铈掺杂磷酸银/卟啉复合光催化剂降解螺旋霉素的研究

张延霖; 范燕平; 高欣; 牛静

doi:10.6054/j.jscnun.2023037

铈掺杂磷酸银/卟啉复合光催化剂降解螺旋霉素的研究

doi: 10.6054/j.jscnun.2023037

张延霖^1, ,,
范燕平²,
高欣¹,
牛静¹

1.
华南师范大学环境学院, 广州 510006
2.
华南师范大学化学学院, 广州 510006

基金项目:

国家自然科学基金项目 51578249

广东省自然科学基金项目 2022A1515011256

详细信息

通讯作者:
张延霖, Email: zhangyl@scnu.edu.cn

中图分类号: O626.13
计量
- 文章访问数: 32
- HTML全文浏览量: 2
- PDF下载量: 2
- 被引次数: 0
出版历程
- 收稿日期: 2022-01-20
- 网络出版日期: 2023-08-26
- 刊出日期: 2023-06-25

The Research on the Degradation of Spiramycin by Cerium-doped Silver Phosphate/Porphyrin Composite Photocatalyst

1.
School of Environment, South China Normal University, Guangzhou 510006, China
2.
School of Chemistry, South China Normal University, Guangzhou 510006, China

摘要

摘要: 通过与5, 10, 15, 20-四(4-羧基苯基)卟啉(TCPP)复合，构筑了Ce-Ag₃PO₄/TCPP异质结复合催化剂，研究其对螺旋霉素(SPM)的催化降解性能。采用SEM、XRD、XPS、UV-Vis DRS和FTIR等方法表征和剖析催化剂材料的微观化学结构、化学组成及光化学性能，并进一步阐明光催化降解SPM的反应机理。Ce-Ag₃PO₄/TCPP光催化剂在可见光照射6 h对SPM的降解率为87.7%，降解速率常数是纯Ag₃PO₄的5.8倍。光电化学测量(光电流响应、电化学阻抗)、ESR测试、自由基捕获和PL光谱分析结果表明：铈离子(Ce³⁺)的掺杂，可有效增大催化剂的比表面积，减少电子-空穴对的复合；引入TCPP能加速电子转移，增强光吸收性能，从而提高光催化活性。这种掺杂复合催化剂为高效光降解SPM提供了一种简捷和高效的途径。
- 磷酸银 /
- 螺旋霉素 /
- 铈 /
- 掺杂 /
- 光催化降解
Abstract: A Ce-Ag₃PO₄/TCPP heterojunction composite catalyst was constructed by combining with 5, 10, 15, 20-tetra (4-carboxylphenyl) porphyrin (TCPP) to investigate its catalytic degradation performance for Spiramycin (SPM). Using SEM, XRD, XPS, UV-Vis DRS and FTIR methods to characterize and analyze the microchemical structure, chemical composition and photochemical properties of the catalysts and further clarify the reaction mechanism of SPM photocatalytic degradation. The Ce-Ag₃PO₄/TCPP photocatalyst has a degradation ratio of 87.7% for SPM under visible light irradiation for 6 h, and the degradation rate constant is 5.8 times that of pure Ag₃PO₄. Photoelectrochemical measurements (photocurrent response, electrochemical impedance), ESR test, radical trapping, and PL spectral analysis results show that the doping of cerium ions (Ce³⁺) can effectively increase the specific surface area of the catalyst and reduce the recombination of electron-hole pairs; the introduction of TCPP can accelerate electron transfer and enhance light absorption performance, thereby enhancing the photocatalytic activity. This doped composite catalyst provides a simple and efficient route for efficient photodegradation of SPM.
- silver phosphate /
- spiramycin /
- cerium /
- doping /
- photocatalytic degradation

