Effect of substrate surface defect on the microstructure and photocatalytic activities of TiO2/Bi2WO6 composites
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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%。
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关键词:
- 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. -
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
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
图 3 不同TiO2/Bi2WO6复合材料的XRD图谱
Figure 3. XRD patterns of different TiO2/Bi2WO6 composites
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
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
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
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
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
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
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
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
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
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 Tcor/℃ 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: Tcor 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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