钛酸钡基纳米材料的压电催化性能研究进展

张鹏; 王欣; 李智

doi:10.13801/j.cnki.fhclxb.20220629.002

钛酸钡基纳米材料的压电催化性能研究进展

doi: 10.13801/j.cnki.fhclxb.20220629.002

西安工业大学　光电工程学院，西安 710072

基金项目: 国家自然科学基金青年基金(51802246)

详细信息

通讯作者:
王欣，博士，副教授，硕士生导师，研究方向为光电功能材料　E-mail: wangx518@163.com

中图分类号: TB332
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出版历程
- 收稿日期: 2022-05-10
- 修回日期: 2022-06-08
- 录用日期: 2022-06-22
- 网络出版日期: 2022-06-30
- 刊出日期: 2023-03-15

Research progress in piezoelectric catalysis of barium titanate nanomaterials

School of Optoelectronic Engineering, Xi'an Technological University, Xi′an 710072, China

Funds: Youth Fund of National Natural Science Foundation of China (51802246)

摘要

摘要: 社会快速发展带来巨大经济效益的同时，也带来了一系列生态环境问题，如水污染、大气污染和污染物排放。催化降解被认为是处理各种污染的一种有效策略，相对于传统的光催化，压电催化是近几年提出的一种全新的催化方式。通过压电催化将机械能转化为化学能是解决当前水污染难题的一个有效手段，大量的压电材料被应用于压电催化降解的研究，其中BaTiO₃基纳米粉体作为一种典型的压电材料，因具有成本低、压电活性强等优点，引起了研究者的广泛关注。本文首先对压电催化的理论和起源进行了概述，列举了一些常用的压电催化材料并针对其压电催化应用进行举例。围绕BaTiO₃介绍了其基本结构、纳米BaTiO₃粉体的常用制备方法和在压电催化领域的应用及一些典型的改性方法。最后对BaTiO₃基纳米粉体在压电催化领域的未来发展趋势进行了展望。
- 钙钛矿 /
- 钛酸钡 /
- 压电催化 /
- 降解 /
- 改性方法
Abstract: The rapid development of society has brought huge economic benefits, but also brought a series of ecological environment problems, such as water pollution, air pollution and pollutant discharge. Catalytic degradation is considered as an effective strategy to deal with various kinds of pollution. Compared with traditional photocatalysis, piezoelectric catalysis is a new catalytic method proposed in recent years. Through the piezoelectric catalytic convert mechanical energy into chemical energy is an effective means of solving the water pollution problem, large numbers of piezoelectric materials have been applied in the research of catalytic degradation of piezoelectric, including BaTiO₃ nano powder as a kind of typical piezoelectric material, because of low cost, the advantages of strong piezoelectric activity, caused the wide attention of researchers. In this paper, the theory and origin of piezoelectric catalysis are summarized, some commonly used piezoelectric catalysis materials are listed and their applications are illustrated. Around BaTiO₃, the basic structure, common preparation methods of nano-BaTiO₃ powder, application in piezoelectric catalysis and some typical modification methods are introduced. Finally, the future development trend of BaTiO₃-based nano-powders in piezoelectric catalysis field is prospected.
- perovskite /
- barium titanate /
- piezoelectric catalysis /
- degradation /
- modified method

HTML全文

图 1 压电催化分解酸性橙7(AO₇)的机制图^[17]

Figure 1. Mechanism diagram of piezoelectrocatalytic decomposition of acidic orange 7 (AO₇)^[17]

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图 2 ABO₃立方钙钛矿结构单元示意图^[46]

Figure 2. Schematic diagram of ABO₃ cubic perovskite structural unit^[46]

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图 3 (a) 甲基橙(MO)溶液在不同条件下的降解能力；(b) MO的降解动力学曲线^[60]

Figure 3. (a) Degradation capability of methyl orange (MO) solutions under different conditions; (b) Kinetic curves of degradation of MO^[60]

NWs—Nanowires; UV—Ultraviolet; C—Absorbance; C₀—Initial absorbance

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图 4 (a) 不同振动时间下罗丹明B(RhB)的UV-vis吸收光谱(插图是RhB的振动-催化分解照片)；(b) 不同条件下RhB的分解效率(插图是在一定温度下保持60 min无振动的情况下加入BaTiO₃的RhB染料分解率)；(c) 2-羟基对苯二甲酸在不同振动时间下捕获BaTiO₃纳米纤维诱导的•OH的荧光光谱(插图是荧光强度对振动时间的响应的线性拟合)；(d) 回收BaTiO₃纳米纤维用于RhB的振动催化分解^[45]

Figure 4. (a) UV-vis absorbance spectra of Rhodamine B (RhB) under different vibration time (Illustration shows the vibro-catalytic decomposition of RhB); (b) Decomposition efficiency of RhB under different conditions (Illustration shows the decomposition rate of RhB dye with BaTiO₃ added when no vibration is maintained for 60 min at a certain temperature); (c) Fluorescence spectra of 2-hydroxyterephthalic acid for trapping the •OH induced by BaTiO₃ nanofibers for different vibration time (Inset is the linear fitting of the response of fluorescence intensity on the vibration time); (d) Recycling BaTiO₃ nanofiber catalysts for the vibration-catalytic decomposition of RhB^[45]

