基底表面缺陷对TiO2/Bi2WO6复合材料微观结构和光催化性能的影响

刘袁; 房国丽; 严祥辉; 沈宏芳

doi:10.13801/j.cnki.fhclxb.20220628.001

基底表面缺陷对TiO₂/Bi₂WO₆复合材料微观结构和光催化性能的影响

刘袁¹,
房国丽^{1, 2, ,},
严祥辉¹,
沈宏芳¹

1.
北方民族大学　材料科学与工程学院，银川 750021
2.
北方民族大学　“碳基先进陶瓷制备技术”国家地方联合工程研究中心，银川 750021

基金项目: 宁夏回族自治区重点研发计划重大(重点)项目(2019 BFG02018)；西夏区科技计划项目；北方民族大学高层次人才计划项目；北方民族大学研究生创新项目(YCX21110)

详细信息

通讯作者:
房国丽，工学博士，教授，硕士生导师，研究方向为纳米复合材料、半导体功能复合材料结构设计与优化　 E-mail: fangguoli999@163.com

中图分类号: TB332；TQ426.64
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出版历程
- 收稿日期: 2022-05-05
- 修回日期: 2022-06-04
- 录用日期: 2022-06-17
- 网络出版日期: 2022-06-28
- 刊出日期: 2023-05-14

Effect of substrate surface defect on the microstructure and photocatalytic activities of TiO₂/Bi₂WO₆ composites

1.
School of Materials Science and Engineering, North Minzu University, Yinchuan 750021, China
2.
Carbon Based Advanced Ceramics Material National Joint Engineering Research Center, North Minzu University, Yinchuan 750021, China

Funds: Ningxia Key R&D Program (2019 BFG2018); Science & Technology Project of Xixia District; High-Level Talents Program of North Minzu University; Program of Graduate Innovation Research in North Minzu University (YCX21110)

摘要

摘要: TiO₂/Bi₂WO₆异质结复合材料是可见光响应光催化活性最高的物质之一，其界面结构和微观形貌是影响光催化性能的重要因素。但是，如何可控“裁剪”TiO₂/Bi₂WO₆异质结复合材料的界面结构与微观形貌仍面临巨大的挑战。本文采用缺陷诱导可控合成TiO₂/Bi₂WO₆异质结复合材料，研究了TiO₂基底表面缺陷尺寸、分布密度等对TiO₂/Bi₂WO₆复合材料微观结构和光催化性能的影响。结果表明：热腐蚀合成温度、腐蚀时间是影响TiO₂纳米带基底表面缺陷尺寸和分布的关键因素。TiO₂纳米带基底表面的缺陷尺寸为26 nm，缺陷分布密度为12个/μm²，有利于合成界面结合良好的TiO₂/Bi₂WO₆异质结复合材料。所得TiO₂/Bi₂WO₆异质结复合材料在可见光辐照12 min后使罗丹明B(RhB)完全降解，辐照20 min后使亚甲基蓝(MB)完全降解，辐照70 min后对苯酚的降解率达43.8%。
- TiO₂/Bi₂WO₆复合材料 /
- 缺陷诱导异质生长 /
- 异质结构 /
- 缺陷分布 /
- 光催化活性
Abstract: TiO₂/Bi₂WO₆ heterojunction composite is one of the most promising visible-light derived photocatalysts. Its photocatalytic performance mainly depends on the interface structure and micro-morphology. However, it is a great challenge to control and tailor the micro-morphology and interface structure of TiO₂/Bi₂WO₆ heterojunction. Herein, TiO₂/Bi₂WO₆ heterojunction was synthesized by defect induced hetero-growth method. The influences of the defect size and distribution density, located on TiO₂ nanobelts substrate, on the microstructure and photocatalytic activity of the TiO₂/Bi₂WO₆ composites was further investigated. The results indicate that the corroding temperature and retention time are the key to modify the defect size and distribution density on the substrates. The defect size and distribution density are 26 nm and 12 per μm² respectively, which facilitate to construct TiO₂/Bi₂WO₆ heterojunction composites with well interface structure. With the as-prepared TiO₂/Bi₂WO₆ heterojunction as photocatalyst under visible light, rhodamine B (RhB) and methylene blue (MB) can be completely photodegraded after irradiation for 12 min and 20 min respectively, and the degradation percentage of phenol also is reached 43.8% after 70 min of irradiation.
- TiO₂/Bi₂WO₆ composite /
- defect inducing hetero-growth /
- heterojunction /
- defect distribution /
- photocalalytic activity

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图 1 缺陷诱导合成TiO₂/Bi₂WO₆异质结的形成示意图

Figure 1. Schematic illustration for the formation of TiO₂/Bi₂WO₆ heterojunction synthesized by defect inducing hetero-growth method

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图 2 热腐蚀时间不同时合成不同TiO₂纳米带基底样品的SEM图像

Figure 2. SEM images of the different TiO₂ nanobelt substrates synthesized with different corrosion time

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图 3 不同TiO₂/Bi₂WO₆复合材料的XRD图谱

Figure 3. XRD patterns of different TiO₂/Bi₂WO₆ composites

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图 4 ((a), (b)) TiO₂/Bi₂WO₆-2 h的SEM和TEM图像；TiO₂/Bi₂WO₆-4 h (c)、TiO₂/Bi₂WO₆-6 h (d)的SEM图像；((e), (f)) TiO₂/Bi₂WO₆-10 h的SEM和TEM图像；(g) TiO₂/Bi₂WO₆-12 h的SEM图像；(h) TiO₂/Bi₂WO₆-14 h的SEM和TEM图像

