超声辅助制备的LaFeO<sub>3</sub>/PS催化可见光芬顿降解盐酸四环素

戈晓东; 孟冠华; 刘宝河; 张林森; 杨建华; 程洛闻

doi:10.13801/j.cnki.fhclxb.20220101.001

超声辅助制备的LaFeO₃/PS催化可见光芬顿降解盐酸四环素

doi: 10.13801/j.cnki.fhclxb.20220101.001

安徽工业大学　能源与环境学院，马鞍山 234002

基金项目: 安徽高校自然科学研究重点项目(KJ2017A065)；2017年度高校优秀骨干青年人才国内外访学研修项目(gxfx2017019)

详细信息

通讯作者:
孟冠华，博士，教授，硕士生导师，研究方向为污水处理及资源化　E-mail：mengguanhua@163.com

中图分类号: TB333
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出版历程
- 收稿日期: 2021-11-15
- 修回日期: 2021-12-16
- 录用日期: 2021-12-26
- 网络出版日期: 2022-01-04
- 刊出日期: 2023-01-15

Study of the degradation of tetracycline by visible photo-Fenton catalyzed by ultrasound-assisted LaFeO₃/PS

School of Energy and Environment, Anhui University of Technology, Ma'anshan 234002, China

Funds: Key Project Funded by the National Science Foundation of the Anhui Higher Education Institutions of China (KJ2017A065); Program of Study Abroad for Young Scholar Sponsored by Anhui Province, China (gxfx2017019)

摘要

摘要: 粉末状LaFeO₃材料具有易团聚、分离困难等缺点，规模化应用中受到限制。聚苯乙烯树脂(PS)上沉积粉末状催化剂，弥补了以上粉末材料的不足。为此，本文采用超声辅助溶胶-凝胶和水热法，在PS上沉积了自组装形成的LaFeO₃凝胶微球，制得了LaFeO₃/PS催化剂，并对其结构和性能进行了系统的研究。LaFeO₃凝胶微球在PS上的分散分布使LaFeO₃的禁带宽度变宽，从而增加了氧化还原能力，并解决了催化剂团聚等问题，提高了LaFeO₃的光芬顿催化活性。在La∶Fe∶柠檬酸(CA)摩尔比=1∶1∶2、超声40 min、水热时间18 h、水热温度90℃、LaFeO₃起始剂/PS质量比=32∶1的制备条件制得的复合材料，在可见光下催化芬顿降解盐酸四环素(TC)，TC的去除率可达96.51%(降解速率k=0.0160 min⁻¹)。自由基捕获实验表明，•O₂⁻是主要活性物种。结合捕获实验提出了TC的降解机制。通过LC/MS分析，得到了TC的降解路径。该技术提高了催化剂的稳定性，高效利用了太阳能，是一种很有前途的有机污染物降解技术。
- 盐酸四环素 /
- 可见光芬顿 /
- 聚苯乙烯树脂 /
- 铁酸镧 /
- 催化降解
Abstract: The powdered LaFeO₃ material had shortcomings such as easy agglomeration and difficult separation, so it was limited in large-scale applications. The deposition of powdered catalysts in polystyrene resin (PS) made up for the above shortcomings of powdered materials. Therefore, in this study, the self-assembled LaFeO₃ gel was deposited on the PS through ultrasound-assisted sol-gel and hydrothermal methods. The dispersion and distribution of LaFeO₃ on PS broadens the forbidden band width of LaFeO₃, improves its redox ability, solves the problem of agglomeration, and consequently improves its photo-Fenton catalytic activity. The LaFeO₃/PS composite prepared under the following experimental conditions shows the highest photocatalytic activity: La∶Fe∶Citric acid(CA) molar ratio=1∶1∶2, ultrasonic time 40 min, hydrothermal temperature 90℃, hydrothermal time 18 h, LaFeO₃ initiator/polystyrene mass ratio=32∶1. The removal rate of tetracycline hydrochloride (TC) is up to 96.51%(rate of degradation k=0.0160 min⁻¹) under visible light irradiation in the Fenton process catalyzed by LaFeO₃/PS. Free radical capture experiments show that •O₂⁻ is the main active species. According to the capture experiment, the degradation mechanism of TC was proposed. Through LC/MS analysis, the degradation path of TC was obtained. The photo-Fenton process catalyzed by LaFeO₃/PS is a promising technology for the degradation of organic pollutants due to the high stability of the catalyst and the efficient use of solar energy.
- tetracycline hydrochloride /
- photo Fenton /
- PS /
- lanthanum ferrite /
- catalytic degradation