HTML全文

图 1 不同催化剂的表征

Figure 1. The characterization of different catalysts

下载: 全尺寸图片幻灯片

图 2 样品的SEM图

Figure 2. The SEM images of samples

下载: 全尺寸图片幻灯片

图 3 Ce-Ag₃PO₄和Ce-Ag₃PO₄/TCPP的XPS谱

Figure 3. The XPS spectra of Ce-Ag₃PO₄ and Ce-Ag₃PO₄/TCPP

下载: 全尺寸图片幻灯片

图 4 Ag₃PO₄、Ce-Ag₃PO₄、TCPP和Ce-Ag₃PO₄/TCPP的红外光谱

Figure 4. The FTIR spectra of Ag₃PO₄, Ce-Ag₃PO₄, TCPP, and Ce-Ag₃PO₄/TCPP

下载: 全尺寸图片幻灯片

图 5 不同样品的UV-Vis DRS谱

Figure 5. The UV-Vis DRS spectra of different samples

下载: 全尺寸图片幻灯片

图 6 催化剂的荧光发射光谱

Figure 6. The fluorescence emission spectra of catalysts

下载: 全尺寸图片幻灯片

图 7 SPM的光催化降解曲线

Figure 7. The curves of photocatalytic degradation for SPM

下载: 全尺寸图片幻灯片

图 8 不同催化剂降解SPM的TOC去除率

Figure 8. The TOC degradation removal rate of SPM with different catalysts

下载: 全尺寸图片幻灯片

图 9 Ag₃PO₄和Ce-Ag₃PO₄/TCPP在可见光下降解SPM的循环性能

Figure 9. The recyclability performance of photocatalytic degradation of SPM by Ag₃PO₄ and Ce-Ag₃PO₄/TCPP under visible light irradiation

下载: 全尺寸图片幻灯片

图 10 Ce-Ag₃PO₄/TCPP在可见光下降解SPM过程中的自由基捕获曲线

Figure 10. The curves of photogenerated reactive species trap of SPM degradation by Ce-Ag₃PO₄/TCPP under visible light

下载: 全尺寸图片幻灯片

图 11 可见光照射前后Ce-Ag₃PO₄和Ce-Ag₃PO₄/TCPP的ESR波谱

Figure 11. The ESR spectra of Ce-Ag₃PO₄ and Ce-Ag₃PO₄/TCPP before and after visible light irradiation

下载: 全尺寸图片幻灯片

图 12 光催化剂的光电转化性能

Figure 12. The photoelectric conversion performance of photocatalysts

下载: 全尺寸图片幻灯片

图 13 可见光催化降解机制

Figure 13. The mechanism of photo-degradation under visible light irradiation

下载: 全尺寸图片幻灯片

参考文献(30)

