Piezo-photocatalytic property of PbTi0.85Ni0.15O3/TiO2 nanorod array composite materials
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摘要: 压电材料诱导的内建电场是调节电荷转移途径和抑制载流子复合的最有效策略之一。采用水热和溶胶凝胶两步法制备了PbTi0.85Ni0.15O3/TiO2纳米棒阵列复合材料。通过降解有机染料，复合材料展现了优异的压电光催化性能。经30 min， PbTi0.85Ni0.15O3/TiO2对亚甲基蓝(MB)的压电光催化降解率达到97.3%，降解反应速率为0.1215 min–1，是光催化降解速率(0.0372 min–1)的3.3倍，是压电催化降解速率(0.0211 min–1)的5.7倍。掺杂Ni后，带隙降低，载流子浓度增大，晶格畸变增大，压电光催化性能增强。添加牺牲剂实验和电子自旋共振波谱(ESR)实验结果表明，压电光催化降解中，•O2−和•OH是最主要的活性物质。此外， PbTi0.85Ni0.15O3/TiO2对不同染料的降解和循环5次后的降解率表明复合材料对多种染料具有良好的压电光催化降解性能和良好的稳定性。根据能带排列，提出压电极化导致的能带倾斜和弯曲可以促进光生载流子分离，从而使 PbTi0.85Ni0.15O3/TiO2具有优异的压电光催化染料降解性能。
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关键词:
- PbTi0.85Ni0.15O3/TiO2 /
- 复合材料 /
- 压电光催化 /
- 降解 /
- 能带倾斜
Abstract: The built-in electric field induced by piezoelectric materials has been proven to be one of the most effective strategies for regulating charge transfer pathways and suppressing carrier recombination. PbTi0.85Ni0.15O3/TiO2 nanorod arrays compsite were fabricated via a two-step process comprising hydrothermal and sol-gel methods. By degrading organic dyes, composite materials exhibit excellent piezo-photocatalytic performance. After 30 minutes, the piezo-photocatalytic degradation rate of methylene blue (MB) by PbTi0.85Ni0.15O3/TiO2 reached 97.3%, with a degradation reaction rate of 0.1215 min–1, which is 3.3 times of the photocatalytic degradation rate (0.0372 min–1) and 5.7 times of the piezoelectric catalytic degradation rate (0.0211 min–1). After doping Ni, the band gap decreases, the carrier concentration increases, the lattice distortion increases, and the piezo-photocatalytic performance enhances. The results of sacrificial agent addition experiments and electron spin resonance spectroscopy (ESR) experiments indicate that •O2− and •OH are the main active spices in piezo-photocatalytic degradation. After doping Ni, the band gap decreases, the carrier concentration increases, and the lattice distortion increases, resulting in superior piezo-photocatalytic performance of PbTi0.85Ni0.15O3/TiO2 compared to PbTiO3/TiO2. In addition, the degradation of different dyes by PbTi0.85Ni0.15O3/TiO2 and the degradation rate after 5 cycles indicate that the composite material has good piezo-photocatalytic degradation property for various dyes and good stability. According to the energy band arrangement, it is proposed that the tilting and bending of the energy band caused by piezoelectric polarization can promote the separation of photogenerated carriers, so that dye degradation has excellent piezoelectric photocatalytic performance.-
Key words:
- PbTi0.85Ni0.15O3/TiO2 /
- composite material /
- piezo-photocatalysis /
- degradation /
- band tilting
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图 1 (a) TiO2、PbTiO3/TiO2和 PbTi0.85Ni0.15O3/TiO2纳米棒阵列的XRD图谱；(b) 2θ=32°附近的放大XRD图谱
FTO—Conductive glass
Figure 1. (a) XRD patterns of TiO2, PbTiO3/TiO2 and PbTi0.85Ni0.15O3/TiO2 nanorods arrays; (b) Magnified XRD patterns around 2θ=32°
图 2 TiO2、PbTiO3/TiO2和 PbTi0.85Ni0.15O3/TiO2的SEM图像和EDS能谱图；(a) TiO2纳米棒阵列的表面图像；(b) TiO2纳米棒阵列的截面图像；(c) PbTiO3/TiO2表面图像；(d) PbTi0.85Ni0.15O3/TiO2表面图像；(e) EDS能谱图
