Preparation of Eu-Doped ZnO/MIL-53(Fe) Photocatalyst and Its Catalytic Performance for Selective Oxidation of Alcohols

doi:10.6023/A19070268

Acta Chimica Sinica ›› 2019, Vol. 77 ›› Issue (11): 1184-1193.DOI: 10.6023/A19070268 Previous Articles Next Articles

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Eu掺杂的ZnO/MIL-53(Fe)光催化剂的合成及其对醇类选择性氧化的催化性能研究

孟双艳^a, 王明明^a, 吕柏霖^a, 薛群基^b^c*, 杨志旺^a*()

^a 西北师范大学化学化工学院生态环境相关高分子材料教育部重点实验室甘肃省高分子材料重点实验室兰州 730070
^b 中国科学院宁波材料技术与工程研究所海洋材料与相关技术重点实验室浙江省海洋材料与防护技术重点实验室宁波 315201
^c 中国科学院兰州化学物理研究所固体润滑国家重点实验室兰州 730000

投稿日期:2019-07-18 发布日期:2019-09-26
通讯作者: 薛群基,杨志旺 E-mail:yangzw@nwnu.edu.cn
基金资助:
国家自然科学基金(21563026);大学长江学者和创新研究团队计划(IRT15R56);甘肃省创新团队基础科学研究(1606RJIA324);生态环境相关高分子材料教育部重点实验室（西北师范大学）以及保水化学功能材料甘肃省国际科技合作基地的资助

Preparation of Eu-Doped ZnO/MIL-53(Fe) Photocatalyst and Its Catalytic Performance for Selective Oxidation of Alcohols

Meng Shuangyan^a, Wang Mingming^a, Lü Bolin^a, Xue Qunji^b^c*, Yang Zhiwang^a*()

^a Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education Key Laboratory of Polymer Materials of Gansu Province Lanzhou, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070
^b Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
^c State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China

Received:2019-07-18 Published:2019-09-26
Contact: Xue Qunji,Yang Zhiwang E-mail:yangzw@nwnu.edu.cn

The novel 3 dimension (3D) nanocomposite photocatalyst Eu-ZnO/MIL-53(Fe) was successfully prepared with in situ synthesis. Firstly the rare earth element Eu was doped into semiconductor ZnO and then Eu-ZnO was combined with MIL-53(Fe). The structure, morphology, optical and electrical properties of the nanocomposites were thoroughly characterized by X-ray diffraction (XRD), fourier infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), N₂ adsorption-desorption isotherms (S_BET), photoluminescence spectra (PL) and electrochemical impedance (EIS) spectra and the like. The FT-IR and XRD results showed that the photocatalysts were successfully prepared and SEM results showed that morphology of the MIL-53(Fe) were all well remained after the preparing process. The photocatalytic experiment data, UV-Vis DRS spectra and PL spectra and the like results showed that the introduction of rare earth elements Eu could greatly improve the photocatalytic efficiency of MIL-53 (Fe), and promote the effective separation of photogenerated electron-hole, which further improved the catalytic activity. The results of electrochemical impedance spectra further supported the conclusion. By exploring the photocatalytic activity of Eu-ZnO/MIL-53(Fe) under visible light conditions, the photocatalyst showed excellent photocatalytic activity. Some derivatives of benzalcohol were more affected by electronic effects, the conversion of the derivative having an electron-withdrawing group was relatively high, and the conversion of the derivative having an electron-donating group was low. The possible mechanism of the photocatalytic reaction was explored via the active species capture experiment and Mott-schottky (M-S) curve test. The results showed that the photocatalytic selective oxidation of alcohols achieved with photogenerated holes (h⁺) and hydroxyl radicals (·OH). The photo stability and thermal stability of the photocatalyst was investigated by cyclic experiments and the structure characterization of the photocatalyst before and after the photoreaction. The results showed that the photocatalyst had outstanding light stability and thermal stability.

