钙钛矿铁电半导体的光催化研究现状及其展望

崔宗杨; 谢忠帅; 汪尧进; 袁国亮; 刘俊明

doi:10.7498/aps.69.20200287

摘要

钙钛矿材料可以分为ABO₃氧化物和ABX₃ (X = Cl, Br或I)卤化物两大类, 它们都具有丰富的物理性质和优异的光电性能, 比如铁电性和光催化性能. 本文介绍了BiFeO₃和MAPbI₃等铁电半导体光催化材料和异质结的制备方法, 总结了它们在光电催化方面的研究进展. 目前研究者已经针对氧化物光催化材料做了各种研究, 包括: 降低吸光层铁电材料的带隙, 制备铁电/窄带半导体吸光层异质结, 制备比表面积很大的纳米片、纳米棒或者其他纳米结构, 以便吸收更多可见光; 让铁电极化及其退极化场垂直于光催化工作电极表面, 通过铁电/半导体异质结能带弯曲提供内电场, 通过外电场进行光电催化, 从而通过内、外电场高效分离光生-电子空穴对; 通过光催化或者光电催化降解染料、分解水制氢、将CO₂转换为燃料; 通过铁电、热释电和压电协同效应提高催化效应和能量转换效率. MAPbI₃等卤素钙钛矿具有优异的半导体性质, 其铁电性可能是引起超长的少数载流子寿命和载流子扩散长度的原因. 通过优化光催化多层膜结构并添加防止电解液渗透的封装层可以避免MAPbI₃被电解液分解, 从而制备了具有很高能量转换效率的光电催化结构. 最后, 我们分析和比较了这些钙钛矿铁电半导体在光电催化领域面临的挑战, 并展望了其应用前景.

关键词:

Abstract

There are two types of perovskites, i.e. ABO₃-type oxides and ABX₃-type (X = F, Cl, Br and I) halides. Both of them exhibit rich physical properties and excellent photoelectric properties, such as ferroelectric and photocatalytic properties. In this paper we introduce the methods of preparing the ferroelectric semiconductors (i.e. BiFeO₃ and MAPbI₃) and their heterogeneous junctions for photocatalytic applications, and summarizes the research progress and applications of photocatalytic devices. Various researches about oxide photocatalytic devices have been carried out. At first, several methods have been developed to absorb more visible light, such as reducing the band gap of ferroelectric materials, preparing junction composed of ferroelectric layer and light absorption layer with narrow-bandgap semiconductor, and growing nanosheet, nanorods or other nanostructures with large specific surface areas. Second, some electric fields are introduced to effectively separate light activated electron-holes pairs. In addition to the external electric field, an inner electric field can be introduced through the ferroelectric polarization perpendicular to the surface and/or the energy band bending at the ferroelectric/semiconductor interface. Thirdly, the degradation of dyes, the decomposition of water into hydrogen and the conversion of CO₂ into fuel have been realized in many photocatalytic or photoelectrocatalytic devices. Fourthly, the synergies of ferroelectric, pyroelectric and piezoelectric effects can largely increase the photocatalytic efficiency and the energy conversion efficiency. Furthermore, MAPbI₃ and other halogen perovskites show excellent semiconductor properties, such as the long carrier diffusion length and long minority carrier lifetime which may originate from ferroelectric dipoles. The MAPbI₃ can be applied to photocatalytic devices with a high energy conversion efficiency by optimizing the photocatalytic multi-layer structure and adding a package layer that prevents electrolyte for decomposing the MAPbI₃. Finally, we analyze the challenges of the high-efficiency photocatalytic devices and look forward to their application prospects.

