Preparation and photo-electrocatalytic performance of Ag-Ti3+-TiO2 nanocone

doi:10.19965/j.cnki.iwt.2023-0173

Abstract

Abstract:

The overuse of antibiotics has caused persistent pollution to the environment，and photo-electrocatalysis is an environmentally friendly and efficient technology for degrading antibiotics，in which the design of photoelectrodes is particularly important. To improve the rate of antibiotic degradation，Ag-Ti³⁺-TiO₂ nanocone composite photoelectrode was prepared by electrochemical reduction and photoreduction methods. Then it was used to simulate the photo-electrocatalytic degradation of tetracycline under visible light irradiation to investigate its photocatalytic performance. The results showed that the composite electrode effectively suppressed the complexation of photogenerated electron-hole pairs and exhibited a lower charge transfer resistance to improve the photo-electrocatalytic performance due to the Ti³⁺ self-doping and the local surface plasmon resonance effect of Ag nanoparticles. The composite photoelectrode degraded 87.9% of tetracycline after 90 min under visible light irradiation，and the degradation rate was maintained at 82.5% after 5 cycles. These results indicated that the Ag-Ti³⁺-TiO₂ nanocone composite photoelectrode had high degradation efficiency，good stability and sustainable recyclability，and was expected to achieve efficient and environmentally friendly photo-electrocatalytic degradation of antibiotics.

Key words: photo-electrocatalysis, TiO₂, tetracycline, visible light

摘要：

抗生素的过度使用对环境造成了持久性的污染，光电催化是降解抗生素的环保、高效技术，其中光电极的设计尤为重要。为提高抗生素降解速率，采用电化学还原和光还原法制备了Ag-Ti³⁺-TiO₂纳米锥复合光电极，并用于模拟可见光照射下光电催化降解四环素的过程，考察其光电催化性能。结果表明，由于Ti³⁺自掺杂和Ag纳米颗粒的局域表面等离子体共振效应，复合电极有效地抑制了光生电子-空穴对的复合，并表现出更低的电荷转移电阻，提高了光电催化性能。复合光电极在可见光照射下，90 min后可降解87.9%的四环素，且5个循环后降解率保持在82.5%。这些结果表明，Ag-Ti³⁺-TiO₂纳米锥复合光电极具有高降解效率、良好的稳定性和可持续的循环利用性，有望实现高效环保地光电催化降解抗生素。

关键词: 光电催化, TiO₂, 四环素, 可见光

CLC Number:

X703

Huixia ZHANG, Chenxin XIE, Lishan ZHOU, Chunyan REN, Hui ZHAO, Taiping LEI, Lingzhi ZHU. Preparation and photo-electrocatalytic performance of Ag-Ti³⁺-TiO₂ nanocone[J]. Industrial Water Treatment, 2024, 44(3): 159-167.

张会霞, 谢陈鑫, 周立山, 任春燕, 赵慧, 雷太平, 朱令之. Ag-Ti³⁺-TiO₂纳米锥的制备及光电催化性能研究[J]. 工业水处理, 2024, 44(3): 159-167.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-0173

https://www.iwt.cn/EN/Y2024/V44/I3/159

Figures/Tables 11

Fig.1 XRD patterns of different photoanodes

Fig.2 XPS spectra of ATT2

Fig.3 SEM images of different photoanodes

Fig.4 EDX spectra （a） and element mapping （b-d）of ATT2

Fig.5 Photoelectric performances of different photoanodes

Fig.6 Effects of ATT2 photoanode on TC degradation under different bias voltage（a），pH（b），experimental system（c），and effects of different photoanodes on degradation of TC（d）

Fig.7 Degradation rates of TC in five cycles experiment（a） and XRD comparison（b） before and after cycling of ATT2 photoanode