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图 5 (a) 在紫外光照射或超声作用下TiO₂纳米纤维(NFs)和BaTiO₃@TiO₂ NFs的催化降解效率随时间的变化及其相应的动力学曲线；(b) 伪一级动力学线性拟合；(c) 不同条件下TiO₂ NFs和BaTiO₃@TiO₂ NFs降解RhB的降解速率常数；(d) BaTiO₃@TiO₂ NFs在协同催化RhB下的循环稳定性^[66]

Figure 5. (a) Catalytic degradation efficiencies of RhB as a function of time and their corresponding kinetic curves for TiO₂ nanofibers (NFs) and BaTiO₃@TiO₂ NFs under ultraviolet light irradiation or ultrasonic; (b) Linear fittings of pseudo-first-order kinetics; (c) Comparisons the corresponding apparent rate constants for degradation of RhB by TiO₂ NFs and BaTiO₃@TiO₂ NFs under various catalytic conditions; (d) Cycling stability of BaTiO₃@TiO₂ NFs for synergetic piezo-photocatalysis of RhB^[66]

w/o—Without; w/—With; P—Polarization; k—Degradation rate

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图 6 p型和n型两种半导体材料间形成p-n结内电场的机制示意图^[75]

Figure 6. Example of the mechanism of electric field in p-n junction between p-type and n-type semiconductor materials figure^[75]

E_C—Conduction band; E_V—Valence band; E_F—Fermi level

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图 7 g-C₃N₄-TiO₂Z型光催化剂紫外光下的电荷转移和分离示意图^[76]

Figure 7. Schematic illustration for the charge transfer and separation in g-C₃N₄-TiO₂ Z-scheme photocatalysts under UV light irradiation^[76]

CB—Conduction band; VB—Valence band

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图 8 Sr_0.3Ba_0.7TiO₃纳米催化剂对于RhB的降解机制^[78]

Figure 8. Scheme the mechanism of RhB degradation mediated by ferroelectric Sr_0.3Ba_0.7TiO₃ catalysts^[78]

Ps—Spontaneous polarization

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图 9 不同条件下BaTi_0.89Sn_0.11O₃纳米颗粒对RhB的压电催化活性 (a)、BaTi_0.89Sn_0.11O₃纳米颗粒的反应速率常数 (b)、35℃下的捕获实验 (c)和BaTi_0.89Sn_0.11O₃纳米颗粒在35℃下降解RhB的回收能力 (d)^[79]

Figure 9. Piezocatalytic activities of RhB with BaTi_0.89Sn_0.11O₃ nanoparticles (a), comparison of reaction rate at different working temperatures (b) under different conditions, trapping experiments for the decomposition of RhB operated at 35℃ (c) and recycling ability of BaTi_0.89Sn_0.11O₃ for the degradation of RhB at 35℃ (d)^[79]

EDTA—Ethylene diamine tetraacetic acid; BTS—BaTi_0.89Sn_0.11O₃

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图 10 (a) BaTiO₃/SrTiO₃NFs的催化降解机制示意图；(b) 直流电场作用下BaTiO₃/SrTiO₃ NFs极化过程示意图；(c) BaTiO₃/SrTiO₃ NFs的压电光催化过程原理图和超声波照射下BaTiO₃/SrTiO₃异质结构的能带图；(d) 紫外光照射下异质结构BaTiO₃/SrTiO₃ NFs中的电子-空穴对分离和转移示意图；(e) 钛酸锶的带隙作为外加电场的函数(插图是钛酸锶的原子结构(左)和计算出的态密度(右))^[82]

Figure 10. Diagram of catalytic degradation mechanism of BaTiO₃/SrTiO₃ NFs(a), Schematic for polarization process of BaTiO₃/SrTiO₃ NFs under DC electric field(b), Schematic for the piezo-photocatalytic process of BaTiO₃/SrTiO₃ NFs and the energy band diagram of BaTiO₃/SrTiO₃ heterostructure under both UV irradiation and ultrasonic (c), Schematic of the electron–hole pairs separation and transfer in heterostructured BTO/STO NFs under UV light irradiation. Principle scheme of the piezo- catalysis of BaTiO₃/SrTiO₃ NFs during action of ultrasonic (d), Band gap of SrTiO₃ as a function of the applied electric field, insets are the atomic configurations (left) and the calculated density of states for SrTiO₃(right) (e) ^[82]

E—Electric field

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表 1 不同形貌BaTiO₃的催化性能

Table 1. Catalytic properties of BaTiO₃ with different morphologies

Catalysts	Dye species	Catalytic method	Degradation rate/min⁻¹	Refs.
BaTiO₃ powder	RhB (10 mg/L)	Ultrasonic	0.0012	[68]
BaTiO₃ powder	RhB (10 mg/L)	Ultraviolet light	0.0096	[68]
BaTiO₃ nanofibers	RhB (7.5 mg/L)	Ultrasonic	0.0736	[69]
BaTiO₃ nanoparticles	RhB (5 mg/L)	Ultrasonic	0.0025	[67]
BaTiO₃ nanowires	MO (5 mg/L)	Ultrasonic	0.0152	[57]
BaTiO₃ nanowires	RhB (5 mg/L)	Ultrasonic	0.0339	[67]

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