BiOBr@CdS/聚氨酯-蚕丝蛋白纳米复合膜的制备及其可见光催化性能

蹇建; 杨德兴; 邝丹妮; 袁正求; 艾秋红; 周虎

doi:10.13801/j.cnki.fhclxb.20211012.002

BiOBr@CdS/聚氨酯-蚕丝蛋白纳米复合膜的制备及其可见光催化性能

doi: 10.13801/j.cnki.fhclxb.20211012.002

蹇建^{1, 2},
杨德兴³,
邝丹妮^{1, 2},
袁正求^{1, 2},
艾秋红³,
周虎^{1, 2, ,}

1.
湖南科技大学　化学化工学院，湘潭 411201
2.
功能膜材料湖南省工程研究中心，湘潭 411201
3.
湘潭大学　化工学院，湘潭 411105

基金项目: 国家自然科学基金(21776067)；湖南省自然科学基金(2021JJ30239；2020JJ2014)

详细信息

通讯作者:
周虎，博士，教授，博士生导师，研究方向为多功能纳米复合膜材料、有机-无机杂化材料　E-mail: hnustchemzhou@163.com

中图分类号: O643
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出版历程
- 收稿日期: 2021-07-27
- 修回日期: 2021-08-31
- 录用日期: 2021-09-13
- 网络出版日期: 2021-10-12
- 刊出日期: 2022-08-31

Synthesis and visible light photocatalystic of BiOBr@CdS/polyurethane-silk fibroin nanocomposite films

JIAN Jian^{1, 2},
YANG Dexing³,
KUANG Danni^{1, 2},
YUAN Zhengqiu^{1, 2},
AI Qiuhong³,
ZHOU Hu^{1, 2
, ,}

1.
College of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, China
2.
Functional Film Materials Engineering Research Center of Hunan Province, Xiangtan 411201, China
3.
College of Chemical Engineering, Xiangtan University, Xiangtan 411105, China

摘要

摘要: 粉末形态的纳米光催化剂在催化降解污染物过程中存在颗粒易团聚、与水体难分离导致二次污染等问题。本文采用共混-湿法相转化-原位合成法制备了系列BiOBr@CdS/聚氨酯-蚕丝蛋白(BiOBr@CdS/PU-SF)纳米复合膜材料，利用XRD、FTIR、SEM、XPS、紫外-可见漫反射光谱(UV-Vis DRS)和光致发光光谱(PL)等表征技术对其物相结构、微观形貌、元素价态和光学性能等进行表征分析。研究结果表明，BiOBr@CdS/PU-SF复合膜中BiOBr与CdS形成的半导体纳米复合物，不仅显著提升了单一半导体的可见光吸收能力，且有效抑制了光生载流子的复合。通过可见光照射下降解以盐酸四环素(TC)为模型的抗生素废水评价其光催化性能，其中Bi与Cd物质的量比为1:1时的(1:1)BiOBr@CdS/PU-SF复合膜对TC的去除率最高，为70.3%，分别是BiOBr/PU-SF和CdS/PU-SF复合膜的1.33倍和2.45倍。另外，该复合膜无需离心与过滤即可实现分离和回收，并且循环使用五次后仍然保持原降解率的80%以上。
- BiOBr /
- CdS /
- 盐酸四环素 /
- 可见光催化 /
- 纳米复合膜
Abstract: The nano photocatalyst in powder form had some problems in the process of catalytic degradation of pollutants, such as easy agglomeration of particles, difficult separation resulted in secondary pollution. A kind of polyurethane-silk fibroin supported BiOBr@CdS (BiOBr@CdS/PU-SF) nanocomposite films were prepared by blending-wet phase transformation in situ synthesis method. The XRD, FTIR, SEM, XPS, UV-Vis diffuse reflectance spectra (UV-Vis DRS) and photoluminescence spectra (PL) were used to characterize the crystal structure, micromorphology, surface element valence and optical properties. The results show that the semiconductor nanocompo-sites are formed between BiOBr and CdS in the BiOBr@CdS/PU-SF composite film, which not only improve the visible light absorption capacity of a single semiconductor, but also effectively inhibit the recombination of photogenerated carriers. The photocatalytic activity was evaluated by degradation of antibiotic wastewater (Tetracycline hydrochloride (TC) as model pollutant) under visible light irradiation. Among them, a 1:1 molar ratio of Bi and Cd for (1:1)BiOBr@CdS/PU-SF composite film shows the highest removal rate of TC (70.3%), which is the 1.33 times and 2.45 times of BiOBr/PU-SF and CdS/PU-SF composite films, respectively. The pseudo-first-order kinetic constants of TC degradation are 1.63 and 3.58 times of BiOBr/PU-SF and CdS/PU-SF composite films, respectively. Moreover, the composite film can be separated and recovered without centrifugation and filtration, and it can still maintain more than 80% of the original degradation rate after recycling for five times.
- BiOBr /
- CdS /
- tetracycline hydrochloride /
- visible light photocatalysis /
- nanocomposite films

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图 1 BiOBr@CdS/PU-SF纳米复合膜的制备过程