Fig.8 The possible degradation pathways of TC by ATT2

Fig.9 Radicals trapping experiments（a） and ESR spectra for TEMPO-h⁺ with ATT2（b）

Fig.10 The band gap energies（a） and VB-XPS spectra（b） of TT photoanode

Fig.11 photo-generated electron-hole pairs separation and transfer mechanism

References 44

1	黄艳芳. 抗生素的分类及应用［J］. 山东医药，2006，46（25）：84-85. doi:10.3969/j.issn.1002-266X.2006.25.063
	HUANG Yanfang. Classification and application of antibiotics［J］. Shandong Medical Journal，2006，46（25）：84-85. doi:10.3969/j.issn.1002-266X.2006.25.063
2	BAALOUDJ O， ASSADI I， NASRALLAH N，et al. Simultaneous removal of antibiotics and inactivation of antibiotic-resistant bacteria by photocatalysis：A review［J］. Journal of Water Process Engineering，2021，42：102089. doi:10.1016/j.jwpe.2021.102089
3	KOVALAKOVA P， CIZMAS L， MCDONALD T J，et al. Occurrence and toxicity of antibiotics in the aquatic environment：A review［J］. Chemosphere，2020，251：126351. doi:10.1016/j.chemosphere.2020.126351
4	KEMPF K， SCHMITT F， BILITEWSKI U，et al. Synthesis，stereochemical assignment，and bioactivity of the Penicillium metabolites penicillenols B₁ and B₂ ［J］. Tetrahedron，2015，71（31）：5064-5068. doi:10.1016/j.tet.2015.05.116
5	ZHANG Qianqian， YING Guangguo， PAN Changgui，et al. Comprehensive evaluation of antibiotics emission and fate in the river basins of China：Source analysis，multimedia modeling，and linkage to bacterial resistance［J］. Environmental Science & Technology，2015，49（11）：6772-6782. doi:10.1021/acs.est.5b00729
6	MARTIN-LAURENT F， TOPP E， BILLET L，et al. Environmental risk assessment of antibiotics in agroecosystems：Ecotoxicological effects on aquatic microbial communities and dissemination of antimicrobial resistances and antibiotic biodegradation potential along the soil-water continuum［J］. Environmental Science and Pollution Research，2019，26（18）：18930-18937. doi:10.1007/s11356-019-05122-0
7	PAZDA M， KUMIRSKA J， STEPNOWSKI P，et al. Antibiotic resistance genes identified in wastewater treatment plant systems：A review［J］. Science of the Total Environment，2019，697：134023. doi:10.1016/j.scitotenv.2019.134023
8	ZHANG Rui， YANG Shu， AN Yuwei，et al. Antibiotics and antibiotic resistance genes in landfills：A review［J］. Science of the Total Environment，2022，806：150647. doi:10.1016/j.scitotenv.2021.150647
9	Jia LÜ， YANG Linsheng， ZHANG Lan，et al. Antibiotics in soil and water in China：A systematic review and source analysis［J］. Environmental Pollution，2020，266：115147. doi:10.1016/j.envpol.2020.115147
10	KLEIN E Y， VAN BOECKEL T P， MARTINEZ E M，et al. Global increase and geographic convergence in antibiotic consumption between 2000 and 2015［J］. Proceedings of the National Academy of Sciences of the United States of America，2018，115（15）：3463-3470. doi:10.1073/pnas.1717295115
11	WU Qiangshun， YANG Hanpei， KANG Li，et al. Fe-based metal-organic frameworks as Fenton-like catalysts for highly efficient degradation of tetracycline hydrochloride over a wide pH range：Acceleration of Fe（Ⅱ）/Fe（Ⅲ） cycle under visible light irradiation［J］. Applied Catalysis B：Environmental，2020，263：118282. doi:10.1016/j.apcatb.2019.118282
12	XU Liangpang， LI Hui， MITCH W A，et al. Enhanced phototransformation of tetracycline at smectite clay surfaces under simulated sunlight via a Lewis-base catalyzed alkalization mechanism［J］. Environmental Science & Technology，2019，53（2）：710-718. doi:10.1021/acs.est.8b06068
13	ALAHABADI A， HOSSEINI-BANDEGHARAEI A， MOUSSAVI G，et al. Comparing adsorption properties of NH₄Cl-modified activated carbon towards chlortetracycline antibiotic with those of commercial activated carbon［J］. Journal of Molecular Liquids，2017，232：367-381. doi:10.1016/j.molliq.2017.02.077
14	尹福斌，詹源航，岳彩德，等. 膜分离技术在大型养殖场沼液处理中的应用与展望［J］. 农业环境科学学报，2021，40（11）：2335-2341. doi:10.11654/jaes.2021-1118
	YIN Fubin， ZHAN Yuanhang， YUE Caide，et al. Research progress on membrane technology for treatment of husbandry biogas slurry and wastewater［J］. Journal of Agro-Environment Science，2021，40（11）：2335-2341. doi:10.11654/jaes.2021-1118
