Properties and mechanisms of tetracycline photocatalytic degradation by hydrothermal synthesis Ag-SrTiO3 in visible-light

doi:10.16085/j.issn.1000-6613.2018-0499

Abstract

Abstract: Nano-Ag-SrTiO₃ visible-light catalyst was prepared by one-step hydrothermal method. Composition, morphology and structure, visible-light absorption performance of Ag-SrTiO₃ were characterized by X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM), and ultraviolet visible absorption spectra(UV-vis), respectively. Photocatalytic property and stability of Ag-SrTiO₃ in visible-light were studied by tetracycline(TC) degradation experiment, and its degradation mechanism for TC was also investigated by photoluminescence spectra(PL), electron spin resonance(ESR) analysis and free radical capture experiment. The results showed that Ag⁺ could be well doped in SrTiO₃, and the absorption spectra of Ag-SrTiO₃ significantly redshifted compared with pure SrTiO₃. The photocatalytic property of Ag-SrTiO₃ for TC degradation was optimal while the molar ratio of AgNO₃ and Sr(NO₃)₂ was 3%, and its degradation rate could reach 79.63% within 120min, 13 times higher than pure SrTiO₃. Furthermore, TC degradation of Ag-SrTiO₃ showed a good compliance with the pseudo-first-order kinetic model. Ag-SrTiO₃ still had excellent photocatalytic degradation activity after 8 times reuse. Electronics generated in SrTiO₃ was captured by Ag⁺ in Ag-SrTiO₃. The compound probability of electron and hole could be effectively restrained, which resulted in the increase of photocatalytic properties. The main active species of Ag-SrTiO₃ was·O₂^-.

Key words: silver-strontium titanate (Ag-SrTiO₃), nanomaterials, electron spin resonance, visible-light photocatalytic, tetracycline

摘要： 采用一步水热法制备纳米Ag-SrTiO₃可见光催化剂，利用X射线衍射、X射线光电子能谱、扫描电镜和紫外可见光吸收光谱等对Ag-SrTiO₃的组成、形貌及吸光性进行表征，通过对四环素（TC）的降解实验研究了其在可见光下的光催化活性和稳定性，并进一步通过光致发光光谱、电子自旋共振和自由基捕获实验探究了其对TC的降解机制。结果表明，Ag⁺可成功掺杂到SrTiO₃中，且Ag-SrTiO₃的吸收光较纯SrTiO₃明显发生红移；当AgNO₃与Sr（NO₃）₂的摩尔分数为3%时，制备的Ag-SrTiO₃对TC的光降解效果最好，120min内降解率可达79.63%，较纯SrTiO₃提高13倍，光催化降解TC反应过程符合准一级动力学模型，且重复使用8次后仍具有较高光催化活性；Ag-SrTiO₃中Ag⁺捕获了SrTiO₃产生的电子，有效抑制了电子和空穴的复合概率，从而增加其光催化活性，且其主要活性物种为·O₂^–。

关键词: 银-钛酸锶（Ag-SrTiO₃）, 纳米材料, 电子自旋共振, 可见光催化, 四环素

CLC Number:

X703

CAO Lili, JIANG Shanqing, LING Zeyu, WANG Chuqiao, XU Xia, WANG Liping. Properties and mechanisms of tetracycline photocatalytic degradation by hydrothermal synthesis Ag-SrTiO₃ in visible-light[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4500-4508.

曹丽丽, 蒋善庆, 凌泽玉, 汪楚乔, 许霞, 王利平. 水热合成Ag⁺掺杂SrTiO₃可见光催化降解四环素性能和机制[J]. 化工进展, 2018, 37(11): 4500-4508.

