S−BiOI/BiOBr吸附型光催化剂的制备及其对2,4−二氯苯氧乙酸的去除性能

姚丹; 阳艺; 郑安妮; 王绍兵; 余关龙

S−BiOI/BiOBr吸附型光催化剂的制备及其对2,4−二氯苯氧乙酸的去除性能

姚丹¹,
阳艺²,
郑安妮²,
王绍兵¹,
余关龙^{2, 3, ,}

1.
湖南省水资源中心, 湖南长沙 410007
2.
长沙理工大学　水利与环境工程学院, 湖南长沙 410114
3.
洞庭湖水环境治理与生态修复湖南重点实验室, 湖南长沙 410114

基金项目: 湖南省水利科技项目 (XSKJ2022068-03，XSKJ2023059-37)；湖南省生态环境厅科研项目 (HBKT-2021012)

详细信息

通讯作者:
余关龙，博士，副教授，硕士生导师，研究方向为光催化材料及污水处理　E-mail：ygl079@csust.edu.cn

中图分类号: O643.36;O644.1;TB332
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出版历程
- 收稿日期: 2023-12-19
- 修回日期: 2024-01-24
- 录用日期: 2024-01-28
- 网络出版日期: 2024-03-08
- 刊出日期: 2024-11-15

Preparation of S−BiOI/BiOBr adsorption photocatalyst and its removal properties for 2,4−dichlorophenoxyacetic acid

1.
Water Resources Center of Hunan Province, Changsha 410007, China
2.
School of Hydraulic and Environmental Engineering, Changsha University of Science & Technology, Changsha 410114, China
3.
Key Laboratory of Dong ting Lake Aquatic Eco−Environmental Control and Restoration of Hunan Province, Changsha 410114, China

Funds: Water technology project of Hunan Province (XSKJ2022068-03, XSKJ2023059-37); Department of Ecology and Environment research project of Hunan Province (HBKT-2021012)

摘要

摘要: 水体的农药污染对人体健康构成潜在威胁。采用一步溶剂热法合成了一种新型S_0.1−(3/7)BiOI/BiOBr(S_0.1BBI_0.3)光催化剂。通过XRD、SEM、XPS、UV−Vis DRS、EIS等手段表征其结构、形貌和光学性能等理化性质。S_0.1BBI_0.3呈二维纳米片堆积而成的花状微球结构，Z型异质结和S掺杂双策略共修饰拓宽了BiOBr的光响应范围，有效防止光生电子−空穴对在S_0.1BBI_0.3内部复合，提高光生载流子的氧化还原能力，同时能够提高比表面积，提供更丰富的介孔结构，显著提升吸附性能，并为光催化反应提供了更多的活性位点。光催化实验结果表明，合成的S_0.1BBI_0.3在可见光下对2,4−二氯苯氧乙酸(2,4−D)具有最佳的吸附和光催化性能，在45 min黑暗和120 min光照条件下，2,4−D去除率最高可达91.8%。ESR技术证实·O₂⁻是S_0.1BBI_0.3的光催化活性物质。
- BiOBr /
- S掺杂 /
- 异质结 /
- 2,4-二氯苯氧乙酸 /
- 农药 /
- 光催化
Abstract: Pesticide pollution of water body is a potential threat to human health. In this study, a new S_0.1−(0.3/0.7)BiOI/BiOBr (S_0.1BBI_0.3) photocatalyst was synthesized by one−step solvothermal method. The structure, morphology and optical properties were characterized by XRD, SEM, XPS, UV−Vis DRS, EIS and other methods. S_0.1BBI_0.3 is a flower−like microsphere structure formed by the accumulation of two−dimensional nanosheets. Z−type heterojunction and S−doped dual−strategy co−modification broaden the photoresponse range of BiOBr, effectively prevent the photogenerated electron−hole pair recombination in S_0.1BBI_0.3, improve the photogenerated carrier redox ability, and increase the specific surface area. It provides more mesoporous structures, significantly improves adsorption properties, and provides more active sites for photocatalytic reactions. The photocatalytic experiment results showed that S_0.1BBI_0.3 had the best adsorption and photocatalytic performance for 2,4−dichlorophenoxyacetic acid (2,4−D) under visible light, and the removal rate of 2,4−D was up to 91.8% under 45 min darkness and 120 min light conditions. ESR technology confirmed that ·O₂⁻ is a photocatalytic active substance of S_0.1BBI_0.3.
- BiOBr /
- S-doped /
- Heterojunction /
- 2,4-dichlorophenoxyacetic acid /
- Pesticide /
- Photocatalysis

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图 1 S_z–(x/y)BiOI/BiOBr(S_zBBI_x)的制备流程图