15	HOMEM V， SANTOS L. Degradation and removal methods of antibiotics from aqueous matrices：A review［J］. Journal of Environmental Management，2011，92（10）：2304-2347. doi:10.1016/j.jenvman.2011.05.023
16	WEI Zhidong， LIU Junying， SHANGGUAN Wenfeng. A review on photocatalysis in antibiotic wastewater：Pollutant degradation and hydrogen production［J］. Chinese Journal of Catalysis，2020，41（10）：1440-1450. doi:10.1016/s1872-2067(19)63448-0
17	WU Suqing， HU Yunhang. A comprehensive review on catalysts for electrocatalytic and photoelectrocatalytic degradation of antibiotics［J］. Chemical Engineering Journal，2021，409：127739. doi:10.1016/j.cej.2020.127739
18	LIU Dong， LI Huijun， GAO Ranpeng，et al. Enhanced visible light photoelectrocatalytic degradation of tetracycline hydrochloride by I and P co-doped TiO₂ photoelectrode［J］. Journal of Hazardous Materials，2021，406：124309. doi:10.1016/j.jhazmat.2020.124309
19	LI Yaping， SUN Xianglin， TANG Yiming，et al. Understanding photoelectrocatalytic degradation of tetracycline over three-dimensional coral-like ZnO/BiVO₄ nanocomposite［J］. Materials Chemistry and Physics，2021，271：124871. doi:10.1016/j.matchemphys.2021.124871
20	MA Enhui， SUN Guolong， DUAN Fanglin，et al. Visible-light-responsive Z-scheme heterojunction MoS₂ NTs/CuInS₂ QDs photoanode for enhanced photoelectrocatalytic degradation of tetracycline［J］. Applied Materials Today，2022，28：101504. doi:10.1016/j.apmt.2022.101504
21	MAFA P J， KUVAREGA A T， MAMBA B B，et al. Photoelectrocatalytic degradation of sulfamethoxazole on g-C₃N₄/BiOI/EG p-n heterojunction photoanode under visible light irradiation［J］. Applied Surface Science，2019，483：506-520. doi:10.1016/j.apsusc.2019.03.281
22	YU Chengze， HOU Jiaqi， ZHANG Bin，et al. In-situ electrodeposition synthesis of Z-scheme rGO/g-C₃N₄/TNAs photoelectrodes and its degradation mechanism for oxytetracycline in dual-chamber photoelectrocatalytic system［J］. Journal of Environmental Management，2022，308：114615. doi:10.1016/j.jenvman.2022.114615
23	MAMBA G， MAFA P J， MUTHURAJ V，et al. Heterogeneous advanced oxidation processes over stoichiometric ABO₃ perovskite nanostructures［J］. Materials Today Nano，2022，18：100184. doi:10.1016/j.mtnano.2022.100184
24	GE Mingzheng， CAO Chunyan， HUANG Jianying，et al. Synthesis，modification，and photo/photoelectrocatalytic degradation applications of TiO₂ nanotube arrays：A review［J］. Nanotechnology Reviews，2016，5（1）：75-112. doi:10.1515/ntrev-2015-0049
25	程翔，毕迎普. TiO₂纳米阵列光阳极光电催化水分解研究进展［J］. 分子催化，2020，34（4）：341-365. doi:10.3724/sp.j.7102727948
	CHENG Xiang， BI Yingpu. Research advancement of the TiO₂ nanoarrays photoanode for photoelectrochemical water splitting［J］. Journal of Molecular Catalysis（China），2020，34（4）：341-365. doi:10.3724/sp.j.7102727948
26	JIA Meiying， YANG Zhaohui， XU Haiyin，et al. Integrating N and F co-doped TiO₂ nanotubes with ZIF-8 as photoelectrode for enhanced photo-electrocatalytic degradation of sulfamethazine［J］. Chemical Engineering Journal，2020，388：124388. doi:10.1016/j.cej.2020.124388
27	PAL D， SARKAR A， GHOSH N G，et al. Integration of LaCo（OH） _x photo-electrocatalyst and plasmonic gold nanoparticles with Sb-doped TiO₂ nanorods for photoelectrochemical water oxidation［J］. ACS Applied Nano Materials，2021，4（6）：6111-6123. doi:10.1021/acsanm.1c00928
28	GAN Ling， WU Yifan， SONG Haiou，et al. Self-doped TiO₂ nanotube arrays for electrochemical mineralization of phenols［J］. Chemosphere，2019，226：329-339. doi:10.1016/j.chemosphere.2019.03.135
29	HONG S P， KIM S， KIM N，et al. A short review on electrochemically self-doped TiO₂ nanotube arrays：Synthesis and applications［J］. Korean Journal of Chemical Engineering，2019，36（11）：1753-1766. doi:10.1007/s11814-019-0365-0
30	SONG Rui， CHI Haibo， MA Qiuling，et al. Highly efficient degradation of persistent pollutants with 3D nanocone TiO₂-based photoelectrocatalysis［J］. Journal of the American Chemical Society，2021，143（34）：13664-13674. doi:10.1021/jacs.1c05008