References

[1] 黄圣琳, 何势, 魏欣, 等.污水处理厂中四环素类抗生素残留及其抗性基因污染特征研究进展[J]. 化工进展, 2015, 34(6):1779-1785. HUANG Shenglin, HE Shi, WEI Xin, et al.Pollution characteristics of tetracycline residues and tetracycline resistance genes in sewage treatment plants:a review[J]. Chemical Industry and Engineering Progress, 2015, 34(6):1779-1785.
[2] 邰义萍, 莫测辉, 李彦文, 等.广州市某绿色和有机蔬菜基地土壤中四环素类抗生素的含量与分布特征[J].农业环境科学学报, 2014, 33(9):1743-1748. TAI Yiping, MO Cehui, LI Yanwen, et al.Concentrations and distributions of tetracycline antibiotics in soils of green and organic vegetable fields in Guangzhou, China[J]. Journal of Agro- Environment Science, 2014, 33(9):1743-1748.
[3] YU X N, LU Z Y, WU D, et al.Heteropolyacid-chitosan/TiO₂ composites for the degradation of tetracycline hydrochloride solution[J]. Reaction Kinetics Mechanisms & Catalysis, 2014, 111(1):347-360.
[4] BRANDT K K, AMEZQUITA A, BACKHAUS T, et al.Ecotoxicological assessment of antibiotics:a call for improved consideration of microorganisms[J].Environment International, 2015, 85:189-205.
[5] 阿山, 于丹丹, 白杰, 等.环境领域的二氧化钛基光催化剂负载和改性技术研究进展[J].化工进展, 2017, 36(11):4043-4050. A Shan, YU Dandan, BAI Jie, et al.Research progress on loading and modification of TiO₂ based photocatalyst in environmental field[J]. Chemical Industry and Engineering Progress, 2017, 36(11):4043-4050.
[6] PEIRIS C, GUNATILAKE S R, MLANA T E, et al.Biochar based removal of antibiotic sulfonamides and tetracyclines in aquatic environments:a critical review[J].Bioresource Technology, 2017, 246:150-159.
[7] AHMED M J.Adsorption of quinolone, tetracycline, and penicillin antibiotics from aqueous solution using activated carbons:review[J].Environmental Toxicology and Pharmacology, 2017, 50:1-10.
[8] 叶林静, 安小英, 姜韵婕, 等.ZnO/CdS复合光催化剂的制备及降解四环素类抗生素[J].化工进展, 2015, 34(11):3944-3950. YE Linjing, AN Xiaoying, JIANG Yunjie, et al.Preparation of ZnO/CdS composite photocatalyst and its degradability on tetracycline antibiotic[J]. Chemical Industry and Engineering Progress, 2015, 34(11):3944-3950.
[9] 唐旭, 倪良, 韩娟, 等.三元磁性氮化碳复合光催化剂的制备和表征及其在可见光下去除四环素的应用[J].催化学报, 2017, 38(3):447-457. TANG Xu, NI Liang, HAN Juan, et al.Preparation and characterization of ternary magnetic g-C₃N₄ composite photocatalysts for removal of tetracycline under visible light[J].Journal of Catalysis, 2017, 38(3):447-457.
[10] MARTINS A C, CAZETTA A L, PEZOTI O, et al.Sol-gel synthesis of new TiO₂/activated carbon photocatalyst and its application for degradation of tetracycline[J].Ceramics International, 2017, 43(5):4411-4418.
[11] 张钱新, 王枫亮, 谢治杰, 等.掺N碳量子点负载于TiO₂的复合催化剂光解甲芬那酸研究[J].中国环境科学, 2017, 37(8):2930-2940. ZHANG Qianxin, WANG Fengliang, XIE Zhijie, et al.Photocatalytic degradation mechanism of mefenamic acid by N-doped carbon quantum dots loaded on TiO₂[J].China Environmental Science, 2017, 37(8):2930-2940.
[12] LEE M C, WANG C Y, CHEN C C, et al.Visible light active photocatalyst from recycled disposable heating pads[J].Journal of Nanophotonics, 2016, 10(1):016016-016022.