Figure 2. SEM images and EDS patterns of TiO2, PbTiO3/TiO2 and PbTi0.85Ni0.15O3/TiO2 samples: (a) Surface of TiO2 nanorods arrays; (b) Cross-section image of TiO2 nanorods arrays; (c) Surface of PbTiO3/TiO2; (d) Surface of PbTi0.85Ni0.15O3/TiO2; (e) EDS mapping
图 3 PbTiO3和PbTi0.85Ni0.15O3的Raman图谱
A—Symmetric vibrations; B—Asymmectric vibrations; E—Elliptic vibrations; TO—Transverse optical mode; LO—Longitudinal optical mode
Figure 3. Raman scattering spectra for the PbTiO3 and PbTi0.85Ni0.15O3 samples
图 4 TiO2、PbTiO3和 PbTi0.85Ni0.15O3的紫外可见吸收光谱(a)和带隙图(b)
α—Absorption coefficient; hν—Photon energy
Figure 4. UV-Vis absorption spectra (a) and band gap (b) of TiO2 nanorod arrays, PbTiO3 and PbTi0.85Ni0.15O3 thin films
图 5 PbTi0.85Ni0.15O3/TiO2复合材料对亚甲基蓝的光催化、压电催化和压电-光催化降解图: (a)降解效率；(b)降解速率k
C0—Initial concentration; Ct—Concentration after degradation
Figure 5. Degradation profiles of methylene blue of photocatalysis, piezocatalysis and piezo-photocatalysis for PbTi0.85Ni0.15O3/TiO2 composite: (a) Degradation efficiency; (b) Degradation rate k
图 6 TiO2、PbTiO3、PbTiO3/TiO2和 PbTi0.85Ni0.15O3/TiO2的压电-光催化活性比较: (a)压电光催化活性；(b)降解速率k
Figure 6. Comparison of piezo-photocatalytic activities for the TiO2, PbTiO3, PbTiO3/TiO2 and PbTi0.85Ni0.15O3/TiO2: (a) Piezo-photocatalytic activity; (b) Degradation rate k
图 7 PbTi0.85Ni0.15O3/TiO2压电光催化降解亚甲基蓝(MB)的稳定性: (a) PbTi0.85Ni0.15O3/TiO2的重复催化活性；(b)催化降解前和降解5次后PbTi0.85Ni0.15O3/TiO2的XRD图谱和SEM图像
Figure 7. Stability of PbTi0.85Ni0.15O3/TiO2 for methylene blue (MB) degradation under ultrasound and light: (a) Repeated piezo-phtocatalytic activity of PbTi0.85Ni0.15O3/TiO2; (b) XRD patterns of original PbTi0.85Ni0.15O3/TiO2 and after five recycles degradation (Inset is SEM image)
图 8 (a)压电和光协同作用时 PbTi0.85Ni0.15O3/TiO2对不同起始浓度MB的降解活性；(b)压电和光协同作用时 PbTi0.85Ni0.15O3/TiO2对不同有机污染物的降解活性(插图为PbTi0.85Ni0.15O3/TiO2的降解反应速率常数k)
MB—Methylene blue; MO—Methyl orange; RhB—Rhodamine B; AO7—Acid orange 7
Figure 8. (a) Different-concentration MB piezophotocatalysis degradation activity; (b) Piezophotocatalysis degradation activity of different organic pollutants in PbTi0.85Ni0.15O3/TiO2 (Inset shows reaction rate constant k for PbTi0.85Ni0.15O3/TiO2 under ultrasound and light)
图 9 (a)添加牺牲剂时PbTi0.85Ni0.15O3/TiO2压电光催化降解MB的效率；(b)相应的反应速率常数k；(c) •OH的ESR图谱；(d) •O2−的ESR图谱
BQ—Benzoquinone; TBA—Tert-butyl alcohol; EDTA-2Na—Ethylenediaminetetraacetic acid disodiu-msodium salt; DMPO—5, 5-dimethyl-1-pyrrolidine nitrogen oxide
Figure 9. (a) Piezo-photocatalytic MB degradation activity with and without scavengers for PbTi0.85Ni0.15O3/TiO2; (b) Corresponding degradation reactive rate k; (c) ESR spectra of •OH; (d) ESR spectra of •O2−
图 10 催化剂的电化学性能：(a) TiO2、PbTiO3/TiO2、PbTi0.85Ni0.15O3/TiO2的电化学阻抗谱；(b) TiO2、PbTiO3和PbTi0.85Ni0.15O3的Mott-Schottky曲线
C—Capacitance
Figure 10. Electrichemical properties of catalyst: (a) EIS of TiO2, PbTiO3/TiO2 and PbTi0.85Ni0.15O3/TiO2; (b) Mott-Schottky plots of TiO2, PbTiO3 and PbTi0.85Ni0.15O3
图 11 PbTi0.85Ni0.15O3的能带排列和压电光催化原理图：(a)仅光照时；(b)超声和光同时作用时
NHE—Normal hydrogen electrode; P—Polarization intensity
Figure 11. Principle scheme of the piezo-photocatalysis contains band tilting and surface reaction for PbTi0.85Ni0.15O3: (a) Illumination only; (b) Ultrasound and light co-effective
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