Construction of Nano Ag Modified TiO2 Nanotube Array Substrate for Surface Enhanced Raman Scattering Detection and Degradation of Tetracycline Hydrochloride

doi:10.19894/j.issn.1000-0518.210349

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (7): 1147-1156.DOI: 10.19894/j.issn.1000-0518.210349

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Construction of Nano Ag Modified TiO₂Nanotube Array Substrate for Surface Enhanced Raman Scattering Detection and Degradation of Tetracycline Hydrochloride

Xiao-Li ZHANG², Yu-Mei PENG¹, Qing-Wei WANG¹, Li-Xia QIN¹(), Xiao-Xia LIU¹, Shi-Zhao KANG¹, Xiang-Qing LI¹()

^1.School of Chemical and Environmental Engineering，Shanghai Institude of Technology，Shanghai 201418，China
^2.School of Chemistry and Chemical Engineering，Shangqiu Normal College，Shangqiu 476000，China

Received:2021-07-19 Accepted:2021-11-23 Published:2022-07-01 Online:2022-07-11
Contact: Li-Xia QIN,Xiang-Qing LI
About author:lxqin@sit.edu.cn
xqli@sit.edu.cn
Supported by:
the National Natural Science Foundation of China(21771125);the Scientific Research Project of Shanghai Municipal Science and Technology Commission(19090503700)

Abstract

Abstract:

By combining anodic oxidation with photo-reduction method， a uniform， stable and recyclable surface enhanced Raman scattering （SERS）-active substrate composed of well-ordered Ag nanoparticles decorated on TiO₂ nanotube arrays （TiO₂NTAs/Ag） is obtained. The composition and structure of the TiO₂NTAs/Ag are characterized using X-ray powder diffraction （XRD）， X-ray photoelectron spectroscopy （XPS）， UV-Vis diffuse reflection spectrum （UV-Vis DRS）， surface enhanced Raman scattering spectroscopy （SERS） and scanning electron microscope （SEM） measurements. The SERS response of the TiO₂NTAS/Ag array to tetracycline hydrochloride （TC-HCl） is further studied， which exhibits superior sensitivity for SERS detection of TC-HCl， and the detection limit could reach 1 × 10^－14 mol/L in water. In addition， the TiO₂NTAs/Ag substrate exhibits excellent degradation activity for TC-HCl under light and could be recycled for at least 8 times. It shows a potential application in SERS detection and degradation of organic contaminants in environment.

Key words: TiO₂ nanotube arrays, Recyclable substrate, Surface enhanced Raman scattering detection, Photo-degradation, Tetracycline hydrochloride

CLC Number:

O657.3

Xiao-Li ZHANG, Yu-Mei PENG, Qing-Wei WANG, Li-Xia QIN, Xiao-Xia LIU, Shi-Zhao KANG, Xiang-Qing LI. Construction of Nano Ag Modified TiO₂Nanotube Array Substrate for Surface Enhanced Raman Scattering Detection and Degradation of Tetracycline Hydrochloride[J]. Chinese Journal of Applied Chemistry, 2022, 39(7): 1147-1156.

Figures/Tables 11

Fig.1 The structure of TC-HCl

Fig.2 Assembly illustration of TiO2NTAs/Ag

Fig.3 XRD patterns of TiO2NTAs （a） and TiO2NTAs/Ag （b）

Fig.4 （A） XPS survey spectrum of TiO2NTAs/Ag； Ti2p XPS spectra （B） and O1s XPS spectra （C） of TiO2NTAs （a） and TiO2NTAs/Ag （b）；（D） Ag3d XPS spectrum of TiO2NTAs/Ag

Fig.5 （A） Raman spectra of TiO2NTAs （a） and TiO2NTAs/Ag （b）；（B） UV-Vis diffuse reflectance spectra of TiO2NTAs （a） and TiO2NTAs/Ag （b）

Fig.6 SEM images of （A） TiO2NTAs and （B） TiO2NTAs/Ag. The insets in （A） and （B）： cross-section of TiO2NTAs and the size distribution histogram for AgNPs on the surface of the TiO2NTAs， respectively

Fig.7 （A） Raman spectra of pure TC-HCl （a） and SERS spectra of the TC-HCl with different concentrations using TiO2NTAs/Ag as SERS substrate： 0.05 g/L （b），0.005 μg/L （c），0.05 μg/L （d），0.5 μg/L （e），5 μg/L （g），50 μg/L （f），100 μg/L （h），200 μg/L （i），300 μg/L （j），400 μg/L （k） and 500 μg/L （l）， respectively；（B），（C） and （D） Plots of the intensity of the Raman bands at 920， 1389 and 1602 cm-1 against the different concentration （c — l） of TC-HCl， respectively

Table 1 Comparison of the LOD for SERS detection TC?HCl on some substrates

材料 Materials	检测限 LOD/（mol?L^-1）	参考文献Ref.
Fe₃O₄@PEI@AgNPs	1 × 10^-8	［27］
Silver colloid	1 × 10^-11	［22］
Chitosan/gold NPs/graphene oxide	1 × 10^-10	［28］
TiO₂NTAs/Ag	1 × 10^-14	This work

Fig.8 （A） SERS spectra of 50 mg/L TC-HCl on TiO2NTAs/Ag（a） and SERS spectra of the sample after being placed for 30 days （b）；（B） SERS cycles of the TiO2NTAs/Ag， and the target molecule is 50 mg/L TC-HCl

Fig.9 SERS spectra of 50 mg/L TC-HCl aqueous solution （a）， diluted milk （b） and diluted milk+TC-HCl at different concentration levels： 100 （c）， 200 （d）， 300 （e）， 400 （f） and 500 μg/L （g）， respectively. SERS spectra are detected on the TiO2NTAs/Ag SERS substrate

Fig.10 Photocatalytic degradation efficiency for TC-HCl. The areas of TiO2NTAs and TiO2NTAs/Ag are 1.0 cm × 1.0 cm （the initial concentration of TH-HCl is 0.1 μmol/L）

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Construction of Nano Ag Modified TiO₂Nanotube Array Substrate for Surface Enhanced Raman Scattering Detection and Degradation of Tetracycline Hydrochloride

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