[13] XING G J, ZHAO L X, TAO S, et al.Hydrothermal derived nitrogen doped SrTiO₃ for efficient visible light driven photocatalytic reduction of chromium(Ⅵ)[J].Springerplus, 2016, 5(1):1132-1144.
[14] 陆玲玮, 孙小琴, 汪亚威, 等.钛基钙钛矿型光催化材料的研究进展[J].应用化学, 2017, 34(11):1221-1239. LU Lingwei, SUN Xiaoqin, WANG Yawei, et al.Research progress of titanium-based perovskite photocatalytic materials[J]. Applied Chemistry, 2017, 34(11):1221-1239.
[15] XIE S, OUYANG K.Degradation of refractory organic compounds by photocatalytic fuel cell with solar responsive WO₃/FTO photoanode and air-breathing cathode[J].Journal of Colloid and Interface Science, 2017, 500:220-227.
[16] 贾玉帅, 赵丹, 李名润, 等.基于镧和铬共掺杂钛酸锶产氢光催化剂构建Z机制全分解水体系[J]. 催化学报, 2018(3):421-430. JIA Yushuai, ZHAO Dan, LI Mingrun, et al.La and Cr co-doped SrTiO₃ as an H₂ evolution photocatalyst for construction of a Z-scheme overall water splitting system[J]. Chinese Journal of Catalysis, 2018(3):421-430.
[17] 樊国栋, 张国贤, 冯昕钰, 等.Ce-TiO₂-SiO₂的制备及其光降解罗丹明B的动力学[J].化工进展, 2017, 36(8):3125-3133. FAN Guodong, ZHANG Guoxian, FENG Xinyu, et al.Preparation of Ce-TiO₂-SiO₂ and the kinetics of RHB photodegradation[J]. Journal of Colloid and Interface Science, 2017, 36(8):3125-3133.
[18] MOREIRA M L, LONGO V M, WALDIR A J, et al.Quantum mechanics insight into the microwave nucleation of SrTiO₃ nanospheres[J].Journal of Physical Chemistry C, 2012, 116(46):24792-24808.
[19] 倪磊, 任新苗, 阮坤, 等.SrTiO₃/CaCu₃Ti₄O₁₂复合陶瓷材料的介电性能[J]. 材料科学与工程学报, 2017, 35(5):695-699, 800. NI Lei, REN Xinmiao, RUAN Kun, et al. Dielectric properties of SrTiO₃/CaCu₃Ti₄O₁₂ composite ceramics[J]. Journal of Materials Science and Engineering, 2017, 35(5):695-699, 800.
[20] 罗清威, 冉阿倩, 李凤华, 等.金属有机沉积法制备SrTiO₃薄膜[J].材料与冶金学报, 2011, 10(3):193-197. LUO Qingwei, RAN Aqian, LI Fenghua, et al.Preparation of SrTiO₃ thin films by metal organic deposition method[J].Journal of Materials and Metallurgy, 2011, 10(3):193-197.
[21] 海参威, 李文戈, 尧巍华, 等.表面改性纳米SrTiO₃粉体制备[J].机械工程材料, 2017, 41(4):54-57. HAI Canwei, LI Wenge, RAO Weihua, et al.Preparation of surface modified nano-SrTiO₃ powders[J].Mechanical Engineering Materials, 2017, 41(4):54-57.
[22] 武松, 闫金良, 焦淑娟.Nb掺杂浓度对SrTiO₃的电子结构和光学性能的影响[J].材料科学与工程学报, 2017, 35(2):209-214. WU Song, YAN Jinliang, JIAO Shujuan.Electronic structures and optical properties of Nb doped SrTiO₃ at different concentrations[J].Journal of Materials Science and Engineering, 2017, 35(2):209-214.
[23] WU G, LI P, XU D, et al.Hydrothermal synthesis and visible-light-driven photocatalytic degradation for tetracycline of Mn-doped SrTiO₃ nanocubes[J]. Applied Surface Science, 2015, 333:39-47.
[24] LI X Y, WANG L P, SHI W D, et al.Hydrothermal synthesis and visible-light-driven photodegradation of antibiotics of Bi₂WO₆ nanostructures[J].Fresenius Environmental Bulletin, 2015, 24(4):1549-1557.
[25] 吴国玲.钛酸锶基复合纳米光催化体系构筑及可见光降解抗生素性能研究[D].镇江:江苏大学, 2016. WU Guoling.Fabrication of strontium titanate-based nanocomposite photocatalysts and performance on antibiotic degradation under visible light[D]. Zhenjiang:Jiangsu University, 2016.
[26] LI P, LIU C B, WU G L, et al.Solvothermal synthesis and visible light-driven photocatalytic degradation for tetracycline of Fe-doped SrTiO₃[J]. RSC Advances, 2014, 88(4):47615-47624.