Keywords:

作者及机构信息

1.
南京理工大学材料科学与工程学院, 南京　210094

2.
南京大学物理学院, 固体微结构物理国家重点实验室, 南京　210093

通信作者: 袁国亮, yuanguoliang@njust.edu.cn

基金项目: 国家级-国家自然科学基金(51790492、51431006、51902159 、61874055)

Authors and contacts

1.
School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

2.
National Laboratory of Solid State Microstructures, School of Physics, Nanjing University, Nanjing 210093, China

Corresponding author: Yuan Guo-Liang, yuanguoliang@njust.edu.cn

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施引文献

图 1 (a) ABX₃型钙钛矿铁电材料结构图; (b) P-E电滞回线; (c) 铁电光催化、热释电催化、压电催化机制及其应用

Fig. 1. (a) Structure diagram of ABX₃ type perovskite ferroelectric material; (b) P-E hysteresis loop. (c) photocatalysis, piezocatalysis and pyrocatalysis of a ferroelectric semiconductor and their application

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图 2 (a) 光催化分解水的基本原理; (b) 光催化产氢、析氧反应步骤^[33]

Fig. 2. (a) Basic principle of photocatalytic water-splitting process; (b) photocatalytic reaction steps for hydrogen and oxygen production^[33]

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图 3 (a), (b) 对BiFeO₃薄膜进行+8 V和–8 V 极化后的能带结构示意图; (c) 极化之前和+8 V和–8 V极化之后BiFeO₃电极测量的外量子效率; (d) 不同铁电极化状态的BiFeO₃工作电极的光电流与电势曲线^[24]

Fig. 3. Energy band structure diagram of the BiFeO₃ thin film after (a) +8 V and (b) –8 V poling; (c) external quantum yield spectra of BiFeO₃ film before poling and after +8 V and –8 V poling; (d) photocurrent–potential characteristics of the photoelectrodes with different polarization states^[24]

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图 4 (a) 三种50 nm厚外延BiFeO₃薄膜光阳极的Mott-Schottky曲线, 相对于Ag/AgCl参比电极的平带电势由曲线斜率与横轴交点决定; (b) 400—800 nm入射光波长范围内的BiFeO₃薄膜的吸光度; (c) 三种外延BiFeO₃薄膜光阳极的能带位置; (d) BiFeO₃薄膜光阳极的电化学阻抗谱^[77]

Fig. 4. (a) Mott-Schottky plots for the 50-nm-thick epitaxial BiFeO₃ thin-film photoanodes with different crystallographic orientations, where the flat-band potentials are obtained from the intercepts of the extrapolated lines; (b) absorbance measurements for these three BiFeO₃ thin films with incident light at 400−800 nm wavelength; (c) band positions for the epitaxial BiFeO₃ thin-film photoanodes; (d) electrochemical impedance spectroscopy spectra of the BiFeO₃ thin-film photoanodes^[77]

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图 5 光催化反应过程中BiFeO₃薄膜作为光阳极的能带图　(a) 不同极化状态下, BiFeO₃薄膜能带结构的改变; (b) (111)_pc BiFeO₃薄膜作为光阳极的光电流密度-电势曲线; (c) 在电势为0 V情况下(001)_pc和(111)_pc BiFeO₃薄膜光阳极的光电流密度-时间曲线^[61]

Fig. 5. Energy band diagrams for BiFeO₃ photoanodes in PEC water splitting cells: (a) Changes in the band structure of BiFeO₃ thin films under different polarization states; (b) linear sweep voltammetry of 50-nm-thick (111)_pc BiFeO₃ thin-film photoanodes in different polarization states; (c) photocurrent density versus time curves for (001)_pc and (111)_pc BiFeO₃ thin-film photoanodes with different polarization states under zero bias (0 V vs. Ag/AgCl)^[61]

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图 6 (a) BiFeO₃@Sn:TiO₂生长机制示意图; (b) TiO₂, Sn:TiO₂与Sn:TiO₂@BiFeO₃作为光阳极时的光电流密度; 铁电极化分别指向(c) 电解液和(d) Sn:TiO₂时, Sn:TiO₂@BiFeO₃的能带示意图^[89]

Fig. 6. (a) Schematic representation for the growth mechanism of Sn:TiO₂@BiFeO₃ nano rods; (b) photocatalysis performance of TiO₂, Sn:TiO₂ and BiFeO₃@Sn:TiO₂ nano rods. Schematic electronic band diagram of (c) positive poling BiFeO₃ and (d) negative poling BiFeO₃^[89]

