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HCS@TiO2光催化复合材料的制备及其染料降解性能

乔瑞泽 侯斌 林杰 汪德昭 高晓红

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): 2534-2545. doi: 10.13801/j.cnki.fhclxb.20230926.005
引用本文: 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): 2534-2545. doi: 10.13801/j.cnki.fhclxb.20230926.005
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): 2534-2545. doi: 10.13801/j.cnki.fhclxb.20230926.005
Citation: 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): 2534-2545. doi: 10.13801/j.cnki.fhclxb.20230926.005

HCS@TiO2光催化复合材料的制备及其染料降解性能

doi: 10.13801/j.cnki.fhclxb.20230926.005
基金项目: 江苏省大学生创新创业训练计划项目 (202310304117Y);江苏省青年基金(BK20210834)
详细信息
    通讯作者:

    高晓红,硕士,教授,硕士生导师,研究方向为功能性纳米材料的制备、功能性纺织品开发、空气净化和印染废水治理 E-mail: gao.xh@ntu.edu

  • 中图分类号: X791;TB332

Preparation and degradation dyestuffs performance of HCS@TiO2 photocatalytic composites

Funds: Jiangsu Province College Students' Innovation and Entrepreneurship Training Program (202310304117Y); Jiangsu Province Youth Found (BK20210834)
  • 摘要: 为了获得性能更加优异的光催化材料,本文通过简单的湿化学法制备了空心碳球(HCS)@TiO2光催化复合材料,并对其进行了表征。形貌与结构的表征结果显示,TiO2纳米颗粒均匀地锚定在HCS表面,形成亲水性强、比表面积大、热稳定性优异的球形复合材料,HCS@TiO2复合材料中TiO2的质量分数为80wt%;光电化学性质分析表明HCS@TiO2复合材料禁带宽度更小,光响应范围更大,光生电子还原能力更强。在模拟太阳光下,以活性红195 (RR195)为实验对象,测试制备的HCS@TiO2复合材料的光催化降解染料的性能和循环稳定性。结果表明:HCS@TiO2光生电子空穴对的分离效率更高,光催化活性优异,在120 min内染料降解率为95.36%,5次循环后仍高达93.34%,稳定性高,且易于回收。同时结合自由基捕获实验及电子顺磁共振光谱,对HCS@TiO2光催化复合材料的光催化机制进行了探究,证实了${\text{•}}{\rm{O}}_2^ - $在光催化反应体系中起主要作用。

     

  • 图  1  空心碳球(HCS)@TiO2 的合成示意图

    PPy—Polypyrrole; TOAC—Titanium oxide precursor

    Figure  1.  Composite diagram of hollow carbon sphere (HCS)@TiO2

    图  2  HCS ((a), (b)) 和HCS@TiO2 ((c), (d))的SEM、TEM图像;(e) HCS@TiO2的EDS元素分布图; HCS@TiO2的HRTEM图像(f)和快速傅里叶变换(FFT)图(g)

    d—Distance

    Figure  2.  SEM and TEM images of HCS ((a), (b)) and HCS@TiO2 ((c), (d)); (e) EDS images of HCS@TiO2; HRTEM image (f) and fast Fourier transform (FFT) image (g) of HCS@TiO2

    图  3  Ar气流下煅烧制备HCS@TiO2的XRD图谱

    Figure  3.  XRD pattern of HCS@TiO2 prepared by calcination under Ar flow

    图  4  不同煅烧温度下制备HCS@TiO2的XRD图谱

    Figure  4.  XRD patterns of HCS@TiO2 prepared at different calcination temperatures

    图  5  TiO2、HCS、HCS@TiO2的XPS图谱

    Figure  5.  XPS spectra of TiO2, HCS and HCS@TiO2

    图  6  HCS和HCS@TiO2的C1s高分辨XPS图谱((a), (b)) 、O1s高分辨XPS图谱((c), (d))及Ti2p高分辨XPS图谱((e), (f))

    Figure  6.  C1s high-resolution XPS spectra ((a), (b)), O1s high-resolution XPS spectra ((c), (d)) and Ti2p high-resolution XPS spectra ((e), (f)) of TiO2 and HCS@TiO2

    图  7  TiO2和 HCS@TiO2的N2吸附-解吸等温线

    V—Adsorption capacity; STP—Standard temperature and pressure

    Figure  7.  N2 adsorption/desorption isotherms of TiO2 and HCS@TiO2

    图  8  HCS@TiO2的热重分析图

    Figure  8.  Thermalgravimetric curves of HCS@TiO2

    图  9  HCS、酸化后的HCS、TiO2、HCS@TiO2的接触角分析

    Figure  9.  Contact angle analysis diagram of HCS, acidified HCS, TiO2, HCS@TiO2

    图  10  TiO2和 HCS@TiO2的UV-Vis DRS光谱(a) 和能隙图(b)

    α—Absorption coefficient; h—Planck's constant; ν—Frequency

    Figure  10.  UV-visible diffuse reflectance spectra (a) and energy gap diagram (b) of TiO2 and HCS@TiO2

    图  11  TiO2和HCS@TiO2的Mott-Schottky 曲线

    C—Interfacial capacitance

    Figure  11.  Mott-Schottky curves of TiO2 and HCS@TiO2

    图  12  TiO2和HCS@TiO2的电化学阻抗谱(a)及瞬态光电流响应图(b)

    Figure  12.  Electrochemical impedance spectra (a) and transient photocurrent response diagram (b) of TiO2 and HCS@TiO2

    图  13  HCS、TiO2和HCS@TiO2对活性红195 (RR195)的降解曲线

    D—Degradation

    Figure  13.  Degradation curves of Reactive Red 195 (RR195) using HCS, TiO2 and HCS@TiO2

    图  14  HCS@TiO2对RR195、活性黑5 (RB5)和碱性蓝9 (MB)的降解曲线

    Figure  14.  Degradation curves of RR195 and Reactive Black 5 (RB5) and Alkaline Blue 9 (MB) using HCS@TiO2

    图  15  HCS@TiO2降解RR195的紫外-可见光吸收光谱图(插图为RR195的颜色变化图)

    Figure  15.  UV-vis adsorption spectra of RR195 by HCS@TiO2 degradation(Illustrated with the color change of RR195)

    图  16  HCS@TiO2降解RR195的循环测试性能

    Figure  16.  Recycling test for the removal of RR195 using HCS@TiO2

    图  17  利用各种捕获剂与HCS@TiO2光催化降解RR195

    BQ—Benzoquinone; EDTA-2 Na—Ethylenediamine tetraacetate sodium; IPA—Isopropyl alcohol

    Figure  17.  Photocatalytic degradation of RR195 using HCS@TiO2 of with various radical scavengers

    图  18  TiO2和HCS@TiO2的四甲基哌啶(TEMPO)-e电子顺磁共振波谱(ESR)

    Figure  18.  Tetramethylpiperidine (TEMPO)-e electron paramagnetic resonance spectroscopy (ESR) of TiO2 and HCS@TiO2

    图  19  HCS@TiO2光催化降解RR195机制

    VB—Valence band; CB—Conduction band

    Figure  19.  Mechanism diagram of photocatalytic degradation of RR195 by HCS@TiO2

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出版历程
  • 收稿日期:  2023-07-24
  • 修回日期:  2023-09-03
  • 录用日期:  2023-09-09
  • 网络出版日期:  2023-09-27
  • 刊出日期:  2024-05-01

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