31	JIA Meiying， YANG Zhaohui， XIONG Weiping，et al. Magnetic heterojunction of oxygen-deficient Ti³⁺-TiO₂ and Ar-Fe₂O₃ derived from metal-organic frameworks for efficient peroxydisulfate（PDS） photo-activation［J］. Applied Catalysis B：Environmental，2021，298：120513. doi:10.1016/j.apcatb.2021.120513
32	FAN Haiyang， YI Guiyun， ZHANG Zhengting，et al. Fabrication of Ag particles deposited BiVO₄ photoanode for significantly efficient visible-light driven photoelectrocatalytic degradation of β-naphthol［J］. Journal of Environmental Chemical Engineering，2022，10（2）：107221. doi:10.1016/j.jece.2022.107221
33	FENG Wenjian， LIN Liangyou， LI Haijin，et al. Hydrogenated TiO₂/ZnO heterojunction nanorod arrays with enhanced performance for photoelectrochemical water splitting［J］. International Journal of Hydrogen Energy，2017，42（7）：3938-3946. doi:10.1016/j.ijhydene.2016.10.087
34	SUN Bojing， ZHOU Wei， LI Haoze，et al. Magnetic Fe₂O₃/mesoporous black TiO₂ hollow sphere heterojunctions with wide-spectrum response and magnetic separation［J］. Applied Catalysis B：Environmental，2018，221：235-242. doi:10.1016/j.apcatb.2017.09.023
35	JIA Yuhong， YE Long， KANG Xi，et al. Photoelectrocatalytic reduction of perchlorate in aqueous solutions over Ag doped TiO₂ nanotube arrays［J］. Journal of Photochemistry and Photobiology A：Chemistry，2016，328：225-232. doi:10.1016/j.jphotochem.2016.05.023
36	HE Shi， YAN Cheng， CHEN Xiaozhen，et al. Construction of core-shell heterojunction regulating α-Fe₂O₃ layer on CeO₂ nanotube arrays enables highly efficient Z-scheme photoelectrocatalysis［J］. Applied Catalysis B：Environmental，2020，276：119138. doi:10.1016/j.apcatb.2020.119138
37	WANG Keyi， LIANG Gaozhou， WAQAS M，et al. Peroxymonosulfate enhanced photoelectrocatalytic degradation of ofloxacin using an easily coated cathode［J］. Separation and Purification Technology，2020，236：116301. doi:10.1016/j.seppur.2019.116301
38	HU Qi， CAO Jiao， YANG Zhaohui，et al. Fabrication of Fe-doped cobalt zeolitic imidazolate framework derived from Co（OH）₂ for degradation of tetracycline via peroxymonosulfate activation［J］. Separation and Purification Technology，2021，259：118059. doi:10.1016/j.seppur.2020.118059
39	LUO Ting， FENG Haopeng， TANG Lin，et al. Efficient degradation of tetracycline by heterogeneous electro-Fenton process using Cu-doped Fe@Fe₂O₃：Mechanism and degradation pathway［J］. Chemical Engineering Journal，2020，382：122970. doi:10.1016/j.cej.2019.122970
40	HAO Zixuan， HOU Wenxin， FANG Chen，et al. Sulfite activation by cobaltosic oxide nanohydrangeas for tetracycline degradation：Performance，degradation pathways and mechanism［J］. Journal of Hazardous Materials，2022，439：129618. doi:10.1016/j.jhazmat.2022.129618
41	CHEN Yanxi， YIN Renli， ZENG Lixi，et al. Insight into the effects of hydroxyl groups on the rates and pathways of tetracycline antibiotics degradation in the carbon black activated peroxydisulfate oxidation process［J］. Journal of Hazardous Materials，2021，412：125256. doi:10.1016/j.jhazmat.2021.125256
42	DONG Haoran， JIANG Zhao， ZHANG Cong，et al. Removal of tetracycline by Fe/Ni bimetallic nanoparticles in aqueous solution［J］. Journal of Colloid and Interface Science，2018，513：117-125. doi:10.1016/j.jcis.2017.11.021
43	ZENG Zhiping， YAN Yibo， CHEN Jie，et al. Boosting the photocatalytic ability of Cu₂O nanowires for CO₂ conversion by MXene quantum dots［J］. Advanced Functional Materials，2019，29（2）：1806500. doi:10.1002/adfm.201806500
44	LI Xibao， KANG Bangbang， DONG Fan，et al. Enhanced photocatalytic degradation and H₂/H₂O₂ production performance of S-pCN/WO_2.72 S-scheme heterojunction with appropriate surface oxygen vacancies［J］. Nano Energy，2021，81：105671. doi:10.1016/j.nanoen.2020.105671

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Preparation and photo-electrocatalytic performance of Ag-Ti³⁺-TiO₂ nanocone

Ag-Ti³⁺-TiO₂纳米锥的制备及光电催化性能研究

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