MoO<sub>3</sub>-Cu<sub>2</sub>O/CN三相复合光催化剂的制备及其降解四环素性能

崔春丽; 郝振华; 舒永春

MoO₃-Cu₂O/CN三相复合光催化剂的制备及其降解四环素性能

崔春丽^{1, 2},
郝振华^{1, 2, ,},
舒永春^{1, 2}

1.
材料科学与工程学院郑州大学, 郑州450001
2.
中原关键金属实验室, 郑州450001

基金项目: 中原关键实验室项目 (GJJSGFYQ202302和GJJSGFZD202303)

详细信息

通讯作者:
郝振华，博士，副教授，硕士生导师，研究方向等离子球化；特种粉体材料；金属3D打印　E-mail: zh_hao@zzu.edu.cn

中图分类号: TB331
计量
- 文章访问数: 43
- HTML全文浏览量: 53
- 被引次数: 0
出版历程
- 收稿日期: 2024-04-11
- 修回日期: 2024-06-02
- 录用日期: 2024-06-08
- 网络出版日期: 2024-06-26

Preparation and tetracycline degradation performance of MoO₃-Cu₂O/CN ternary photocatalyst

CUI Chunli^{1, 2},
HAO Zhenhua^{1, 2
, ,},
SHU Yongchun^{1, 2}

1.
School of Material Science and Engineering, Zhengzhou University, Zhengzhou 450001, China
2.
Zhongyuan Critical Metals Laboratory, Zhengzhou 450001, China

Funds: Project of Zhongyuan Critical Metals Laboratory (GJJSGFZD202303 and GJJSGFYQ202302).

摘要

摘要: 本文通过水热法先在g-C₃N₄(CN)上原位生长MoO₃，继而在其表面电沉积Cu₂O构建了MoO₃-Cu₂O/CN三相复合光催化剂。采用XRD、SEM、TEM、XPS和FTIR等手段对催化剂进行表征，证明了复合光催化剂的成功制备。以四环素为目标污染物，探究了所制备光催化剂对四环素的降解效果及光催化剂的作用机制。结果表明，在可见光下，1.5 MoO₃-Cu₂O-100/CN复合材料对四环素的降解效果最佳，150 min时降解率为97.75%，分别是CN(45.28%)和1.5 MoO₃/CN(63.24%)的2.2和1.5倍。采用自由基捕获实验及电子顺磁共振光谱(EPR)对机制进行了探究，证实了羟基自由基(·OH)和超氧自由基(·O₂⁻)是光催化过程的主要活性物质。综合各项测试计算 CN、MoO₃ 和Cu₂O 的价带和导带位置，表明三相复合光催化剂形成了双Z型异质结。同时光催化活性的提高主要归因于双Z机制的构建，拓宽了可见光吸收范围，保留了氧化还原能力较高的空穴电子，降低了光生电子与空穴的复合率。稳定性实验结果表明制备的催化剂在经过四次循环后，对四环素的降解率仍达到90%以上，具有优异的稳定性，可循环使用。
- MoO₃-Cu₂O/CN /
- 双Z机制 /
- 四环素 /
- 降解 /
- 光催化
Abstract: In this paper, MoO₃ was in-situ grown on g-C₃N₄ (CN) by hydrothermal method, followed by the electrodeposition of Cu₂O to construct a ternary MoO₃-Cu₂O/CN composite photocatalyst. The catalyst was characterized by XRD, SEM, TEM, XPS and FTIR, which proved the successful preparation of the composite photocatalyst. Taking tetracycline as the target pollutant, the degradation effect of the prepared photocatalyst on tetracycline and the action mechanism of the photocatalyst were investigated. The results showed that 1.5 MoO₃-Cu₂O-100/CN composite had the best degradation effect of tetracycline at 150 min under visible light, up to 97.75%. They are 2.2 and 1.5 times of CN (45.28%) and 1.5 MoO₃/CN (63.24%) respectively. The mechanism was investigated by free radical capture experiment and electron paramagnetic resonance spectroscopy (EPR). It was confirmed that hydroxyl radical (·OH) and superoxide radical (·O₂⁻) were the main active substances in the photocatalytic process. The valence band and conduction band positions of CN, MoO₃, and Cu₂O are calculated based on various tests. It is shown that the double Z-type heterojunction is formed by the ternary composite photocatalyst. At the same time, the improvement of photocatalytic activity is mainly due to the construction of double Z mechanism, which widens the visible light absorption range, retains the hole electrons with high REDOX ability, and reduces the recombination rate of photogenerated electrons and holes. The results of stability test show that the catalytic degradation rate of tetracycline is still over 90% after four cycles, which has excellent stability and can be recycled.The results of stability test show that the catalytic degradation rate of tetracycline is still over 90% after four cycles, which has excellent stability and can be recycled.
- MoO₃-Cu₂O/CN /
- dual Z-scheme /
- tetracycline /
- degradation /
- photocatalytic