Figure 4. ((a), (b)) SEM and TEM images of TiO₂/Bi₂WO₆-2 h; SEM images of TiO₂/Bi₂WO₆-4 h (c) and TiO₂/Bi₂WO₆-6 h (d); ((e), (f)) SEM and TEM images of TiO₂/Bi₂WO₆-10 h; (g) SEM image of TiO₂/Bi₂WO₆-12 h; (h) SEM and TEM images of TiO₂/Bi₂WO₆-14 h

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图 5 可见光下不同TiO₂/Bi₂WO₆复合材料对罗丹明B(RhB)的光催化活性：(a) RhB浓度随辐照时间的演化图谱；(b) RhB光降解速率的一阶动力学拟合曲线

C₀—Initial concentration of RhB solution; C—Instantaneous concentration of RhB solution for different irradiation times;

Figure 5. Photocatalytic activities of the different TiO₂/Bi₂WO₆ composites for the degradation of rhodamine B (RhB) under visible light irradiation: (a) Evolution of RhB concentration over irradiation time; (b) Corresponding first-order kinetic linear fitting curves for photo-degradation of RhB

(1–C/C₀)×100%—Photo-degradation percentage of RhB

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图 6 不同TiO₂/Bi₂WO₆复合材料中Bi (a)、W (b)、Ti (c)和O (d) 元素的高分辨XPS图谱

Figure 6. High resolution XPS spectra of Bi (a), W (b), Ti (c) and O (d) for different TiO₂/Bi₂WO₆ composites

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图 7 不同腐蚀温度处理的TiO₂纳米带基底样品的SEM图像

Figure 7. SEM images of TiO₂ nanobelt substrates prepared at different corroding temperature

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图 8 不同腐蚀温度时TiO₂/Bi₂WO₆复合材料的XRD图谱

Figure 8. XRD patterns of the different TiO₂/Bi₂WO₆ composites prepared at different corroding temperature

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图 9 TiO₂/Bi₂WO₆-60℃ (a)、TiO₂/Bi₂WO₆-100℃ (b)和TiO₂/Bi₂WO₆-140℃ (c) 复合材料的TEM图像

Figure 9. TEM images of TiO₂/Bi₂WO₆-60℃ (a), TiO₂/Bi₂WO₆-100℃ (b) and TiO₂/Bi₂WO₆-140℃ (c) composites

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图 10 TiO₂/Bi₂WO₆-60℃、TiO₂/Bi₂WO₆-100℃及TiO₂/Bi₂WO₆-140℃复合材料中Bi (a) 和W (b) 的高分辨XPS图谱

Figure 10. High resolution XPS spectra of Bi (a) and W (b) elements for TiO₂/Bi₂WO₆-60℃, TiO₂/Bi₂WO₆-100℃ and TiO₂/Bi₂WO₆-140℃ composites

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图 11 可见光下不同TiO₂/Bi₂WO₆复合材料对RhB的光催化降解率

Figure 11. Degradation rates of RhB using different TiO₂/Bi₂WO₆ composites as photocatalyst under visible light

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图 12 TiO₂/Bi₂WO₆-100℃异质结在可见光下对RhB、亚甲基蓝(MB)、盐酸四环素(TC-HCl)和苯酚的光催化降解率

Figure 12. Degradation rates of RhB, methylene blue (MB), tetracycline hydrochloride (TC-HCl) and phenol with TiO₂/Bi₂WO₆-100℃ heterojunction as photocatalyst under visible light

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表 1 不同热腐蚀合成温度和时间TiO₂纳米带基底的比表面积

Table 1 Specific surface area of the TiO₂ nanobelts substrates synthesized for different corroding time and temperature

Sample	T_cor/℃	Time/h	Special surface area/(m²·g⁻¹)	Resulted composites
TiO₂-0	—	—	13.95	TiO₂/Bi₂WO₆-0
TiO₂-2 h	100	2	14.68	TiO₂/Bi₂WO₆-2 h
TiO₂-4 h	100	4	15.78	TiO₂/Bi₂WO₆-4 h
TiO₂-6 h	100	6	18.71	TiO₂/Bi₂WO₆-6 h
TiO₂-8 h	100	8	21.64	TiO₂/Bi₂WO₆-8 h
TiO₂-10 h	100	10	22.18	TiO₂/Bi₂WO₆-10 h
TiO₂-12 h	100	12	24.40	TiO₂/Bi₂WO₆-12 h
TiO₂-14 h	100	14	36.41	TiO₂/Bi₂WO₆-14 h
TiO₂-60℃	60	10	24.08	TiO₂/Bi₂WO₆-60℃
TiO₂-80℃	80	10	21.23	TiO₂/Bi₂WO₆-80℃
TiO₂-100℃	100	10	21.92	TiO₂/Bi₂WO₆-100℃
TiO₂-120℃	120	10	22.96	TiO₂/Bi₂WO₆-120℃
TiO₂-140℃	140	10	30.51	TiO₂/Bi₂WO₆-140℃
Notes: T_cor and time—Corroding temperature and maintaining time during the synthesis of TiO₂ nanobelts substrates; Sample TiO₂-10 h and TiO₂-100℃—Prepared using the same procedure, except the concentration of H₂SO₄ solution has a small error between them.

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