[27] ZHANG C L, HUA H, LIU J L, et al. Enhanced photocatalytic activity of nanoparticle-aggregated Ag-AgX(X=Cl, Br)@TiO₂ microspheres under visible light[J].Nano-Micro Letters, 2017, 9(4):49-61.
[28] 何飞, 李亚林, 胡雪利, 等.SrTiO₃/g-C₃N₄/Bi₂O₃复合物的可见光催化性能[J].硅酸盐学报, 2017, 45(10):1486-1494. HE Fei, LI Yalin, HU Xueli, et al.Synthesis of Bi₂O₃/g-C₃N₄ composites and photodegradation of methylene blue under visible-light irradiation[J].Journal of the Chinese Ceramic Society, 2017, 45(10):1486-1494.
[29] 苏巧智, 韩清珍, 高锦花, 等.过渡金属掺杂锐钛矿TiO₂(101)表面的改性[J]. 物理学报, 2017, 66(6):214-222. SU Qiaozhi, HAN Qingzhen, GAO Jinghua, et al.Modification of transition metal-doped anatase TiO₂(101) surface[J].Chinese Journal of Physics, 2017, 66(6):214-222.
[30] ZHU Z, LU Z Y, WANG D D, et al.Construction of high-dispersed Ag/Fe₃O₄/g-C₃N₄, photocatalyst by selective photo-deposition and improved photocatalytic activity[J]. Applied Catalysis B:Environmental, 2016, 182:115-122.
[31] XIA Y M, HE Z M, LU Y L, et al.Fabrication and photocatalytic property of magnetic SrTiO₃/NiFe₂O₄ heterojunction nanocomposites[J]. RSC Advances, 2018, 8(10):5441-5450.
[32] FU S, DENG B, MA D, et al.Visible-light-driven photocatalytic fuel cell with an Ag-TiO₂ carbon foam ando for simultaneous 4-chlorophenol degradation and energy recovery[J]. ChemEngineering, 2018, 2(2):20-29.
[33] YANG C X, LIU T Y, CHENG Z J, et al.Study on Mn-doped SrTiO₃ with first principle calculation[J].Physica B:Condensed Matter, 2012, 407(5):844-848.
[34] SOFIANOU M V, TASSI M, PSYCHARIS V, et al.Solvothermal synthesis and photocatalytic performance of Mn⁴⁺-doped anatase nanoplates with exposed facets[J]. Applied Catalysis B:Environmental, 2015, 162:27-33.
[35] CHEN F, YANG H, LUO W, et al.Selective adsorption of thiocyanate anions on Ag-modified g-C₃N₄ for enhanced photocatalytic hydrogen evolution[J].Chinese Journal of Catalysis, 2017, 38(12):1990-1998.
[36] FNEG J, LI B, JIANG J L, et al.Visible light accelerated vinyl C-H arylation in Pd-catalysis:application in the synthesis of ortho tetra-substituted vinylarene:atropisomers[J]. Chinese Journal of Chemistry, 2018, 36(1):11-14.
[37] CAO S W, LIU X F, YUAN Y P, et al.Artificial photosynthetic hydrogen evolution over g-C₃N₄ nanosheets coupled with cobaloxime[J].Physical Chemistry Chemical Physics, 2013, 15(42):18363-18366.
[38] 方俊华, 张凯, 张伟, 等.Sb₂O₃/BiOBr复合物的制备及其对RhB的去污作用[J]. 化工进展, 2017, 36(3):1140-1146. FANG Junhua, ZHANG Kai, ZHANG Wei, et al.Preparation of novel Sb₂O₃/BiOBr composite and decontamination of RhB[J]. Chemical Industry and Engineering Progress, 2017, 36(3):1140-1146.
[39] JIN J, YU J G, GUO D P, et al.A hierarchical z-scheme CdS-WO₃ photocatalyst with enhanced CO₂ reduction activity[J].Small, 2015, 11(39):5262-5271.
[40] 蔡伟民, 龙明策.环境光催化材料与光催化净化技术[M].上海:上海交通大学出版社, 2011. CAI Weimin, LONG Mingce. Environmental photocatalytic materials and photocatalytic purification technology[M].Shanghai:Shanghai Jiaotong University Press, 2011.