HTML全文

图 1 MoO₃-Cu₂O/ g-C₃N₄(CN)光催化剂的制备过程示意图

Figure 1. Schematic diagram of the preparation of MoO₃-Cu₂O/ g-C₃N₄ (CN) photocatalysts

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图 2 CN、1.5MoO₃/CN和1.5MoO₃-Cu₂O-100/CN催化剂的 (a) XRD图谱和 (b) FT-IR图

Figure 2. (a) XRD patterns and (b) FTIR spectra of CN, 1.5MoO₃/CN and 1.5MoO₃-Cu₂O-100/CN catalysts

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图 3 (a) CN，(b) MoO₃，(c) 1.5MoO₃/CN和 (d) 1.5MoO₃-Cu₂O-100/CN的SEM图像

Figure 3. SEM images of (a) CN, (b) MoO₃, (c) 1.5MoO₃/CN and (d) 1.5MoO₃-Cu₂O -100/CN

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图 4 (a) 1.5MoO₃-Cu₂O-100/CN的TEM图像, (b) 1.5MoO₃-Cu₂O-100/CN的STEM-EDX图像以及(c) 显示了C、N、O、Mo和Cu的元素分布图

Figure 4. (a) 1.5MoO₃-Cu₂O-100/CN; (b) TEM images of 1.5MoO₃-Cu₂O-100/CN and (c) STEM-EDX images of 1.5MoO₃-Cu₂O-100/CN showing the element distribution mappings of C, N, O, Mo and Cu

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图 5 1.5MoO₃-Cu₂O-100/CN催化剂中 (a) C，(b) N，(c) O，(d) Mo和 (e) Cu元素的高分辨率XPS光谱

Figure 5. High-resolution XPS spectra of (a) C, (b) N, (c) O, (d) Mo and (e) Cu in 1.5MoO₃-Cu₂O-100/CN catalyst

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图 6 (a) CN、1.5MoO₃/CN和1.5MoO₃-Cu₂O-100/CN的UV -Vis DRS图。由Tauc计算出的 (b) CN, 1.5MoO₃/CN和1.5MoO₃-Cu₂O-100/CN的带隙

Figure 6. UV-Vis-DRS of (a) CN, 1.5MoO₃/CN and 1.5MoO₃-Cu₂O-100/CN. Calculated band gap from the Tauc plot of (b) CN, 1.5MoO₃/CN and1.5MoO₃-Cu₂O-100/CN

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图 7 (a) 不同光催化剂对四环素的 (a) 降解曲线, (b) 一级动力学曲线，(c) 降解速率常数 (k, min⁻¹), (d) 不同MoO₃含量的四环素光降解效率

Figure 7. (a) Tetracycline degradation curves, (b) first-order kinetics curves, and (c) degradation rate constants (k, min⁻¹) of different photocatalysts,(d) Tetracycline photo-degradation efficiency of with different MoO₃ contents