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图 7 (a) BiVO₄/BiFeO₃光阳极的电子能级及结构示意图; (b) BiVO₄/Co-Pi, BiVO₄和BiVO₄/BiFeO₃三种结构的光电流密度-电势曲线; (c)不同铁电极化状态下BiVO₄/BiFeO₃光阳极的光电流密度-电势曲线; (d) 在工作电极的电势为0.6 V时, 三种结构的光电流密度-时间的曲线^[102]

Fig. 7. (a) Electron energy levels of BiVO₄/BiFeO₃ photoanode and the structural representation; (b) the photocurrent density curves of three different structures of BiVO₄/Co-Pi, BiVO₄ and BiVO₄/BiFeO₃; (c) photocurrent density versus potential curves at three statuses of ferroelectric polarization; (d) long-term photostability of three photoanodes at 0.6 V (V vs. Ag/AgCl)^[102]

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图 8 SrTiO₃/CaRuO₃/Bi₂FeCrO₆样品在Bi₂FeCrO₆ 的(a)初始极化状态、(b) +P (即P_up)、(c) –P(即P_down)时的结构示意图和在光阴极时Bi₂FeCrO₆薄膜的光电流-电势(vs. Ag/AgCl)曲线图^[15]; (d) 在光阳极时SrTiO₃/SrRuO₃/Bi₂FeCrO₆/NiO异质结的光电催化示意图和(e)其光电流-电势曲线^[62]

Fig. 8. Schematic illumination and variations of the photocurrent density with applied voltage (vs. Ag/AgCl) in 1 mol/L Na₂SO₄ at pH 6.8 under chopped simulated sunlight illumination (AM1.5G) of SrTiO₃/CaRuO₃/Bi₂FeCrO₆ sample: (a) Before, (b) after negative (P_up, –25 V) and (c) and positive poling (P_down, 25 V)^[15]; (d) schematic diagram of the experimental setup and (e) photocurent versus potential (vs. RHE) curves of SrTiO₃/SrRuO₃/Bi₂FeCrO₆/NiO^[62]

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图 9 (a) BaTiO₃铁电材料的能带结构及其退极化场E_P分离光生电子-空穴对的示意图; (b) 太阳光照射下不同催化剂对罗丹明B的光致脱色特性^[43]; (c) Glass/500 nm-BaTiO₃/67 nm-MoO₃异质结的能带结构和载流子分离示意图; (d) 该异质结在紫外可见光和可见光分别照射下分离罗丹明B的效果图^[44]; (e) 可见光(λ > 400 nm)照射下BaTiO₃-CdS复合材料的光生空穴-电子对分离、载流子迁移以及光催化产生氢气的示意图; (f) 原始CdS, 纯BaTiO₃和BaTiO₃-CdS (wt 20%)复合材料的光电流-时间曲线(电极0.5 cm × 0.5 cm)^[118]

Fig. 9. (a) Schematic of BaTiO₃-Ag composites with the effect of free carrier reorganization on band structure and photoexcited carriers, and (b) photodecolorization profiles of RhB with different catalysts under solar simulator^[43]; (c) schematic representation of the 500 nm-BaTiO₃/67 nm-MoO₃ heterostructure on glass substrate, and (d) its photodecolorization profiles of RhB under UV-visible and visible light (sun light)^[44]; (e) schematic of photoinduced hole and electron migration in BaTiO₃-CdS composites and photocatalytic hydrogen process under visible light (λ > 400 nm), and (f) its photoelectrochemical properties of pristine CdS, pure BaTiO₃ and BaTiO₃-CdS (wt 20%) composite^[118]

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图 10 (a) TiO₂@BaTiO₃ (BTO)纳米线的能带结构示意图; (b) 铁电极化后TiO₂@BaTiO₃纳米线光阳极的光电流密度-电势曲线^[5]; (c) 在FTO玻璃上制备TiO₂@ BTO/Ag₂O纳米棒的示意图; (d) 在标准太阳光照射下, TiO₂, TiO₂@BTO, 初始TiO₂@BTO/Ag₂O, 铁电极化指向TiO₂的TiO₂@BTO/Ag₂O四种纳米棒阵列的光电流-电势曲线^[66]

