Bi2O3-TiO2复合氧化物光催化环己烷选择氧化

郑小强; 佟占鑫; 吴健博; 廖诗艺; 王海鹏; 陈丽娟

doi:10.13801/j.cnki.fhclxb.20210906.005

Bi₂O₃-TiO₂复合氧化物光催化环己烷选择氧化

doi: 10.13801/j.cnki.fhclxb.20210906.005

郑小强^{1, 2},
佟占鑫^{1, 2},
吴健博^{1, 2},
廖诗艺^{1, 2},
王海鹏^{1, 2},
陈丽娟^{1, 2, ,}

1.
湖南科技大学　材料科学与工程学院，湘潭 411201
2.
新能源储存与转换先进材料湖南省重点实验室，湘潭 411201

基金项目: 国家自然科学基金 (21406058)；湖南省自然科学基金(2021JJ30237)

详细信息

通讯作者:
陈丽娟，博士，教授，硕士生导师，研究方向为光催化、多相催化　E-mail: ljchen11@163.com

中图分类号: TQ233.1；TQ234.21；TQ426
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- 被引次数: 0
出版历程
- 收稿日期: 2021-06-07
- 修回日期: 2021-07-26
- 录用日期: 2021-08-14
- 网络出版日期: 2021-09-06
- 刊出日期: 2022-07-30

Photocatalytic selective oxidation of cyclohexane with Bi₂O₃-TiO₂ composite oxide

ZHENG Xiaoqiang^{1, 2},
TONG Zhanxin^{1, 2},
WU Jianbo^{1, 2},
LIAO Shiyi^{1, 2},
WANG Haipeng^{1, 2},
CHEN Lijuan^{1, 2
, ,}

1.
School of Materials Science and Engineering, Hunan University of Science and Technology, Xiangtan 411201, China
2.
Hunan Key Laboratory of Advanced Materials for New Energy Storage and Conversion, Xiangtan 411201, China

摘要

摘要: 环己烷选择性氧化生成的环己醇和环己酮是己内酰胺合成中的重要中间体，在尼龙生产中具有重要作用，但工业路线条件苛刻，效率低。温和条件下环己烷选择性氧化引起极大关注，而光催化在低温环境压力下的饱和C—H活化和氧化具有独特优势。本文采用水热法制备了一系列Bi₂O₃-TiO₂复合催化剂，对其结构、形貌、光学与光电化学性质通过多种方法包括SEM、XRD、N₂吸脱附、UV-Vis、光致发光光谱、瞬态光电流响应等进行详细表征。在室温、0.1 MPa氧气为氧化剂、500 W氙灯模拟太阳光条件下比较了纯TiO₂、Bi₂O₃和Bi₂O₃-TiO₂复合物对环己烷选择性氧化的催化性能，结果表明，复合Bi₂O₃后提高了TiO₂的催化活性，其中9%Bi₂O₃-TiO₂的活性最高，在反应条件下，转化率达13.32%；环己酮/醇总选择性为95.5%，其中环己酮的选择性为57.3%、环己醇的选择性为38.2%、酮醇比为1.5。表征结果证实复合催化剂具有更宽的光吸收频率范围，能有效促进光生电子-空穴分离；同时，比表面积表征也表明复合催化剂比表面积比TiO₂和Bi₂O₃更高，有利于增加表面活性中心浓度。
- Bi₂O₃-TiO₂复合催化剂 /
- 光催化 /
- 环己烷 /
- 环己酮 /
- 选择性氧化
Abstract: The selective oxidation of cyclohexane to cyclohexanol and cyclohexanone is an important process to synthesis of caprolactam, which is an important raw material in the production of nylon. However, the industrial route suffered from the disadvantages such as harsh reaction conditions and low reactivity, therefore, selective oxidation of cyclohexane under mild conditions attracted great attention. Since photocatalysis has unique advantages in saturated C—H activation and oxidation, in this paper, a series of Bi₂O₃-TiO₂ composite photocatalysts were prepared by hydrothermal method. Their structure, morphology, optical and photoelectrochemical properties were characterized in detail by various techniques such as SEM, XRD, N₂ physical absorption and desorption, UV-Vis, photoluminescence spectroscopy, and transient photocurrent response. The photocatalytic performance of pure TiO₂, Bi₂O₃ and Bi₂O₃-TiO₂ composites toward selective oxidation of cyclohexane was compared under the reaction conditions of ambient temperature, 0.1 MPa of oxygen, and 500 W xenon lamp simulating solar light source. The results show that the catalytic activities of hybrid Bi₂O₃-TiO₂ composites are higher than that of pure TiO₂. Among them, 9%Bi₂O₃-TiO₂ exhibits the highest activity, the conversion is 13.32%, and the total selectivity (cyclohexanone and cyclohexanol) is 95.5%. The selectivity of cyclohexanone and cyclohexanol is 57.3% and 38.2%, respectively, and the ketone to alcohol ratio is 1.5. The characterization results confirm that the composite catalyst has a wider light absorption frequency range and can effectively promote the separation of photogenerated electrons and holes. In addition, the Bi₂O₃-TiO₂ composites possess higher specific surface area than pure TiO₂, which is conducive to increasing the concentration of surface active centers.
- Bi₂O₃-TiO₂ composite catalyst /
- photocatalysis /
- cyclohexane /
- cyclohexanone /
- selective oxidation

