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Research progress and prospects of photocatalytic devices with perovskite ferroelectric semiconductors

Cui Zong-Yang Xie Zhong-Shuai Wang Yao-Jin Yuan Guo-Liang Liu Jun-Ming

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Research progress and prospects of photocatalytic devices with perovskite ferroelectric semiconductors

Cui Zong-Yang, Xie Zhong-Shuai, Wang Yao-Jin, Yuan Guo-Liang, Liu Jun-Ming
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  • 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.
      Corresponding author: Yuan Guo-Liang, yuanguoliang@njust.edu.cn
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  • 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

    Figure 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

    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]

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

    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]

    Figure 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]

    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]

    Figure 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]

    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]

    Figure 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]

    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]

    Figure 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]

    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]

    Figure 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]

    图 8  SrTiO3/CaRuO3/Bi2FeCrO6样品在Bi2FeCrO6 的(a)初始极化状态、(b) +P (即Pup)、(c) –P(即Pdown)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]

    Figure 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 (Pup, –25 V) and (c) and positive poling (Pdown, 25 V)[15]; (d) schematic diagram of the experimental setup and (e) photocurent versus potential (vs. RHE) curves of SrTiO3/SrRuO3/Bi2FeCrO6/NiO[62]

    图 9  (a) BaTiO3铁电材料的能带结构及其退极化场EP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]

    Figure 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]

    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]

    Figure 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]

    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Kobs (即KMB); (d) 光催化产氢速率[46]

    Figure 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]

    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]

    Figure 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]

    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Kobs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Kobs(即k)对比[50]; (d) ZnSnO3–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]

    Figure 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 (Kobs) 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) Kobs (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 ZnSnO3–x nanowires as a function of time under applying light and ultrasonic vibration simultaneously[52]

    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]

    Figure 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].

    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]

    Figure 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]

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

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

    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]

    Figure 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]

    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[69]

    Figure 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]

    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2.18紫外可见光甲基橙8 h降解90%[14]
    FTO玻璃/BiVO4/BiFeO3/CuInS22.1—2.7可见光对硝基苯酚Kobs = 0.02 min–1 相对稳定/5次循环[56]
    NaNbO3纳米棒3.3光+超声振动甲基蓝98%/3次循环[42]
    BaTiO3@Ag纳米颗粒3.2罗丹明BKobs = 0.087 min–1 [43]
    BaTiO3/MoO33.2紫外-可见光罗丹明B60 min降解86%95%/5次循环[44]
    BaTiO3/Ag2O纳米棒3.2紫外光+ 超声振动罗丹明B
    (c = 15 mg·L–1 )
    Kobs = 0.031 min–1 50%/5次循环[18]
    BaTiO3@非晶BaTiO3–x3.2可见光甲基蓝5 h降解62.4%97%/5次循环[45]
    PbTiO3/TiO2纳米片3.6氙灯可见光甲基蓝Kobs = 0.057 min–1
    132.6 μmol·h–1 ·g–1 产H2
    [46]
    KNbO3/g-C3N43.28氙灯可见光180 μmol·h–1 ·g–1 产H295%/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[48]
    KNbO3颗粒3.28罗丹明BKobs = 0.317 min–1 [49]
    KNbO3纳米片3.07可见光+超声振动罗丹明BKobs = 0.022 min–1 2 h降解92.6%[50]
    FTO玻璃/ZnSnO3纳米线3.7光+压力甲基蓝Kobs = 0.007 min–1 90%/1 h[51]
    FTO/ZnSnO3–x纳米线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
    在振动下相对稳定/7 h[52]
    FTO/Zn1–xSnO3 纳米线2.4—3.7紫外光+振动甲基蓝Kobs = 0.015 min–1 [53]
    PZT@TiO2核壳结构3.6光+搅拌罗丹明B80 min完全降解[54]
    BiOI-BaTiO3纳米粒子3.2可见光甲基橙90 min降解95.4%[55]
    ZnO纳米线压电3.37光+摇摆甲基蓝Kobs = 0.025 min–1 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Kobs = 0.038 min–1 相对稳定/11 h[58]
    Ag-ZnO纳米线压电3.37光+弯折罗丹明BKobs = 0.052 min–1 90%/8次循环[59]
    DownLoad: CSV

    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 In0.51Bi0.325Sn0.165 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/Au2.16—2.70.1 mol/L KClAM1.5G0 V vs. Ag/AgCl0.05[60]
    SrTiO3/SrRuO3/(111)BiFeO32.16—2.70.5 mol/L Na2SO4AM1.5G0 V vs. Ag/AgCl0.08100%/700 s[61]
    SrTiO3/CaRuO3/(111) Bi2FeCrO61.9—2.11 mol/L Na2SO4AM1.5G0 V vs. Ag/AgCl–2.02[15]
    SrTiO3/SrRuO3/Bi2FeCrO6/ NiO1.8— –2.71 mol/L Na2SO4AM1.5G1.2 V vs. RHE0.995%/7 h[62]
    TiO2@PbTiO3 核壳结构3.6氙灯100 mW·cm–2132 μmol·g–1 H2[63]
    FTO/NaNbO33.370.5 mol/L Na2SO4AM1.5G1 V vs. Ag/AgCl0.51[64]
    ITO/KNbO3纳米片2.860.5 mol/L Na2SO4AM1.5G0 V vs. Ag/AgCl0.82[50]
    (001) LiNbO3单晶3.26mol/LK3PO4AM1.5G1.23 V vs. RHE0.15[65]
    FTO/TiO2@BaTiO3/Ag2O3.21 mol/LNaOHAM1.5G0.8 V vs. Ag/AgCl1.897%/1 h[66]
    FTO/TiO2@SrTiO3
    (10 nm四方铁电相)
    3.21 mol/LNaOHAM1.5G1.23 V vs. RHE1.43[67]
    Glass/FTO/m-TiO2/CH3NH3PbI3/
    Spiro-MeOTAD/Au/Ni
    14.41.5AM1.5G1.0 V vs. SHE17.466%/1 h[68]
    FTO/PEDOT:PSS/CH3NH3PbI3/
    PCBM/PEIE/Ag/FM
    7.71.5AM1.5G1.2 V vs. RHE15.080%/1 h[69]
    ITO/NiO/CH3NH3PbI3/
    PCBM/Ag/Ti/Pt
    16.11.50.5 mol/L H2SO4AM1.5G1.2 V vs. RHE1870%/12 h[70]
    CH3NH3PbI3 solar cells,
    a cell for H2O splitting
    15.71.5AM1.5G1075%/10 h[71]
    FTO/BiVO4/black-phosphorene/
    NiOOH
    2.4—2.50.5 mol/L KH2PO4 K2HPO4AM1.5G1.23 V vs. RHE4.4899%/60 h[72]
    FTO/H:TiO21.633.21 mol/LNaOHAM1.5G–0.6 V vs. Ag/AgCl1.9794%/28 h[73]
    DownLoad: CSV
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Metrics
  • Abstract views:  34561
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Publishing process
  • Received Date:  25 February 2020
  • Accepted Date:  06 April 2020
  • Published Online:  20 June 2020

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