高等学校化学学报 ›› 2022, Vol. 43 ›› Issue (1): 20210613.doi: 10.7503/cjcu20210613
收稿日期:
2021-08-25
出版日期:
2022-01-10
发布日期:
2021-10-08
通讯作者:
张冀杰
E-mail:zhangjijie@nankai.edu.cn
基金资助:
SHI Xiaofan, ZHU Jian, BAI Tianyu, FU Zixuan, ZHANG Jijie(), BU Xianhe
Received:
2021-08-25
Online:
2022-01-10
Published:
2021-10-08
Contact:
ZHANG Jijie
E-mail:zhangjijie@nankai.edu.cn
Supported by:
摘要:
光催化分解水是将太阳能转化为化学能的有效手段之一. 相比于粉末光催化, 采用H型电解池的光 电催化方法具有材料选择范围大、 载流子迁移和分离效率高、 电极易于回收等优点. 近年来, 金属有机框架 材料(MOFs)在光电催化水分解领域得到越来越多的应用. 相比于传统无机催化剂, MOFs光电极具有比表面积大、 结构易于调控等独特优势. 本文按照MOFs的应用形式分为纯MOFs、 MOFs与其它催化剂的复合结构和MOFs衍生物3类, 总结了近年来MOFs在光电催化水分解领域的研究现状和进展, 介绍了光催化/电催化领域的部分典型研究成果, 最后讨论了MOFs在光电催化水分解领域研究的重点和热点, 并对其未来发展做出了展望.
中图分类号:
TrendMD:
史潇凡, 朱剑, 白田宇, 付子萱, 张冀杰, 卜显和. 金属-有机框架材料在光电催化水分解领域的研究进展. 高等学校化学学报, 2022, 43(1): 20210613.
SHI Xiaofan, ZHU Jian, BAI Tianyu, FU Zixuan, ZHANG Jijie, BU Xianhe. Research Status and Progress of MOFs with Application in Photoelectrochemical Water-splitting. Chem. J. Chinese Universities, 2022, 43(1): 20210613.
Fig.1 Basic structure of PEC water?splitting system(A)[2], representation of the six types of low?lying excited states found in MOFs as a result of the different characters of the valence band and conduction band edges(B)[54](A) Copyright 2018, Wiley?VCH; (B) Copyright 2020, Wiley?VCH.
Fig.2 2D Co?MOFs using as the photoanode for photoelectrochemical water?splitting(A)[65], crystal and facet structure of MOF?71(B)[66](A) Copyright 2019, American chemical society; (B) Copyright 2020, Open access.
Fig.3 TiO2@MIL?125?NH2 photoanode(A)[72] and BiVO4@CoNi?MOF photoanode for PEC water?splitting(B)[75](A) Copyright 2019, Elsevier; (B) Copyright 2020, Elsevier.
Fig.4 Conjugated π electrons of MOFs driving charge separation for enhanced photoelectrochemical water oxidation(A)[83], mechanisms for explaining the enhanced PEC water splitting efficiency of the ZnO@ZIF?8/ZIF?67 photoelectrode(B)[87](A) Copyright 2021, Wiley?VCH; (B) Copyright 2018, Elsevier.