Fig. 10. (a) Energy band diagram of nanowire photocatalytic reaction of TiO₂@BaTiO₃ nanowires; (b) photocurrent density versus potential curve of TiO₂@BaTiO₃ nanowires at three polarization statuses^[5]; (c) scheme of the fabrication process of TiO₂@BTO/Ag₂O nanorod array, and (d) photocurrent-potential curves in the dark and under Xe lamp irradiation of the different photoanodes^[66]

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图 11 (a) 铁电极化垂直于表面时, (001) PbTiO₃单晶单畴纳米片在200—350 nm不同厚度时的能带图; (b) 通过开尔文探针力显微镜测量的表面光伏电压SPV^[124]; (c) (001) PbTiO₃单晶纳米片、TiO₂粉体、铁电极化指向或背向TiO₂层或没有特定指向情况下的PbTiO₃/TiO₂纳米片的光催化分解甲基蓝的速率常数K_obs (即K_MB); (d) 光催化产氢速率^[46]

Fig. 11. (a) Schematic of energy band in thinner (001) PbTiO₃ (PTO) with smaller built-in voltages (ΔV) and thicker nanosheet with larger ΔV; (b) correlation between surface photovoltaic value measured by Kelvin probe force microscopy and nanosheet thickness^[124]; (c) the reaction rate of blank control and photodegradation of MB under visible light (λ ≥ 420 nm) irradiation with (001) PTO, TiO₂ and heterostructured TiO₂/PTO composites; (d) H₂ evolution rate of water splitting under visible light (λ ≥ 420 nm) irradiation^[46]

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图 12 (a) 铁电极化指向底电极时FTO/NaNbO₃光阳极的能带结构示意图; (b) 在0.5 mol/L Na₂SO₄电解质中以100 mW/cm²的紫外-可见光线照射下, 不同极化条件下光阳极的电流-电位曲线^[64]; (c) 铁电极化指向底电极时PVDF/Cu/NaNbO₃/PVDF的能带结构示意图; (d) 不同极化条件下NaNbO₃/PVDF薄膜的光电流密度-时间曲线^[126]

Fig. 12. (a) Band bending of FTO/NaNbO₃ for negative polarized; (b) current-potential curves of photoanodes with different polarization conditions^[64]; (c) band bending of PVDF/Cu/PVDF-NaNbO₃ for negative polarized; (d) current density versus time curves of NaNbO₃/PVDF films with different polarization conditions^[126]

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图 13 (a) 铁电、热电和压电材料中自由载流子重组和光激发载流子分离的示意图^[140]; (b) 在紫外光照射、超声振动分别和同时存在时, BCT-0和BCT-0.2降解甲基橙染料的K_obs对比^[150]; (c) 在氙灯可见光、超时振动分别和同时存在时, KNbO₃纳米管(NC)和纳米片(NS)的降解甲基橙染料的K_obs(即k)对比^[50]; (d) ZnSnO_3–_x 纳米线在超声振动和氙灯光照情况下降解罗丹明B染料和(e)分解水产氢的对比图^[52]

Fig. 13. (a) Schematic understanding of free carrier reorganization and photo-excited carrier separation in ferroelectric, pyroelectric and piezoelectric materials under the influence of ferroelectric, pyroelectric and piezoelectric effects respectively^[140]; (b) degradation reaction kinetic rate constants (K_obs) of methyl orange over BCT-0 and BCT-0.2 under UV light, ultrasonic vibration and the simultaneous assistance of ultrasonic vibration and UV light^[150]; (c) K_obs (i.e. k) of the RhB solution over the KNbO₃ nanosheet (NS) and nanotube (NC) under different conditions^[50]; (d) the RhB dye solution degradation activity and (e) the amount of hydrogen evolution of ZnSnO_3–_x nanowires as a function of time under applying light and ultrasonic vibration simultaneously^[52]

