负载CuO的Ti<sup>3+</sup>/TiO<sub>2</sub>催化剂制备及其光催化甲苯降解性能

周文君; 沈伯雄; 张芹; 王欣怡; 卢凤菊

负载CuO的Ti³⁺/TiO₂催化剂制备及其光催化甲苯降解性能

河北工业大学能源与环境工程学院, 天津 300401

基金项目:

国家重点研发计划项目 2018YFB0605101

天津自然科学基金重点 18JCZDJC39800

天津科技重大专项 18ZXSZSF00040

天津市科普项目 18KPXMSF00080

唐山市科技项目 18130211A

详细信息

中图分类号: X511
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- 被引次数: 0
出版历程
- 收稿日期: 2018-09-13
- 修回日期: 2018-10-30
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-02-10

Preparation of the Ti³⁺/TiO₂ supported CuO catalyst and its photocatalytic performance in the degradation of toluene

School of Energy & Environmental Engineering, Hebei University of Technology, Tianjin 300401, China

Funds:

the National Important Research and Development Plan 2018YFB0605101

Key Project Natural Science Foundation of Tianjin 18JCZDJC39800

the Project of Science and Technology of Tianjin 18ZXSZSF00040

Tianjin Science Popularization Project 18KPXMSF00080

Tangshan Science and Technology Project 18130211A

More Information

Corresponding author: SHEN Bo-xiong, E-mail: shenboxiong0722@sina.com

摘要

摘要: 通过在锐钛矿TiO₂载体表面上负载Cu-BTC（BTC，1，3，5-苯甲酸）前驱体，还原处理制备光催化剂CuO-Ti³⁺/TiO₂（Cu-TiMB），对其在可见光条件下气相甲苯净化催化性能进行了研究。结果表明，该改良方法制备的CuO-Ti³⁺/TiO₂（Cu-TiMB）催化剂的活性是浸渍法所得催化剂CuO-TiO₂（Cu-TiD）的2.68倍。CuO-Ti³⁺/TiO₂（Cu-TiMB）具有更大的比表面积（147 m²/g）和较小的颗粒粒径（0.45 μm），呈现多孔状，CuO的分散度较高；催化剂表面Ti³⁺提供了大量的氧缺位，在400-800 nm波段的光响应能力显著增强。CuO-Ti³⁺/TiO₂（Cu-TiMB）催化剂中Cu²⁺、Cu⁺与Ti³⁺形成的异质结构进一步增多了氧缺位数量，延缓e^--h⁺的复合时间；氧缺陷增强了捕获吸附氧能力，通过金属氧化物价态变化增强化学吸附能力，提高了光催化性能。
- Ti³⁺/TiO₂ /
- CuO /
- 甲苯脱除 /
- Cu-BTC /
- 光催化
Abstract: The CuO-Ti³⁺/TiO₂(Cu-TiMB) pholocatalyst was prepared by reducing TiO₂ loaded with Cu-BTC (BTC, 1, 3, 5-benzoic acid) precursor; its photocatalytic performance in the removal of gaseous toluene was investigated. The result indicated that the toluene removal efficiency of CuO-Ti³⁺/TiO₂(Cu-TiMB) by visible irradiation was 2.68 time higher than that of CuO-TiO₂(Cu-TiD) prepared by impregnation. The CuO-Ti³⁺/TiO₂(Cu-TiMB) catalyst shows relatively high surface area (147 m²/g), small particle size (0.45 μm), porous structure and high CuO dispersion; Ti³⁺ may provide a large number of oxygen vacancies, which can significantly enhance the photocatalytic response at 400-800 nm. In addition, Cu²⁺ and Cu⁺ may form heterogeneous structure with Ti³⁺, which can further increase the number of oxygen vacancies and delay the electron-hole pairs (e^--h⁺) recombination time. The oxygen vacancies are effective in enhancing the ability for capturing adsorption oxygen, promoting the chemisorption ability by changing the valence state of metal oxides, and then improving the photocatalytic performance.
- Ti³⁺/TiO₂ /
- CuO /
- toluene removal /
- Cu-BTC /
- photocatalysis

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图 1 固定床流动反应装置示意图

Figure 1 Schematic diagram of the fixed bed flow reactor

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图 2 样品的XRD谱图

Figure 2 XRD pattern of various samples

a: TiO₂; b: Cu-TiD; c: CuBTC-Ti; d: Cu-TiM; e: Cu-TiMB

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图 3 样品的DTG (a)和DSC(b)谱图

Figure 3 DTG (a) and DSC (b) of various samples

a: TiO₂; b: Cu-TiD; c: CuBTC-Ti; d: Cu-TiM; e: Cu-TiMB

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图 4 Cu-TiD (a), Cu-TiMB (b)扫描电镜照片和Cu-TiMB (c)的透射电镜照片

Figure 4 SEM images of Cu-TiD (a), Cu-TiMB (b) and TEM of Cu-TiMB (c)

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图 5 样品的紫外-可见分光光谱谱图

Figure 5 UV-vis DRS spectra of various samples

a: TiO₂; b: Cu-TiD; c: CuBTC-Ti; d: Cu-TiM; e: Cu-TiMB

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图 6 样品的荧光光谱谱图

Figure 6 PL spectra of various samples

a: TiO₂; b: Cu-TiD; c: CuBTC-Ti; d: Cu-TiM; e: Cu-TiMB

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图 7 样品暗实验的脱除效率

Figure 7 Efficiency of various samples in dark experiment

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图 8 样品对甲苯脱除效率的影响

Figure 8 Toluene removal efficiency of various samples

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图 9 Cu-TiD和Cu-TiMB的稳定性实验

Figure 9 Stability of Cu-TiD and Cu-TiMB for toluene removal upon repetitive usage

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图 10 O₂浓度对催化效率的影响

Figure 10 Effect of O₂ concentration on the toluene removal efficiency over Cu-TiMB and Cu-TiD

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图 11 电子自旋共振谱图

Figure 11 ERS curve of Cu-TiMB

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图 12 反应前后Cu-TiMB的XPS谱图

Figure 12 XPS spectra of Cu-TiMB before and after reaction

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表 1 样品的比表面积、孔容、孔径及SEM平均颗粒粒径

Table 1 Specific surface area, pore volume, pore size and SEM average particle size of various catalyst samples

Sample	Surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Average pore diameter d/nm	Particle size (SEM) d/μm
TiO₂	139.2	0.41	12.74	1.48
CuBTC-Ti	191.4	0.55	11.55	3.63
Cu-TiM	129.3	0.38	12.62	0.49
Cu-TiMB	147.4	0.37	9.91	0.45
Cu-TiD	109.3	0.44	16.21	1.71

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表 2 Cu-TiMB反应前后元素的含量比

Table 2 Element ratio before and after reaction of Cu-TiMB

Sample	Reaction	Cu⁺/Cu²⁺	O_ab/O	O_v/O	O_L/O	Ti³⁺/Ti⁴⁺	Ti²⁺/Ti³
Cu-TiMB	before	1.23	24.7	53.01	27.09	2.78	0.12
	after	1.75	10.89	62.08	23.3	3.94	0.19

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