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图 8 (a) 初始四环素浓度；(b)溶液pH值对1.5MoO₃-Cu₂O-100/CN光催化剂降解四环素的影响

Figure 8. Effects of (a) initial tetracycline concentration; (b) solution pH on the degradation of tetracycline in the presence of 1.5MoO₃-Cu₂O-100/CN photocatalyst

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图 9 (a) 1.5MoO₃-Cu₂O-100/CN对四环素降解的四次稳定性循环测试和降解四环素前后的XRD图谱

Figure 9. (a) Four cycling tests of tetracyclinphotocatalytic degradation with 1.5MoO₃-Cu₂O-100/CN and (b) before and after photocatalytic degradation of tetracycline

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图 10 (a) 1. MoO₃-Cu₂O-100/CN在不同清除剂存在下对四环素的降解曲线, (b) DMPO-捕获·OH和 (c) ·O₂⁻与1.5MoO₃-Cu₂O-100/CN复合材料的EPR光谱

Figure 10. (a) Degradation curve of tetracycline by 1.5MoO₃-Cu₂O-100/CN in the presence of different scavengers, EPR spectra of (b) DMPO⁻ to capture ·OH and (c)·O₂⁻ with 1.5MoO₃-Cu₂O-100/CN composite

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图 11 CN、1.5MoO₃/CN和1.5MoO₃-Cu₂O-100/CN样品的 (a) PL光谱，(b) 瞬态光电流响应和 (c) EIS谱图

Figure 11. (a) PL spectra, (b) transient photocurrent responses, (c) EIS of CN, 1.5MoO₃/CN and 1.5MoO₃-Cu₂O-100/CN samples

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图 12 不同MoO₃含量下样品的(a) 瞬态光电流响应和 (b) EIS谱图

Figure 12. (a) Transient photocurrent responses and (b) EIS of the samples with different MoO₃ contents

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图 13 (a) MoO₃和 (b) Cu₂O样品的(αhν)²对hν的曲线；(c) CN, (d) MoO₃和 (e) Cu₂O的XPS价带谱

Figure 13. (αhν)² vs radiation energy (hv) plots for (a) MoO₃ and (b) Cu₂O samples. Valence-band XPS spectrum of the sample (c) CN; (d) MoO₃ and(e) Cu₂O

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图 14 1.5MoO₃-Cu₂O-100/CN复合催化剂的反应机制

Figure 14. Possible reaction mechanism of 1.5MoO₃-Cu₂O-100/CN composite catalyst

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图 15 1.5MoO₃-Cu₂O-100/CN 催化剂降解四环素的路径示意图

