BiVO<sub>4</sub>/MOF复合材料的合成及其光催化性能

翟勃银; 陈颖; 梁宇宁; 李永超; 梁宏宝

BiVO₄/MOF复合材料的合成及其光催化性能

1.
东北石油大学化学化工学院, 石油与天然气化工省重点实验室, 黑龙江大庆 163318
2.
东北石油大学机械科学与工程学院, 黑龙江大庆 163318

基金项目:

国家自然科学基金 51146008

详细信息

中图分类号: TQ174
计量
- 文章访问数: 255
- HTML全文浏览量: 84
- PDF下载量: 23
- 被引次数: 0
出版历程
- 收稿日期: 2018-11-12
- 修回日期: 2019-02-18
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-04-10

Modifying BiVO₄ with metal-organic frameworks for enhanced photocatalytic activity under visible light

1.
Key Laboratory of Petroleum and Natural Gas Chemical Industry, College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318, China
2.
College of Mechanical Science and Engineering, Northeast Petroleum University, Daqing 163318, China

Funds:

the National Natural Science Foundation of China 51146008

More Information

Corresponding author: CHEN Ying, Tel: 0459-6503786, E-mail: 1308852974@qq.com

摘要

摘要: 通过简单溶剂热法制备了一种新型复合光催化剂BiVO₄/MIL-53（Fe）；运用XRD、SEM/EDS、FT-IR、N₂吸附-脱附和UV-vis DRS等手段对其进行表征，并对其光催化降解RhB活性进行了研究，提出了相应的光催化降解RhB的可能机理。结果表明，相较于单一BiVO₄材料，复合催化剂的比表面积增大，且其光催化效率相较于纯BiVO₄和MIL-53（Fe）也有了较大的提高；其中，BF-2复合材料的光催化活性最高，分别约为纯MIL-53（Fe）和BiVO₄的5.2倍和8.1倍。同时，BiVO₄/MIL-53（Fe）复合光催化剂经过四次循环实验后，仍能保持较稳定的光催化活性和结构。
- BiVO₄ /
- MOF /
- 光催化活性 /
- RhB降解
Abstract: A new composite photocatalyst, viz., BiVO₄/MIL-53(Fe), was prepared through a simple hydrothermal approach and characterized by means of X-ray diffraction, scanning electron microscopy, energy dispersive spectrometry, Fourier transform infrared spectroscopy, N₂ absorption-desorption and UV-visual diffuse reflectance spectroscopy. The photocatalytic activity of prepared BiVO₄/MIL-53(Fe) catalysts was investigated in the degradation of RhB as a simulated pollutant and a possible reaction mechanism for the photocatalytic degradation of RhB was then proposed. The results indicate that after modifying BiVO₄ with metal-organic frameworks (MOFs), the surface area of BiVO₄/MIL-53(Fe) is improved greatly; moreover, the BiVO₄/MIL-53(Fe) composite also exhibits much higher photocatalytic activity than pristine BiVO₄ and MIL-53(Fe). In particular, the photocatalytic activity of BF-2 composite is about 5.2 and 8.1 times higher than those of pure MIL-53 (Fe) and BiVO₄, respectively. In addition, BiVO₄/MIL-53(Fe) composite photocatalyst is rather stable and can keep its photocatalytic activity and structure after four recycling tests.
- BiVO₄ /
- metal-organic framework /
- photocatalytic activity /
- RhB degradation

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图 1 BiVO₄/MIL-53(Fe)复合材料的理想合成示意图

Figure 1 Synthesis diagram of BiVO₄/MIL-53(Fe)

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图 2 BiVO₄(a)、MIL-53(Fe)(b)、BF-2(c)的SEM照片和BF-2(d)的EDS谱图

Figure 2 SEM images of BiVO₄(a), MIL-53(Fe)(b), BF-2(c) and EDS spectra of BF-2(d)

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图 3 BiVO₄、MIL-53(Fe)及BiVO₄/MIL-53(Fe)复合材料的XRD谱图(a)和BiVO₄/MIL-53(Fe)在5°-18°的XRD谱图(b)