Figure 1. Preparation process of BiOBr@CdS/PU-SF nanocomposite films

DMF—Dimethyl formamide

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图 2 PU与PU-SF复合膜的表面SEM图像：((a)~(c)) PU；((d)~(f)) PU-SF

Figure 2. Surface SEM images of PU and PU-SF composite films: ((a)-(c)) PU; ((d)-(f)) PU-SF

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图 3 PU ((a)~(c))、PU-SF ((d)~(f))、BiOBr/PU-SF ((g)~(i))、CdS/PU-SF ((j)~(l)) 和BiOBr@CdS/PU-SF ((m)~(o)) 复合膜的截面SEM图像

Figure 3. Cross-sectional SEM images of PU ((a)-(c)), PU-SF ((d)-(f)), BiOBr/PU-SF ((g)-(i)), CdS/PU-SF ((j)-(l)) and BiOBr@CdS/PU-SF ((m)-(o)) composite films

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图 4 PU-SF、BiOBr/PU-SF、CdS/PU-SF和BiOBr@CdS/PU-SF复合膜的XRD图谱

Figure 4. XRD patterns of PU-SF, BiOBr/PU-SF, CdS/PU-SF and BiOBr@CdS/PU-SF composite films

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图 5 PU-SF、BiOBr/PU-SF、CdS/PU-SF和BiOBr@CdS/PU-SF复合膜的FTIR图谱

Figure 5. FTIR spectra of PU-SF, BiOBr/PU-SF, CdS/PU-SF and BiOBr@CdS/PU-SF composite films

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图 6 BiOBr@CdS/PU-SF复合膜的XPS图谱：(a) 全谱；(b) Bi4f ；(c) Br3d；(d) C1s；(e) O1s；(f) Cd3d

Figure 6. XPS spectra of BiOBr@CdS/PU-SF composite film: (a) Full spectrum; (b) Bi4f; (c) Br3d; (d) C1s; (e) O1s; (f) Cd3d

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图 7 (a) PU-SF、BiOBr/PU-SF、CdS/PU-SF和BiOBr@CdS/PU-SF复合膜的紫外-可见漫反射光谱(UV-Vis DRS)图谱；(b) BiOBr/PU-SF的(αhν)²~hν曲线和CdS/PU-SF的(αhν)^1/2~hν曲线

Figure 7. (a) UV-Vis diffuse reflectance (UV-Vis DRS) spectra of PU-SF, BiOBr/PU-SF, CdS/PU-SF and BiOBr@CdS/PU-SF composite films; (b) (αhν)²-hν curve of BiOBr/PU-SF and (αhν)^1/2-hν curve of CdS/PU-SF sample

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图 8 BiOBr/PU-SF、CdS/PU-SF和BiOBr@CdS/PU-SF复合膜的荧光光谱(PL)

Figure 8. Photoluminescence spectra (PL) of BiOBr/PU-SF, CdS/PU-SF and BiOBr@CdS/PU-SF composite films

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图 9 BiOBr@CdS/PU-SF复合膜可见光降解盐酸四环素(TC)曲线 (a) 及其动力学拟合曲线 (b)

Figure 9. Photocatalytic degradation of tetracycline hydrochloride (TC) under visible light illumination in the presence of BiOBr@CdS/PU-SF composite films (a) and kinetic linear simulation curves (b)

C—Final concentration of TC; C₀—Initial concentration of TC

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图 10 BiOBr@CdS/PU-SF复合膜循环降解TC曲线 (a) 及使用前后XRD图谱 (b)

Figure 10. Cycling runs of TC photocatalytic degradation in the presence of BiOBr@CdS/PU-SF composite film (a) and XRD patterns of the BiOBr@CdS/PU-SF composite film before and after the cycling runs experiment (b)

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图 11 加入不同捕获剂后BiOBr@CdS/PU-SF复合膜在可见光下对TC的降解率

Figure 11. Various degradation values of BiOBr@CdS/PU-SF composite film for TC degradation after introduction of different scavengers

IPA—Isopropanol; TEOA—Triethanolamine; TEMPO—4-Hydroxy-2, 2, 6, 6-tetramethylpiperidine-1-O radical

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图 12 可见光照射下BiOBr@CdS/PU-SF复合膜降解TC的光催化机制示意图

Figure 12. Proposed mechanism for TC photodegradation under visible light irradiation over an BiOBr@CdS/PU-SF composite film

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表 1 不同BiOBr@CdS/聚氨酯-蚕丝蛋白(BiOBr@CdS/PU-SF)纳米复合膜的组成

Table 1. Compose of different BiOBr@CdS/polyurethane-silk fibroin (BiOBr@CdS/PU-SF) nanocomposite films

Number	Molar ratio of Bi and Cd	Name
1	4:1	(4:1)BiOBr@CdS/PU-SF
2	3:2	(3:2)BiOBr@CdS/PU-SF
3	1:1	(1:1)BiOBr@CdS/PU-SF
4	2:3	(2:3)BiOBr@CdS/PU-SF

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