Figure 15. Tetracycline degradation pathway by 1.5MoO₃-Cu₂O-100/CN catalyst

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[1]	LEON S, Li D, HAPGOOG K, et al. Ni(OH)₂ decorated rutile TiO₂ for efficient removal of tetracycline from wastewater[J]. Applied Catalysis B Environmental, 2016, 198: 224-233. doi: 10.1016/j.apcatb.2016.05.043
[2]	熊维, 李奥祥, 谢金玺, 等. 氮掺杂的硫化镉锌光催化降解水中抗生素[J]. 中国环境科学, 2024, 44(1): 499-509. XIONG Wei, LI Aoxiang, XIE Jinxi, et al. Photocatalytic degradation of antibiotics by Nitrogen-doped Zinc cadmium sulfide[J]. China Environmental Science 2024, 44(1): 499-509(in Chinese).
[3]	ZHI D, WANG J B, ZHOU Y Y, et al. Development of ozonation and reactive electrochemical membrane coupled process: enhanced tetracycline mineralization and toxicity reduction[J]. Chemical Engineering Journal, 2020, 283: 123149.
[4]	尹泽, 高博熠, 刘愿强, 等. 花状 g-C₃N₄/Pd/Bi₂WO₆光催化剂协同降解苯扎贝特机制研究[J]. 中国环境科学, 2024. YIN Ze, GAO Yibo, LIU Yuanqiang, et al. Study on Flower-like g-C₃N₄/Pd/Bi₂WO₆ Heterostructure and Its Synergistic Degradation Mechanism of Bezafibrate[J]. China Environmental Science, 2024(in Chinese).
[5]	WU Y, WANG H, TU W G, et al. Effects of composition faults in ternary metal chalcogenides (Zn_xIn₂S_3+x, x=1-5) layered crystals for visible light-driven catalytic hydrogen generation and carbon dioxide reduction[J]. Applied Catalysis B Environmental, 2019, 256: 117810. doi: 10.1016/j.apcatb.2019.117810
[6]	ZHANG J J, WANG H, YUAN X Z, et al. Tailored indium sulfide-based materials for solar-energy conversion and utilization[J]. Journal of Photochemistry and Photobiology C: Photochemistry, Review, 2019, 38: 1-26. doi: 10.1016/j.jphotochemrev.2018.11.001
[7]	LIU Q, GUO Y R, CHEN Z C, et al. Constructing a novel ternary Fe(III)/graphene/g-C₃N₄ composite photocatalyst with enhanced visible-light driven photocatalytic activity via interfacial charge transfer effect[J]. Applied Catalysis B Environmental, 2016, 183: 231-241. doi: 10.1016/j.apcatb.2015.10.054
[8]	HE F, WANG Z X, LI Y X, et al. The nonmetal modulation of composition and morphology of g-C₃N₄-based photocatalysts[J]. Applied Catalysis B: Environmental, 2020, 269: 118828. doi: 10.1016/j.apcatb.2020.118828
[9]	刘权锋, 彭炜东, 钟承韡, 等. g-C₃N₄-Ag/SiO₂ 复合材料光催化降解甲醛的应用[J]. 复合材料学报, 2022, 39(2): 628-636. LIU Quanfeng, PENG Weidong, ZHONG Chengwei, et al. Application of photocatalytic degradation of formaldehyde by g-C₃N₄-Ag/SiO₂ heterostructure composites[J]. Acta Materiae Compositae Sinica, 2022, 39(2): 628-636(in Chinese).
[10]	王晓爽, 李育珍, 易思远, 等. Bi₂MoS₂O₄ 改性 g-C₃N₄ 光催化降解罗丹明B[J]. 复合材料学报, 2022, 39(8): 3845-3851. WANG Xiaoshuang, LI Yuzhen, YI Siyuan, et al. Bi₂MoS₂O₄ modified g-C₃N₄ photocatalytic degradation of Rhodamine B[J]. Acta Materiae Compositae Sinica, 2022, 39(8): 3845-3851(in Chinese).
[11]	TANG M L, AO Y H, WANG C, et al. Facile synthesis of dual Z-scheme g-C₃N₄/Ag₃PO₄/AgI composite photocatalysts with enhanced performance for the degradation of a typical neonicotinoid pesticide[J]. Applied Catalysis B Environmental, 2020, 268: 118395 doi: 10.1016/j.apcatb.2019.118395
[12]	ZHAO G S, DING J, ZHOU F Y, et al. Construction of a visible-light-driven magnetic dual Z-scheme BiVO₄/g-C₃N₄/NiFe₂O₄ photocatalyst for effective removal of ofloxacin: mechanisms and degradation pathway[J]. Chemical Engineering Journal, 2021, 384: 126704.