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图 1 Bi₂O₃、TiO₂、9%Bi₂O₃-TiO₂复合催化剂的XRD图谱

Figure 1. XRD patterns of Bi₂O₃, TiO₂, 9% Bi₂O₃-TiO₂ composite catalyst

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图 2 Bi₂O₃-TiO₂复合催化剂的XPS总图谱(a)以及Bi4f (b)、Ti2p (c)和O1s (d)的高分辨率XPS图谱

Figure 2. XPS total spectrum of Bi₂O₃-TiO₂ composite catalyst (a) and high-resolution XPS spectra of Bi4f (b), Ti2p (c) and O1s (d)

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图 3 Bi₂O₃、TiO₂和9%Bi₂O₃-TiO₂的SEM图像

Figure 3. SEM images of Bi₂O₃, TiO₂ and 9%Bi₂O₃-TiO₂

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图 4 TiO₂和9%Bi₂O₃-TiO₂的N₂吸附-脱附和孔径分布曲线

Figure 4. N₂ adsorption desorption and pore size distribution curves of TiO₂ and 9% Bi₂O₃-TiO₂ ((a) TiO₂; (b) 9%Bi₂O₃-TiO₂)

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图 5 TiO₂、Bi₂O₃和不同组成Bi₂O₃-TiO₂复合物的UV-Vis漫反射光谱(a)、(Ahν)^1/2-hν图(b)以及Bi₂O₃的(Ahν)²-hν图(b)

Figure 5. UV-Vis diffuse reflectance spectra (a), (Ahν)^1/2-hν diagrams (b) of TiO₂, Bi₂O₃ and Bi₂O₃-TiO₂ composites with different compositions and (Ahν)²-hν diagrams (b) of Bi₂O₃

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图 6 TiO₂、Bi₂O₃和Bi₂O₃-TiO₂复合材料的PL图谱

Figure 6. Fluorescence spectra of TiO₂, Bi₂O₃ and Bi₂O₃-TiO₂ composite materials

λ_Ex—Excitation wavelength

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图 7 TiO₂、Bi₂O₃和9%Bi₂O₃-TiO₂的光电流响应和阻抗谱

Figure 7. Photocurrent response and impedance of TiO₂, Bi₂O₃ and 9%Bi₂O₃-TiO₂

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表 1 不同样品的BET表面积、孔体积和平均孔径

Table 1. BET surface area, pore volume and average pore diameter of different samples

Sample	BET surface area/(m²·g⁻¹)	Pore volume/(cm³·g⁻¹)	Average pore size/nm
TiO₂	74.3	0.300	12.9
Bi₂O₃	1.3	0.004	7.9
9%Bi₂O₃-TiO₂	104.0	0.580	21.1

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表 2 Bi₂O₃-TiO₂复合物光催化氧化环己烷性能

Table 2. Photocatalytic oxidation of cyclohexane by Bi₂O₃-TiO₂ composite

catalyst	Conversion rate/%	Selectivity/%		Keto alcohol ratio
catalyst	Conversion rate/%	Cyclohexanone	Cyclohexanol	Keto alcohol ratio
TiO₂	10.5	60.9	34.0	1.8
Bi₂O₃	-	-	-	-
3%Bi₂O₃-TiO₂	10.4	57.9	37.1	1.6
6%Bi₂O₃-TiO₂	11.1	58.0	36.9	1.6
9%Bi₂O₃-TiO₂	13.3	57.3	38.2	1.5
12%Bi₂O₃-TiO₂	10.7	60.1	34.7	1.7
15%Bi₂O₃-TiO₂	9.5	64.7	30.2	2.2

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