HTML全文

图 1 (a) LaFeO₃/聚苯乙烯树脂(PS)样品制备流程图；(b) XPA-7(G4)光催化反应仪

Figure 1. (a) Sample preparation flow chart of LaFeO₃/polystyrene resin (PS); (b) XPA-7 (G4) photocatalytic reaction instrument

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图 2 La∶ Fe∶ CA的摩尔比对LaFeO₃/PS催化性能的影响(超声波功率100 W，频率40 kHz，超声辅助时间40 min，水热温度90℃，水热时间18 h，LaFeO₃起始剂/PS质量比=32∶1)

Figure 2. Influence of the molar ratio of La∶ Fe∶ CA on the catalytic performance of LaFeO₃/PS (P=100 W, f=40 kHz, t_u=40 min, T=90°C, t_h=18 h, LaFeO₃ initiator/PS mass ratio=32∶1. P—Power; f—Frequency; t_u—Time of ultrasonic; T—Temperature of the hydrothermal; t_h—Time of the hydrothermal)

CA—Citric acid; C₀—Initial concentration of tetracycline hydrochloride (TC); C_t—Concentration of TC at time t; k—Degradation rate; R—Correlation index

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图 3 (a) 超声时间对LaFeO₃/PS催化性能的影响(La∶Fe∶CA的摩尔比=1∶1∶2，超声功率100 W，频率40 kHz，水热温度90℃，水热时间18 h，LaFeO₃起始剂/聚苯乙烯质量比=32∶1)；(b) 水热温度对LaFeO₃/PS催化性能的影响(La∶Fe∶CA的摩尔比=1∶1∶2，超声功率为100 W，频率40 kHz，超声辅助时间为40 min，水热时间18 h，LaFeO₃起始剂/PS质量比=32∶1)

Figure 3. (a) Effect of ultrasound time on the catalytic performance of LaFeO₃/PS (Molar ratio of La∶Fe∶CA=1∶1∶2, P=100 W, f=40 kHz, T=90°C, t_h=18 h, LaFeO₃ initiator/polystyrene mass ratio=32∶1); (b) Influence of hydrothermal temperature on the catalytic performance of LaFeO₃/PS (Molar ratio of La∶Fe∶CA = 1∶1∶2, P= 100 W, f=40 kHz, t_u=40 min, T=90°C ,t_h=18 h, LaFeO₃ initiator/PS mass ratio=32∶1)

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图 4 水热时间对LaFeO₃/PS催化性能的影响(La∶Fe∶CA的摩尔比=1∶1∶2，超声功率100 W，频率40 kHz，超声辅助时间为40 min，水热温度为90℃，LaFeO₃起始剂/PS质量比=32∶1)

Figure 4. Influence of hydrothermal time on the catalytic performance of LaFeO₃/PS (Molar ratio of La∶Fe∶CA=1∶1∶2, P=100 W, f=40 kHz, t_u=40 min, T=90℃, LaFeO₃ initiator/PS mass ratio=32∶1)

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图 5 LaFeO₃起始剂/PS的质量比对LaFeO₃/PS催化性能的影响(La∶Fe∶CA的摩尔比=1∶1∶2，超声功率为100 W，频率40 kHz，超声辅助时间40 min，水热温度90℃，水热时间18 h)

Figure 5. Effect of LaFeO₃ initiator/PS mass ratio on the catalytic performance of LaFeO₃/PS (Molar ratio of La∶Fe∶CA=1∶1∶2 , P= 100 W, f=40 kHz, t_u= 40 min, T=90℃, t_h=18 h)

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图 6 不同体系下LaFeO₃/PS催化光芬顿降解TC去除效率的对比

Figure 6. Comparison of LaFeO₃/PS catalyzed photo-Fenton degradation TC removal efficiency in different systems

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图 7 (a) LaFeO₃/PS光芬顿反应体系中TC去除率及其矿化度；(b)催化剂可重复利用性测试

Figure 7. (a) TC and TOC removal rate of LaFeO₃/PS photo-Fenton degradation system; (b) Catalyst reusability test