[13]	Alex K, Aarya Prabhakaran A, Jayakrishnan K, et al. Charge coupling enhanced photocatalytic activity of BaTiO₃/MoO₃ heterostructures[J]. ACS Applied Materials Interface, 2019, 11(43): 40114-40124. doi: 10.1021/acsami.9b14919
[14]	Adhikari S, Lee H, Kim D, et al. Efficient visible-light induced electron-transfer in Z-Scheme MoO₃/Ag/C₃N₄ for excellent photocatalytic removal of antibiotics of both ofloxacin and tetracycline[J]. Chemical Engineering Journal, 2020, 391: 123504. doi: 10.1016/j.cej.2019.123504
[15]	XIE Z J, FENG Y P, WANG F L, et al. Construction of carbon dots modified MoO₃/g-C₃N₄ Z-Scheme photocatalyst with enhanced visible-light photocatalytic activity for the degradation of tetracycline[J]. Applied Catalysis B: Environmental, 2018, 229: 96-104. doi: 10.1016/j.apcatb.2018.02.011
[16]	HU F, ZOU Y Z, WANG L L, et al. Photostable Cu₂O photoelectrodes fabricated by facile Zn-doping electrodeposition[J]. International Journal of Hydrogen Energy, 2016, 34: 15172-15180.
[17]	FATTAHIMOGHADDAM H, MAHVELATI-SHAMSABADI T, LEE B K, Effcient Photodegradation of Rhodamine B and Tetracycline over Robust and Green g-C₃N₄ Nanostructures: Supramolecular Design[J]. Journal of Hazardous Materials, 2021, 403: 123703–123736.
[18]	RAJENDRAN R, VIGNESH S, SASIREKA A, et al. Investigation on novel Cu₂O modified g-C₃N_4/ZnO heterostructures for efficient photocatalytic dye degradation performance under visible-light exposure[J]. Colloid and Interface Science Communications, 2021, 44: 100480.
[19]	WANG F L, CHEN P, FENG Y P, Facile synthesis of N-doped carbon dots/g-C₃N₄ photocatalyst with enhanced visible-light photocatalytic activity for the degradation of indomethacin[J]. Applied Catalysis B Environmental, 2017, 207, 103-113.
[20]	LI X D, FENG Y, LI M C, et al. Smart hybrids of Zn2GeO4 nanoparticles and ultrathin g-C₃N₄ layers: synergistic lithium storage and excellent electrochemical performance[J]. Advanced Functional Materials, 2015, 25: 6858-6866. doi: 10.1002/adfm.201502938
[21]	ADHIKARI S, KIM D-H. Heterojunction C₃N₄/MoO₃ microcomposite for highly efficient photocatalytic oxidation of Rhodamine B[J]. Applied Surface Science, 2020, 511: 145595. doi: 10.1016/j.apsusc.2020.145595
[22]	HOSSAIN M, AI-GAASHANI R, HAMOUD H, et al. Controlled growth of Cu₂O thin films by electrodeposition approach[J]. Materials Science Semicondductor Processing, 2017, 63: 203-211. doi: 10.1016/j.mssp.2017.02.012
[23]	乔瑞泽, 侯斌, 林杰, 等. HCS@TiO₂ 光催化复合材料的制备及其染料降解性能[J]. 复合材料学报, 2024, 41(5): 2527-2538. QIAO Ruize, HOU Bin, LIN Jie, et al. Preparation and degradation dyestuffs performance of HCS@TiO₂ photocatalytic composites[J]. Acta Materiae Compositae Sinica, 2024, 41(5): 2527-2538(in Chinese).
[24]	XIONG J, LI X B, HUANG J T, et al. C₃N₄/rGO@BPQDs high-low junctions with stretching spatial charge separation ability for photocatalytic degradation and H₂O₂ production[J]. Applied Catalysis B Environmental, 2020, 266: 118602. doi: 10.1016/j.apcatb.2020.118602
[25]	申久英, 刘碧雯, 赵宇翔, 等. CuS-Bi₂WO₆/活性纳米碳纤维的制备及其光催化性能[J]. 复合材料学报, 2022, 39(3): 1163-1172. SHEN Jiuying, LIU Bixia, ZHAO Yuxiang, Preparation and photocatalytic properties CuS-Bi₂WO₆/carbon nanofibers composites[J]. Acta Materiae Compositae Sinica, 2022, 39(3): 1163-1172(in Chinese).