[1]	常海莎, 闫豫君, 鲁建江, 等. 螺旋霉素在水溶液中的光降解[J]. 环境化学, 2018, 37(6): 1343-1350. https://www.cnki.com.cn/Article/CJFDTOTAL-HJHX201806019.htm CHANG H S, YAN Y J, LU J J, et al. Photodegradation of spiramycin in aqueous solution[J]. Environmental Chemistry, 2018, 37(6): 1343-1350. https://www.cnki.com.cn/Article/CJFDTOTAL-HJHX201806019.htm
[2]	魏晓东, 刘叶新, 周志洪, 等. 广州典型排放源废水中抗生素的污染特征和去除效果[J]. 华南师范大学学报(自然科学版), 2018, 50(1): 11-20. doi: 10.6054/j.jscnun.2018010 WEI X D, LIU Y X, ZHOU Z H, et al. Occurrence and removal of antibiotics from wastewater of typical emission sources in Guangzhou, China[J]. Journal of South China Normal University (Natural Science Edition), 2018, 50(1): 11-20. doi: 10.6054/j.jscnun.2018010
[3]	ZHANG L W, ZHU Y F. A review of controllable synthesis and enhancement of performances of bismuth tungstate visible-light-driven photocatalysts[J]. Catalysis Science & Technology, 2012, 2(4): 694-706.
[4]	BI Y P, OUYANG S X, UMEZAWA N, et al. Facet effect of single-crystalline Ag₃PO₄ sub-microcrystals on photocatalytic properties[J]. Journal of the American Chemical Society, 2011, 133(17): 6490-6492. doi: 10.1021/ja2002132
[5]	YI Z G, YE J H, KIKUGAWA N K, et al. An orthophosphate semiconductor with photooxidation properties under visible-light irradiation[J]. Nature Materials, 2010, 9(7): 559-564. doi: 10.1038/nmat2780
[6]	刘一鸣, 张曦, 陈芳艳, 等. Ag₃PO₄/Bi₂O₃异质结光催化剂的制备及其光催化性能研究[J]. 江苏科技大学学报(自然科学版), 2019, 33(5): 89-96. https://www.cnki.com.cn/Article/CJFDTOTAL-HDCB201905014.htm LIU Y M, ZHANG X, CHEN F Y, et al. Preparation and photocatalytic activity of heterojunction-structured photocatalysts Ag₃PO₄/Bi₂O₃[J]. Journal of Jiangsu University of Science and Technology (Natural Science Edition), 2019, 33(5): 89-96. https://www.cnki.com.cn/Article/CJFDTOTAL-HDCB201905014.htm
[7]	郭玉玮, 刘旭东, 赵建军, 等. 原位化学沉积法制备AgBr/Ag₃PO₄光催化剂及其催化性能[J]. 石油学报(石油加工), 2020, 36(3): 484-491. https://www.cnki.com.cn/Article/CJFDTOTAL-SXJG202003008.htm GUO Y W, LIU X D, ZHAO J J, et al. Preparation of AgBr/Ag₃PO₄ composite photocatalyst by in-situ chemical deposition and its photocatalytic performance[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2020, 36(3): 484-491. https://www.cnki.com.cn/Article/CJFDTOTAL-SXJG202003008.htm
[8]	TUDISCO C, PULVIRENTI L, COOL P, et al. Porphyrin functionalized bismuth ferrite for enhanced solar light photocatalysis[J]. Dalton Transactions, 2020, 49(25): 8652-8660. doi: 10.1039/C9DT04514G
[9]	HUANG Y, ZHAO P, MIAO H C, et al. Organic-inorganic TCPP/BiOCl hybrids with accelerated interfacial charge separation for boosted photocatalytic performance[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 616: 126367/1-12.
[10]	MARZIEH Y B, BAHRAM B, SOLMAZ Z. Synthesis, characterization, and design of a photocatalyst based on BiOBr nanoplates and tin porphyrin with enhanced visible light photocatalytic activity[J]. Research on Chemical Intermediates, 2020, 46(1): 197-213. doi: 10.1007/s11164-019-03943-9
[11]	袁潮苇. La掺杂光催化剂的制备及净化空气中NO的反应机理研究[D]. 重庆: 重庆工商大学, 2021. YUAN C W. Investigation ofphotocatalytic no oxidation and reaction mechanism via La doping in photocatalyst[D]. Chongqing: Chongqing Technology and Business University, 2021.
[12]	ZHANG Y, SUN A, SUONAN Z, et al. Effect of rare-earth (Sm, Ce, and La) ions doping on the lattice structure and magnetic properties of Zn-Ba-Co ferrites by sol-gel auto-combustion method[J]. Journal of Materials Science: Materials in Electronics, 2021, 32(12): 16505-16518. doi: 10.1007/s10854-021-06207-8
[13]	GUO Q, LI H, ZHANG Q, et al. Fabrication, characterization and mechanism of a novel Z-scheme Ag₃PO₄/NG/Polyimide composite photocatalyst for microcystin-LR degradation[J]. Applied Catalysis B: Environmental, 2018, 229: 192-203. doi: 10.1016/j.apcatb.2018.02.023
[14]	XU H, WANG C, SONG Y, et al. CNT/Ag₃PO₄ composites with highly enhanced visible light photocatalytic activity and stability[J]. Chemical Engineering Journal, 2014, 241(4): 35-42.
[15]	BORJIGIN B, DING L, LI H Q, et al. A solar light-induced photo-thermal catalytic decontamination of gaseous benzene by using Ag/Ag₃PO₄/CeO₂ heterojunction[J]. Chemical Engineering Journal, 2020, 402: 126070/1-14.