Key words: Eu-ZnO, MIL-53(Fe), visible light catalysis, oxidation of alcohol

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Meng Shuangyan, Wang Mingming, Lü Bolin, Xue Qunji, Yang Zhiwang. Preparation of Eu-Doped ZnO/MIL-53(Fe) Photocatalyst and Its Catalytic Performance for Selective Oxidation of Alcohols[J]. Acta Chimica Sinica, 2019, 77(11): 1184-1193.

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Fig. & Tab. 13

Figure 1. XRD patterns of the samples

Figure 2. FT-IR spectra of the samples

Figure 3. SEM images of MIL-53(Fe) (a), ZnO (b), Eu-ZnO (c), 12Eu- ZnO/MIL-53 (Fe) (d), mapping images of 12% Eu-ZnO/MIL-53(Fe) (e~j) and Elemental analysis of 12Eu-ZnO/MIL-53(Fe) (k, l)

Figure 4. XPS spectra of 12Eu-ZnO/MIL-53 (Fe) composite survey spectrum (a), C 1s (b), O 1s (c), Fe 2p (d), Zn 2p (e) and Eu 3d (f)

Figure 5. UV-Vis DRS (a) and fluorescence spectra (b, c) of the samples

Figure 6. Nitrogen adsorption-desorption isotherms (a) and pore size distribution curves (b) of the samples

Figure 7. EIS Nyquist plot of the samples

Entry	Catalyst	Con.^b/%	Sel.^c/%
^a Conditions: catalyst (5 mg), benzalcohol (0.2 mmol), CCl₄ (6 mL), visible light illumination, 9 h.
1	MIL-53(Fe)	38	＞99
2	ZnO	5	＞99
3	2% Eu-ZnO	12	＞99
4	4Eu-ZnO/MIL-53(Fe)	49	＞97
5	8Eu-ZnO/MIL-53(Fe)	70	＞97
6	12Eu-ZnO/MIL-53(Fe)	74	＞97
7	16Eu-ZnO/MIL-53(Fe)	52	＞97

Table 1. Photocatalytic oxidation of benzalcohol with different catalysts

Entry	Solvent	Con./%	Sel./%
^a Conditions: 12Eu-ZnO/MIL-53(Fe) (5 mg), benzalcohol (0.2 mmol), visible light illumination, 9 h.
1	Carbon tetrachloride	72	＞98
2	Ethyl acetate	57	＞98
3	Acetonitrile	23	＞99
4	1, 2-Dichloroethane	9	＞99
5	Absolute ethanol	—	—
6	N, N-Dimethylformamide	—	—
7	Anhydrous methanol	—	—

Table 2. Photocatalytic oxidation of benzalcohol oxidations in different solvents

Entry	Substrate	Product	Con.^b/%	Sel.^b/%
^a Conditions: substrate (0.2 mmol), 12Eu-ZnO/MIL-53(Fe) (5 mg), CCl₄ (6 mL), visible light illumination, 9 h. ^b Calculated by GC analysis.
1			56	81
2			82	98
3			56	94
4			26	＞99
5			21	90
6			37	92
7			75	96
8			75	100
9			9	90
10			77	100
11			30	100

Table 3. Photocatalytic oxidation of benzalcohol derivatives catalyzed by 12Eu-ZnO/MIL-53(Fe) under visible light

Figure 8. Effect of different active species capture agents on photocatalytic oxidation of benzalcohol by 12Eu-ZnO/MIL-53(Fe)

Figure 9. Mott-Schottky plot (M-S) of the samples

Figure 10. Cyclic results of 12Eu-ZnO/MIL-53(Fe) composites in the oxidation of benzalcohol

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Eu掺杂的ZnO/MIL-53(Fe)光催化剂的合成及其对醇类选择性氧化的催化性能研究

Preparation of Eu-Doped ZnO/MIL-53(Fe) Photocatalyst and Its Catalytic Performance for Selective Oxidation of Alcohols

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