Preparation and degradation dyestuffs performance of HCS@TiO2 photocatalytic composites
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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。Abstract: In order to obtain more efficient photocatalytic materials, hollow carbon sphere (HCS)@TiO2 photocatalytic composites was prepared by a facile wet-chemical method and characterized. The results of structural and morphology characterization showed that TiO2 nanoparticles were anchored uniformly on the surface of HCS, forming a spherical composites with high hydrophilia and specific surface area and excellent thermostability, the mass percentage of TiO2 anchored on HCS@TiO2 composites was 80wt%. The analysis of photoelectric chemical properties showed that HCS@TiO2 composites had smaller bandgap width, wider light response range, and stronger photogenic electron reduction ability. Using Reactive Red 195 (RR195) as the experimental object, the photocatalytic degradation dyes performance and cyclic stability of HCS@TiO2 composites were tested under simulated sunlight. The results show that the separation efficiency of photogenic electron hole pairs in the HCS@TiO2 is higher, and the photocatalytic activity is excellent. The degradation rate is 95.36% within 120 min, and it still reaches 93.34% after 5 cycles, with high stability and easy recovery. At the same time, the photocatalytic mechanism of HCS@TiO2 photocatalytic composites was proposed by combining free radical capture experiment and electron paramagnetic resonance spectroscopy. It was confirmed that ${\text{•}}{\rm{O}}_2^ - $ plays a major role in the photocatalytic reaction system.
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Key words:
- wet chemical method /
- titanium dioxide /
- hollow carbon spheres /
- photocatalytic /
- composites /
- degradation /
- Reactive Red 195
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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 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 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
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