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图 14 (a) 半导体催化剂中光照产生电子-空穴对, 电子空穴对分离, 空穴氧化H₂O并产生氧气, 电子还原CO₂和H₂O并产生燃料; (b) 几种半导体光催化剂的导带、价带电势和带隙, 参与CO₂还原的化合物在pH=7时的氧化还原电势^[158]

Fig. 14. (a) Schematic illustration of photoinduced generation of an electron-hole pair in semiconductor that transfers to the surface for CO₂ photoredox; (b) conduction band, valence band potentials, and band gap energies of various semiconductor photocatalysts relative to the redox potentials at pH 7 of compounds involved in CO₂ reduction^[158].

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图 15 (a) SrBi₄Ti₄O₁₅的铁电极化增强光生电子-空穴对分离效率的示意图; (b) SrBi₄Ti₄O₁₅的能级图; (c) SrBi₄Ti₄O₁₅, Bi₄Ti₃O₁₂, P25和BiOBr通过光催化产生CH₄和CO的速率; (d) 不同退火温度的SrBi₄Ti₄O₁₅通过光催化生产CH₄的数量-时间曲线^[164]

Fig. 15. (a) Schematic diagram of polarization-field enhanced separation of photogenerated charge carriers; (b) diagram for the band energy levels of SrBi₄Ti₄O₁₅; (c) the corresponding rates over SrBi₄Ti₄O₁₅, Bi₄Ti₃O₁₂, P25 and BiOBr; (d) CH₄ yield curves of SrBi₄Ti₄O₁₅ with different annealing temperatures^[164]

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图 16 (a) CH₃NH₃PbI₃晶体在204 K时的介电常数实部ε_re和虚部ε_im与外电压的曲线; (b) 通过对ε_im进行积分得到的P-E电滞回线^[174]

Fig. 16. (a) Dielectric response at 204 K of a CH₃NH₃PbI₃ crystal, showing that ε_re dominates the dielectric response; (b) P-E hysteresis loop obtained from integration of ε_im over applied electric field^[174]

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图 17 (a) CH₃NH₃PbI₃薄膜光伏电池和串联催化装置的宏观结构示意图; (b) 材料能带-电荷输运示意图; (c)钙钛矿串联电池两个NiFe-LDH电极之间的光电流密度-电压曲线; (d) 光伏电池串联催化分解水装置的光电流密度-时间曲线^[71]

Fig. 17. (a) Schematic diagram of the water-splitting device based on CH₃NH₃PbI₃ film; (b) generalized energy schematic of the perovskite tandem cell for water splitting; (c) J-V curves of the perovskite tandem cell, and the NiFe/Ni foam electrodes in a two-electrode configuration; (d) current density-time curve of the integrated water-splitting device^[71]

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图 18 (a) FTO/m-TiO₂/CH₃NH₃PbI₃/Spiro-MeOTAD/Au/Catalyst光催化结构的集成光电解装置示意图; (b) 在模拟光照下Au表面含Ni催化剂(红色曲线)和不含Ni催化剂(蓝色曲线)时钙钛矿光阳极的光电流-外电势曲线^[68]; (c) FTO/PEDOT:PSS/CH₃NH₃PbI₃/PCBM/PEIE/Ag的材料能带和功函数匹配图; (d) 光催化器件在开关光循环条件下的I-V图^[69]

Fig. 18. (a) Schematic diagram of FTO/m-TiO₂/CH₃NH₃PbI₃/Spiro-MeOTAD/Au/Catalyst integrated photoelectrolysis device with perovskite photoelectrode; (b) photocurrent verus potential comparison diagram of perovskite photoanode with Ni catalyst and Ni catalyst under simulated light^[68]; (c) energy and work function matching of FTO/PEDOT:PSS/CH₃NH₃PbI₃/PCBM/PEIE/Ag; (d) photocurrent verus potential diagram of photocatalytic device switching^[69]

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表 1 部分压电和铁电材料的光催化降解甲基橙染料或CO₂的性能比较

Table 1. Photocatalytic degradation of organic compounds using a variety of catalytic methods.