Figure 1. Flow chart of preparation of S_z–(x/y)BiOI/BiOBr (S_zBBI_x)

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图 2 BiOBr、BiOI和S_0.1BBI_0.3的XRD图谱(a)和FT−IR图谱(b)

Figure 2. XRD patterns (a) and FT−IR patterns (b) of BiOBr, BiOI and S_0.1BBI_0.3

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图 3 BiOBr(a)、BiOI(b)和S_0.1BBI_0.3(c)的SEM图像

Figure 3. SEM image of BiOBr, BiOI and S_0.1BBI_0.3

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图 4 S_0.1BBI_0.3的EDS图像

Figure 4. EDS diagram of S_0.1BBI_0.3

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图 5 BiOBr、BiOI和S_0.1BBI_0.3的N₂吸附−脱附等温线和BJH孔径分布曲线(插图)

Figure 5. N₂ adsorption−desorption isotherm curves and pore size distribution by BJH method (inset part) of BiOBr, BiOI and S_0.1BBI_0.3

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图 6 BiOBr、BiOI和S_0.1BBI_0.3样品的XPS图谱：(a) 全谱；(b) Br 3d；(c) I 3d；(d) O 1s；(e) Bi 4f

Figure 6. XPS spectra of BiOBr, BiOI and S_0.1BBI_0.3 samples: (a) survey, (b) Br 3d, (c) I 3d, (d) O 1s and (e) Bi 4f

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图 7 BiOBr、BiOI、BBI_0.3、S_0.1BiOBr和S_0.1BBI_0.3的UV−Vis DRS图(a)和E_g图(b)

Figure 7. UV−Vis diffuse reflectance spectrum (a) and band gap diagram (b) of BiOBr, BiOI, BBI_0.3, S_0.1BiOBr and S_0.1BBI_0.3

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图 8 BiOBr、BiOI、BBI_0.3、S_0.1BiOBr和S_0.1BBI_0.3的EIS图谱(a)和光电流图谱(b)

Figure 8. EIS Nyquist plots (a) and photocurrent curve (b) of BiOBr, BiOI, BBI_0.3, S_0.1BiOBr and S_0.1BBI_0.3

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图 9 BiOBr、BiOI、BBI_0.3、S_0.1BBI_x和S_zBBI_0.3去除2,4−D曲线((a)、(b))、准一级动力学拟合((c)、(d))、不同S_0.1BBI_0.3投加量和去除不同浓度2,4−D曲线((e)、(f))

Figure 9. Removal curves of 2,4−D by BiOBr, BiOI, BBI_0.3, S_0.1BBI_x and S_zBBI_0.3 ((a), (b)), quasi−first−order kinetic fitting ((c), (d)), and Curves of different dosages of S_0.1BBI_0.3 and removal of different concentrations of 2,4−D ((e)、(f))

Notes: C/C₀: The ratio of the residual concentration of 2,4−D to its initial concentration

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图 10 S_0.1BBI_0.3的ESR光谱：(a) DMPO−·O₂⁻；(b) TEMPO−h⁺；(c) DMPO−·OH

Figure 10. ESR spectra of S_0.1BBI_0.3: (a) DMPO−·O₂⁻, (b) TEMPO−h⁺ and (c) DMPO−·OH

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图 11 BiOBr、BiOI、BBI_0.3、S_0.1BiOBr和S_0.1BBI_0.3的VB−XPS光谱

Figure 11. VB−XPS spectra of BiOBr, BiOI, BBI_0.3, S_0.1BiOBr and S_0.1BBI_0.3

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图 12 S_0.1BBI_0.3光催化机制示意图

Figure 12. Schematic diagram of the photocatalytic mechanism of S_0.1BBI_0.3

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表 1 S_0.1BiOBr、S_0.1BiOI和S_0.1BBI_0.3的EDS数据

Table 1. EDS data for S_0.1BiOBr, S_0.1BiOI and S_0.1BBI_0.3

Sample	Relative content of element /wt%
Sample	O	Bi	Br	I	S
S_0.1BiOBr	7.10	68.87	23.71	-	0.33
S_0.1BiOI	8.08	68.39	-	23.53	-
S_0.1BBI_0.3	11.06	68.09	17.90	2.91	0.03

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表 2 BiOBr、BiOI和S_0.1BBI_0.3的BET数据

Table 2. BET data for BiOBr, BiOI and S_0.1BBI_0.3

Sample	S_BET/ (m²·g⁻¹)	V_p/ (cm³·g⁻¹)	Pore Size/ nm
BiOBr	18.68	0.108	19.60
BiOI	17.99	0.115	19.87
S_0.1BBI_0.3	26.09	0.123	15.83
Notes: S_BET: Specific surface are; V_p: Total pore volume

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