像 ((a)、(b)) 与EDS图像 ((c)~(g))

Figure 7. SEM images ((a), (b)) and EDS images ((c)-(g)) of FCTE coating

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图 8 1-2FCTE涂层：(a) 表面除灰测试；(b) 耐水冲测试；(c) 砂纸打磨测试；(d) 热重分析

Figure 8. 1-2FCTE coatings: (a) Ash adhesion resistance test; (b) Water flushing test; (c) Sandpaper abrasion test; (d) Thermogravimetric analysis

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图 9 自清洁光催化FCTE涂层在紫外光下 (a)、可见光下 (b) 和可见光下循环5次 (c) 对NO的光降解效率

Figure 9. Photodegradation efficiency of the self-cleaning photocatalytic FCTE coating for NO under UV light (a), visible light (b), and visible light for five cycles (c)

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表 1 碳量子点(CQDs)@一维TiO₂纳米管(TNs)复合光催化剂及其对应涂层的命名

Table 1. Naming of carbon quantum dots (CQDs)@unidimensional TiO₂ nanotubes (TNs) composite photocatalyst and corresponding coating

Composite photocatalyst	Mass ratio CQDs:TNs	Coating
1-1CQDs@TNs	1∶1	1-1FCTE
1-2CQDs@TNs	1∶2	1-2FCTE
1-4CQDs@TNs	1∶4	1-4FCTE
Note: FCTE—Fluorosilane/CQDs@TNs/epoxy resin.

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表 2 TNs、1-1CQDs@TNs、1-2CQDs@TNs、1-4CQDs@TNs的BET测试结果

Table 2. BET test results of TNs, 1-1CQDs@TNs, 1-2CQDs@TNs and 1-4CQDs@TNs

Sample type	Specific surface area/(m²·g⁻¹)
TNs	199.53
1-1CQDs@TNs	202.75
1-2CQDs@TNs	237.06
1-4CQDs@TNs	209.67

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表 3 1-xFCTE涂层对水、橄榄油及丙三醇的接触角(CA)

Table 3. Contact angles (CA) of 1-xFCTE coating on water, olive oil and glycerol

Coating type	1-1FCTE coating/(°)	1-2FCTE coating/(°)	1-4FCTE coating/(°)
Water	158.1	160.4	150.2
Olive oil	129.3	130.2	125.8
Glycerol	149.5	151.5	144.4

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表 4 紫外老化前后1-2FCTE涂层对水、乙二醇及丙三醇的CA

Table 4. CA of 1-2FCTE coatings to water, ethylene glycol and glycerol before and after UV aging

Solvent type	Water/(°)	Ethylene glycol/(°)	Glycerol/(°)
CA before UV aging	160.4	146.1	151.5
CA after UV aging for 2 d	158.0	140.5	143.0
CA after UV aging for 5 d	154.3	137.9	139.5

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