Properties and mechanisms of tetracycline photocatalytic degradation by hydrothermal synthesis Ag-SrTiO₃ in visible-light

水热合成Ag⁺掺杂SrTiO₃可见光催化降解四环素性能和机制

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	YANG Ying, HOU Haojie, HUANG Rui, CUI Yu, WANG Bing, LIU Jian, BAO Weiren, CHANG Liping, WANG Jiancheng, HAN Lina. Coal tar phenol-based carbon nanosphere prepared by Stöber method for adsorption of CO₂ [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 5011-5018.
[2]	YIN Xinyu, PI Pihui, WEN Xiufang, QIAN Yu. Application of special wettability materials for anti-hydrate-nucleation and anti-hydrate-adhesion in oil and gas pipelines [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4076-4092.
[3]	XU Peiyao, CHEN Biaoqi, KANKALA Ranjith Kumar, WANG Shibin, CHEN Aizheng. Research progress of nanomaterials for synergistic ferroptosis anticancer therapy [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3684-3694.
[4]	XU Chunshu, YAO Qingda, LIANG Yongxian, ZHOU Hualong. Effects of graphene oxide/carbon nanotubes on the properties of several typical polymer materials [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3012-3028.
[5]	ZHANG Chenyu, WANG Ning, XU Hongtao, LUO Zhuqing. Performance evaluation of the multiple layer latent heat thermal energy storage unit combined with nanoparticle for heat transfer enhancement [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2332-2342.
[6]	CHEN Shaohua, WANG Yihua, HU Qiangfei, HU Kun, CHEN Li’ai, LI Jie. Research progress on detection of Cr(Ⅵ) by electrochemically modified electrode [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2429-2438.
[7]	YIN Ming, GUO Jin, PANG Jifeng, WU Pengfei, ZHENG Mingyuan. Deactivation mechanisms and stabilizing strategies for Cu based catalysts in reactions with hydrogen [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1860-1868.
[8]	GE Weitong, LIAO Yalong, LI Mingyuan, JI Guangxiong, XI Jiajun. Preparation and dechlorination kinetics of Pd-Fe/MWCNTs bimetallic catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1885-1894.
[9]	WAN Maohua, ZHANG Xiaohong, AN Xingye, LONG Yinying, LIU Liqin, GUAN Min, CHENG Zhengbai, CAO Haibing, LIU Hongbin. Research progress on the applications of MXene in the fields of biomass based energy storage nanomaterials [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1944-1960.
[10]	SI Yinfang, HU Yujie, ZHANG Fan, DONG Hao, SHE Yuehui. Biosynthesis of zinc oxide nanoparticles and its application to antibacterial [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2013-2023.
[11]	GUO Shuaishuai, CHEN Jinlu, JIN Liangchenglong, TAO Zui, CHEN Xiaoli, PENG Guowen. Research progress of porous aromatic frameworks based on uranium extraction from seawater [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1426-1436.
[12]	CHEN Yi, GUO Yaoli, YE Haixing, LI Yuxuan, NIU Q.Jason. Application of two-dimensional nanomaterials in pervaporation desalination membrane [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1437-1447.
[13]	XUE Bo, YANG Tingting, WANG Xuefeng. Research progress of polyaniline/carbon nanotube gas sensing materials [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1448-1456.
[14]	HAO Xubo, NIU Baolian, GUO Haotian, XU Xianghe, ZHANG Zhongbin, LI Yinglin. Modification of microencapsulated phase change material and its utilization in photothermal conversion [J]. Chemical Industry and Engineering Progress, 2023, 42(2): 854-871.
[15]	HU Jinjian, LI Long, DONG Zijing. Application of carbon nanomaterials in PU yarn-based flexible strain sensors [J]. Chemical Industry and Engineering Progress, 2023, 42(2): 872-883.