Figure 3 XRD patterns of BiVO₄, MIL-53(Fe), and BiVO₄/MIL-53(Fe) composite (a) and XRD patterns of BiVO₄/MIL-53(Fe) at 5°-18° (b)

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图 4 BiVO₄、MIL-53(Fe)及BiVO₄/MIL-53(Fe)复合材料的FT-IR谱图

Figure 4 FT-IR spectra of BiVO₄, MIL-53(Fe)及BiVO₄/MIL-53(Fe) composite materials

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图 5 MIL-53(Fe) (a)、BiVO₄ (b)及BF-2复合材料的N₂吸附-脱附等温线及孔径分布

Figure 5 Nitrogen adsorption-desorption isotherms of MIL-53(Fe) (a), BiVO₄ (b) and BF-2 (c)

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图 6 BiVO₄、MIL-53(Fe)及BiVO₄/MIL-53(Fe)复合材料的紫外可见漫反射光谱图(a)和(αhv)²与禁带宽度(hv)之间的关系图(b)

Figure 6 UV-vis diffuse reflectance spectra of BiVO₄, MIL-53(Fe) and BiVO₄/MIL-53(Fe) (a) and relationships between (αhv)² and photo energy (hv) (b)

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图 7 不同催化剂的光催化活性比较(a)和不同催化剂下光催化降解RhB的伪一阶动力学(b)

Figure 7 Comparison of various catalysts in their photocatalytic activity under visible light irradiation (a) and the related pseudo first-order kinetic of RhB degradation lines (b)

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图 8 不同RhB浓度对光降解性能的影响(a)和降解不同RhB浓度的伪一阶动力学(b)

Figure 8 Influence of RhB concentration on the photodegradation performance (a) and the pseudo first-order kinetic of RhB degradation in different RhB concentrations (b)

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图 9 BF-2光降解RhB的使用寿命(a)和反应前后的XRD谱图(b)

Figure 9 Recyclability of BF-2 for the RhB photodegradation (a) and XRD patterns of BF-2 samples before and after the reaction tests (b)

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图 10 可见光照射下BiVO₄/MIL-53(Fe)复合材料降解RhB的示意图

Figure 10 A schematic illustration of the RhB degradation over BiVO₄/MIL-53(Fe) composite under visible light irradiation

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表 1 不同催化剂样品的比表面积和孔径

Table 1 Surface area and pore size of different catalysts

Photocatalyst	MIL-53(Fe)	BiVO₄	BF-1	BF-2	BF-3
A_BET/(m²·g^-1)	26.5	10.9	20.5	18.5	16.4
Pore diameter d/nm	2.93	12.43	4.36	5.84	6.53

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表 2 不同材料光降解RhB的伪一级动力学参数

Table 2 Pseudo-first-order kinetic parameters for the RhB photodegradation over various catalysts

Catalyst	Pseudo-first-order kinetic equation	R²	k/min^-1	t_1/2=ln2·k^-1/min
BiVO₄	ln(C₀/C_t)=0.00267t+ 0.09035	0.95917	0.00267	259
MIL-53(Fe)	ln(C₀/C_t)=0.00418t+ 0.09839	0.969	0.00418	165
BF-1	ln(C₀/C_t)=0.01238t- 0.00295	0.9647	0.01238	55
BF-2	ln(C₀/C_t)=0.02167t+ 0.01574	0.98845	0.02167	31
BF-3	ln(C₀/C_t)=0.01518t+ 0.076	0.99035	0.01518	45

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表 3 BF-2光降解不同RhB浓度的伪一级动力学参数

Table 3 Pseudo-first-order kinetic parameters for the RhB photodegradation over BF-2 with different RhB concentrations

RhB concentration/ (mg·L^-1)	Pseudo-first-order kinetic equation	R²	k/min^-1	t_1/2=ln2·k^-1/min
45	ln(C₀/C_t)=0.02015t-0.03439	0.99566	0.02015	34
50	ln(C₀/C_t)=0.034t-0.02619	0.96387	0.034	20
55	ln(C₀/C_t)=0.00493t+0.06765	0.99505	0.00493	140
60	ln(C₀/C_t)=0.00359t+ 0.02577	0.98845	0.00359	193

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