材料及结构 (铁电材料为粗体)	铁电	带隙/eV	激励源	催化降解物	催化活性	污染性	稳定性(性能/时间)	文献
BiFeO₃纳米粉体	强	2.18	紫外可见光	甲基橙	8 h降解90%	中	—	[14]
FTO玻璃/BiVO₄/BiFeO₃/CuInS₂	强	2.1—2.7	可见光	对硝基苯酚	K_obs = 0.02 min^–1	中	相对稳定/5次循环	[56]
NaNbO₃纳米棒	强	3.3	光+超声振动	甲基蓝	—	弱	98%/3次循环	[42]
BaTiO₃@Ag纳米颗粒	强	3.2	光	罗丹明B	K_obs = 0.087 min^–1	弱		[43]
BaTiO₃/MoO₃	强	3.2	紫外-可见光	罗丹明B	60 min降解86%	弱	95%/5次循环	[44]
BaTiO₃/Ag₂O纳米棒	强	3.2	紫外光+ 超声振动	罗丹明B (c = 15 mg·L^–1 )	K_obs = 0.031 min^–1	弱	50%/5次循环	[18]
BaTiO₃@非晶BaTiO_3–_x	强	3.2	可见光	甲基蓝	5 h降解62.4%	弱	97%/5次循环	[45]
PbTiO₃/TiO₂纳米片	强	3.6	氙灯可见光	甲基蓝	K_obs = 0.057 min^–1 132.6 μmol·h^–1 ·g^–1 产H₂	强	—	[46]
KNbO₃/g-C₃N₄	强	3.28	氙灯可见光	—	180 μmol·h^–1 ·g^–1 产H₂	弱	95%/4次循环	[47]
{001} Bi₃TiNbO₉纳米片	—	3.3	氙灯可见光	—	342.6 μmol·h^–1 ·g^–1 产H₂	中	—	[48]
KNbO₃颗粒	强	3.28	光	罗丹明B	K_obs = 0.317 min^–1	弱	—	[49]
KNbO₃纳米片	强	3.07	可见光+超声振动	罗丹明B	K_obs = 0.022 min^–1 2 h降解92.6%	弱	—	[50]
FTO玻璃/ZnSnO₃纳米线	弱	3.7	光+压力	甲基蓝	K_obs = 0.007 min^–1	弱	90%/1 h	[51]
FTO/ZnSnO_3–_x纳米线	弱	2.4—3.7	光、超声振动、光和超声振动	—	3562, 3453, 3882 μmol·h^–1 ·g^–1 产H₂	弱	在振动下相对稳定/7 h	[52]
FTO/Zn_1–_xSnO₃ 纳米线	弱	2.4—3.7	紫外光+振动	甲基蓝	K_obs = 0.015 min^–1	弱	—	[53]
PZT@TiO₂核壳结构	强	3.6	光+搅拌	罗丹明B	80 min完全降解	强	—	[54]
BiOI-BaTiO₃纳米粒子	强	3.2	可见光	甲基橙	90 min降解95.4%	弱	—	[55]
ZnO纳米线	压电	3.37	光+摇摆	甲基蓝	K_obs = 0.025 min^–1	弱	99%/3次循环	[57]
ZnO纳米片/TiO₂纳米颗粒	压电	3.37	可见光	甲基橙	K_obs = 0.038 min^–1	弱	相对稳定/11 h	[58]
Ag-ZnO纳米线	压电	3.37	光+弯折	罗丹明B	K_obs = 0.052 min^–1	弱	90%/8次循环	[59]

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表 2 近年部分铁电材料光电催化分解水的研究进展(这里ITO, FTO, SrTiO₃, Nb-SrTiO₃和glass是薄膜基片, PCBM是[6,6]-苯基C61-丁酸甲酯, PEIE是乙氧基化聚乙烯亚胺; PEDOT:PSS是聚苯乙烯磺酸盐(3, 4-乙撑二氧噻吩))