[16]	GAO H Y, WANG J Y, JIA M Y, et al. Construction of TiO₂ nanosheets/tetra (4-carboxyphenyl) porphyrin hybrids for efficient visible-light photoreduction of CO₂[J]. Chemical Engineering Journal, 2019, 34: 684-693.
[17]	李德芝. 金属卟啉框架、铜/碳材料的合成及性质研究[D]. 大连: 大连理工大学, 2020. LI D Z. Synthesis of metal-porphyrin framework and Cu/C composites for their photothermal and electrocatalytic properties[D]. Dalian: Dalian University of Technology, 2020.
[18]	KOBAYASHI T, KUROKAWA F, UYEDA N. The metal-ligand vibrations in the infrared spectra of various metal phthalocyanines[J]. Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy, 1970, 26(6): 1305-1311. doi: 10.1016/0584-8539(70)80036-8
[19]	曾锦萍, 袁晓玲, 邓记华. 若干5, 10, 15, 20-四(4-羧基苯基)卟啉金属配合物的合成与表征[J]. 宜春学院学报, 2010, 32(4): 14-17. https://www.cnki.com.cn/Article/CJFDTOTAL-YCSB201004005.htm ZENG J P, YUAN X L, DENG J H. Synthesis and characterization of some metallic(Ⅱ) complexes with 5, 10, 15, 20-tetra (4-carboxyphenyl) porphyrin ligand[J]. Journal of Yichun College, 2010, 32(4): 14-17. https://www.cnki.com.cn/Article/CJFDTOTAL-YCSB201004005.htm
[20]	LIN P Y, SHEN J, PRASAD C, et al. The synergetic effect of carbon nanotubes and MoS₂ as co-catalysts for enhancing the photocatalytic oxygen evolution of Ag₃PO₄[J]. Ceramics International, 2019, 45(17): 21120-21126. doi: 10.1016/j.ceramint.2019.07.088
[21]	李向源. 基于5, 10, 15, 20-四(4-羧基苯基)卟啉桥联配体的纳米MOFs的合成及性能研究[D]. 济南: 山东师范大学, 2018. LI X Y. Synthesis and properties of nano MOFs based on 5, 10, 15, 20-tetra (4-carboxyphenyl) porphyrin bridging ligand[D]. Jianan: Shandong Normal University, 2018.
[22]	梅光泉, 袁晓玲, 曾锦萍. 5, 10, 15, 20-四(4-羧基苯基)卟啉及其钯(Ⅱ)配合物的合成与表征[J]. 化学试剂, 2008, 11: 809-812;815. https://www.cnki.com.cn/Article/CJFDTOTAL-HXSJ201104005.htm MEI G Q, YUAN X L, ZENG J P. Study on simultaneous determination of pyrocatechol, resorcinol and hydroquinone by supporting vector regression robust modeling[J]. Chemical Reagents, 2008, 11: 809-812;815. https://www.cnki.com.cn/Article/CJFDTOTAL-HXSJ201104005.htm
[23]	曾锦萍, 梅光泉, 刘万云, 等. 5, 10, 15, 20-四(4-羧基苯基)卟啉铂(Ⅱ)配合物的合成与热谱研究[J]. 宜春学院学报, 2009, 31(2): 1-3. https://www.cnki.com.cn/Article/CJFDTOTAL-YCSB201004006.htm ZENG J P, MEI G Q, LIU W Y. Study on synthesis and thermograms of platinum (Ⅱ) complex with 5, 10, 15, 20-tetra (4-carboxyphenyl) porphyrin ligand[J]. Journal of Yichun College, 2009, 31(2): 1-3. https://www.cnki.com.cn/Article/CJFDTOTAL-YCSB201004006.htm
[24]	CHEN L, MA W, DAI J D, et al. Facile synthesis of highly efficient graphitic-C₃N₄/ZnFe₂O₄ heterostructures enhanced visible-light photocatalysis for spiramycin degradation[J]. Journal of Photochemistry and Photobiology A-Chemistry, 2016, 328: 24-32. doi: 10.1016/j.jphotochem.2016.04.026
[25]	CHICHE D, SCHWEITZER J M. Investigation of competitive COS and HCN hydrolysis reactions upon an industrial catalyst: Langmuir-Hinshelwood kinetics modeling[J]. Applied Catalysis B: Environmental, 2017, 205: 189-200. doi: 10.1016/j.apcatb.2016.12.002
[26]	CHEN S F, LEI J, TANG W M, et al. Fabrication, characterization and mechanism of a novel Z-scheme photocatalyst NaNbO₃/WO₃ with enhanced photocatalytic activity[J]. Dalton Transactions, 2013, 42(30): 10759-10768. doi: 10.1039/c3dt50699a
[27]	GUO X Y, LI X Q, QIN L X, et al. A highly active nano-micro hybrid derived from Cu-bridged TiO₂/porphyrin for enhanced photocatalytic hydrogen production[J]. Applied Catalysis B: Environmental, 2019, 243: 1-9. doi: 10.1016/j.apcatb.2018.10.030
[28]	CHEN C, MA W, ZHAO J. Semiconductor-mediated photodegradation of pollutants under visible-light irradiation[J]. Chemical Society Reviews, 2010, 39: 4206-4219. doi: 10.1039/b921692h
[29]	XU D F, CHENG B, CAO S W, et al. Enhanced photocatalytic activity and stability of Z-scheme Ag₂CrO₄-GO composite photocatalysts for organic pollutant degradation[J]. Applied Catalysis B: Environmental, 2015, 164(5): 380-388.
[30]	CHEN F, YANG Q, LI X M, et al. Hierarchical assembly of graphene-bridged Ag₃PO₄/Ag/BiVO₄ (040) Z-scheme photocatalyst: an efficient, sustainable and heterogeneous catalyst with enhanced visible-light photoactivity towards tetracycline degradation under visible light irradiation[J]. Applied Catalysis B: Environmental, 2017, 200: 330-334.