TOC—Total organic carbon

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图 8 LaFeO₃/PS和PS样品的SEM图像、负载前后实际图像及SEM元素映射图像：((a)、(b)) PS的SEM图像；((c)、(d)) LaFeO₃/PS的SEM图像；(e) PS and LaFeO₃/PS的照片；(f) LaFeO₃/PS的映射点；((g)、(h)) LaFeO₃/PS的元素映射

Figure 8. SEM images of the LaFeO₃/PS and PS sample, the actual pictures before and after loading, and SEM element mapping images: ((a), (b)) SEM images of PS; ((c), (d)) SEM images of LaFeO₃/PS; (e) Pictures of PS and LaFeO₃/PS; (f) Mapping spot of LaFeO₃/PS; ((g), (h)) Elemental mapping of LaFeO₃/PS

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图 9 (a) PS和 LaFeO₃/PS的EDS图谱；(b) LaFeO₃、LaFeO₃/PS和PS的FTIR图谱；

Figure 9. (a) EDS spectra of PS and LaFeO₃/PS; (b) FTIR spectra of LaFeO₃, LaFeO₃/PS and PS

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图 10 (a) LaFeO₃、LaFeO₃/PS和PS的XRD图谱；(b) PS、LaFeO₃和LaFeO₃/PS的紫外-可见漫反射光谱

Figure 10. (a) XRD patterns of LaFeO₃, LaFeO₃/PS and PS; (b) UV-V is DRS spectra of PS, LaFeO₃ and LaFeO₃/PS

α—Absorption coefficient; E—Photoenergy

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图 11 LaFeO₃和LaFeO₃/PS的XPS图谱

Figure 11. XPS spectra of LaFeO₃ and LaFeO₃/PS

VB—Valence band

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图 12 (a) 不同捕获剂对光芬顿降解TC的影响；(b) LaFeO₃/PS催化光芬顿降解TC的机制图

Figure 12. (a) Effects of different trapping agents on degradation of TC by photo-Fenton; (b) Mechanism diagram of the degradation of TC by LaFeO₃/PS catalyzed by photo-Fenton

TBA—Tertiary butyl alcohol; PBQ—p-Benzoquinone; DMSO—Dimethyl sulfoxide; CB—Conduction band; h—Planck's constant; ν—Frequency

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图 13 TC可能的降解路径

Figure 13. Possible degradation pathways of TC

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表 1 LaFeO₃、LaFeO₃/PS和PS材料的物理性质和零电荷点

Table 1. Physical properties and zero charge point of LaFeO₃, LaFeO₃/PS and PS materials

Sample	Specific surface area/(m²·g⁻¹)	Micropore area/(m²·g⁻¹)	Pore volume/ (cm³·g⁻¹)	Average pore diameter/nm	Point of zero charge (pH_pzc)
PS	837.41	4.71	1.15000	5.74	6.74
LaFeO₃/PS	756.89	53.67	1.02000	5.62	3.08
LaFeO₃	0.03	0.13	0.00007	0.70	3.00

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表 2 LaFeO₃/PS催化光芬顿降解TC去除率同近年来报道的方法的比较

Table 2. Removal efficiency of TC by LaFeO₃/PS catalyzed by photo-Fenton compared with approaches reported in recent years

Material	Method	Removal efficiency	Parameter	Reference
Biochar/Geopolymer	Fenton	92.55%	pH=5.0, 11 h, 50 mg/L	[41]
LaFeO₃/Persulfate	Photo-Fenton	92.60%	pH=4.4, 1 h, 40 mg/L	[42]
s-MnFe₂O₄	Fenton	87.60% (TOC_RT=47.50%)	pH=3.0, 3 h, 30 mg/L	[43]
Fe₃O₄@C	UV-Fenton	79.25% (TOC_RT=43.50%)	pH=4.0-5.0, 2 h, 43.7 mg/L	[44]
CuFeO₂/Biochar	Photo-Fenton	97.40% (TOC_RT=39.00%)	pH=4.0-5.0, 2 h, 20 mg/L	[45]
LaFeO₃/Diaion^TM HP21	Photo-Fenton	90.80% (TOC_RT=73.00%), 73.00% (3rd cycle)	pH=4.0-5.0, 3 h, 10 mg/L	[18]
LaFeO₃/PS	Photo-Fenton	98.01% (TOC_RT=73.25%), 90.93% (7rd cycle)	pH=4.75, 5 h, 16.73 mg/L	This study
Note: TOC_RT—TOC removal rate.

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