Table 2. Photoelectrochemical water splitting of ferroelectric materials in recent years, where ITO, FTO, SrTiO₃, Nb-SrTiO₃ and glass are substrate of films, PCBM is [6,6]-phenyl-C61-butyric acid methyl ester, PEIE is ethoxylated polyethylenimine, PEDOT:PSS is poly(3, 4-ethylenedioxythiophene) polystyrene sulfonate and FM is In_0.51Bi_0.325Sn_0.165 as protective layer

材料和结构 (铁电材料为粗体)	铁电	PCE/%	带隙/eV	电解液	光源	工作电极电势	光电流密度/ mA·cm^–2	污染性	稳定性 (性能/时间)	文献
ITO/BiFeO₃/Au	强	—	2.16—2.7	0.1 mol/L KCl	AM1.5G	0 V vs. Ag/AgCl	0.05	弱	—	[60]
SrTiO₃/SrRuO₃/(111)BiFeO₃	强	—	2.16—2.7	0.5 mol/L Na₂SO₄	AM1.5G	0 V vs. Ag/AgCl	0.08	弱	100%/700 s	[61]
SrTiO₃/CaRuO₃/(111) Bi₂FeCrO₆	强	—	1.9—2.1	1 mol/L Na₂SO₄	AM1.5G	0 V vs. Ag/AgCl	–2.02	弱	—	[15]
SrTiO₃/SrRuO₃/Bi₂FeCrO₆/ NiO	强	—	1.8— –2.7	1 mol/L Na₂SO₄	AM1.5G	1.2 V vs. RHE	0.9	弱	95%/7 h	[62]
TiO₂@PbTiO₃ 核壳结构	强	—	3.6	—	氙灯100 mW·cm^–2	—	132 μmol·g^–1 H₂	强	—	[63]
FTO/NaNbO₃	强	—	3.37	0.5 mol/L Na₂SO₄	AM1.5G	1 V vs. Ag/AgCl	0.51	弱	—	[64]
ITO/KNbO₃纳米片	强	—	2.86	0.5 mol/L Na₂SO₄	AM1.5G	0 V vs. Ag/AgCl	0.82	弱	—	[50]
(001) LiNbO₃单晶	强	—	3.26	mol/LK₃PO₄	AM1.5G	1.23 V vs. RHE	0.15	弱	—	[65]
FTO/TiO₂@BaTiO₃/Ag₂O	强	—	3.2	1 mol/LNaOH	AM1.5G	0.8 V vs. Ag/AgCl	1.8	弱	97%/1 h	[66]
FTO/TiO₂@SrTiO₃ (10 nm四方铁电相)	弱	—	3.2	1 mol/LNaOH	AM1.5G	1.23 V vs. RHE	1.43	弱	—	[67]
Glass/FTO/m-TiO₂/CH₃NH₃PbI₃/ Spiro-MeOTAD/Au/Ni	弱	14.4	1.5	—	AM1.5G	1.0 V vs. SHE	17.4	强	66%/1 h	[68]
FTO/PEDOT:PSS/CH₃NH₃PbI₃/ PCBM/PEIE/Ag/FM	弱	7.7	1.5	—	AM1.5G	1.2 V vs. RHE	15.0	强	80%/1 h	[69]
ITO/NiO/CH₃NH₃PbI₃/ PCBM/Ag/Ti/Pt	弱	16.1	1.5	0.5 mol/L H₂SO₄	AM1.5G	1.2 V vs. RHE	18	强	70%/12 h	[70]
CH₃NH₃PbI₃ solar cells, a cell for H₂O splitting	弱	15.7	1.5	—	AM1.5G	—	10	强	75%/10 h	[71]
FTO/BiVO₄/black-phosphorene/ NiOOH	无	—	2.4—2.5	0.5 mol/L KH₂PO₄ K₂HPO₄	AM1.5G	1.23 V vs. RHE	4.48	强	99%/60 h	[72]
FTO/H:TiO₂	无	1.63	3.2	1 mol/LNaOH	AM1.5G	–0.6 V vs. Ag/AgCl	1.97	弱	94%/28 h	[73]

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