Metal center | Photoelectrode | Light source | Electrolyte | Potential/V (vs. RHE) | Photocurrent density/ (mA·cm-2) |
---|---|---|---|---|---|
Ti | TiO2@NH2?MIL?125[ | Xenon lamp | Artificial seawater | 1.21 | 3.04 |
TiO2/NH2?MIL?125[ | AM 1.5G | 1 mol/L NaOH | 1.23 | 1.63 | |
Fe/Co/Ni | BiVO4@Co2(bim)4[ | AM 1.5G | 0.5 mol/L Na2SO4 | 1.23 | 1.20 |
Fe2O3/NH2?MIL?101(Fe)[ | AM 1.5G | 1 mol/L NaOH | 1.23 | 2.27 | |
Ti doped Fe2O3@ZIF?67 | AM 1.5G | 1 mol/L KOH | 1.23 | 0.80 | |
Fe@Ni?MOF/Fe2O3:Ti[ | AM 1.5G | 1 mol/L KOH | 1.23 | 2.30 | |
BiVO4@CoNi?MOF[ | AM 1.5G | 0.5 mol/L Na2SO4 | 1.23 | 3.20 | |
FeNi?MOF/TNTA[ | AM 1.5G | 0.1 mol/L Na2SO4 | 1.23 | 1.90 | |
Fe2O3/MIL?88B@ZIF?67[ | AM 1.5G | 1 mol/L NaOH | 1.23 | 2.52 | |
Zr | TiO2//UiO?67[ | Xenon lamp(280―800 nm) | 1 mol/L H2SO4 | 1.23 | 2.10 |
0.5 mol/L Na2SO4 | 1.91 | ||||
1 mol/L KOH | 2.38 | ||||
ZnO/Zr?MOF?25%[ | AM 1.5G | Acetonitrile solution with 1 mmol/L I2 | 1.20 | 4.12 | |
Zn | ZnO/ZIF?8@N?CDs[ | AM 1.5G | 0.5 mol/L Na2SO4 | 1.23 | 0.35 |
ZnO@ZIF?8/ZIF?67[ | AM 1.5G | 0.5 mol/L Na2SO4 | 1.23 | 0.11 | |
Co3O4@NH2?MOF?5/NF[ | Visible light | 1 mol/L KOH | 1.49 | 32.93 | |
ZnNi?MOF@ZnO[ | AM 1.5G | 0.5 mol/L Na2SO4 | 1.20 | 1.40 |
Table 1 Performance of reported MOFs-based heterostructure photoelectrodes
Metal center | Photoelectrode | Light source | Electrolyte | Potential/V (vs. RHE) | Photocurrent density/ (mA·cm-2) |
---|---|---|---|---|---|
Ti | TiO2@NH2?MIL?125[ | Xenon lamp | Artificial seawater | 1.21 | 3.04 |
TiO2/NH2?MIL?125[ | AM 1.5G | 1 mol/L NaOH | 1.23 | 1.63 | |
Fe/Co/Ni | BiVO4@Co2(bim)4[ | AM 1.5G | 0.5 mol/L Na2SO4 | 1.23 | 1.20 |
Fe2O3/NH2?MIL?101(Fe)[ | AM 1.5G | 1 mol/L NaOH | 1.23 | 2.27 | |
Ti doped Fe2O3@ZIF?67 | AM 1.5G | 1 mol/L KOH | 1.23 | 0.80 | |
Fe@Ni?MOF/Fe2O3:Ti[ | AM 1.5G | 1 mol/L KOH | 1.23 | 2.30 | |
BiVO4@CoNi?MOF[ | AM 1.5G | 0.5 mol/L Na2SO4 | 1.23 | 3.20 | |
FeNi?MOF/TNTA[ | AM 1.5G | 0.1 mol/L Na2SO4 | 1.23 | 1.90 | |
Fe2O3/MIL?88B@ZIF?67[ | AM 1.5G | 1 mol/L NaOH | 1.23 | 2.52 | |
Zr | TiO2//UiO?67[ | Xenon lamp(280―800 nm) | 1 mol/L H2SO4 | 1.23 | 2.10 |
0.5 mol/L Na2SO4 | 1.91 | ||||
1 mol/L KOH | 2.38 | ||||
ZnO/Zr?MOF?25%[ | AM 1.5G | Acetonitrile solution with 1 mmol/L I2 | 1.20 | 4.12 | |
Zn | ZnO/ZIF?8@N?CDs[ | AM 1.5G | 0.5 mol/L Na2SO4 | 1.23 | 0.35 |
ZnO@ZIF?8/ZIF?67[ | AM 1.5G | 0.5 mol/L Na2SO4 | 1.23 | 0.11 | |
Co3O4@NH2?MOF?5/NF[ | Visible light | 1 mol/L KOH | 1.49 | 32.93 | |
ZnNi?MOF@ZnO[ | AM 1.5G | 0.5 mol/L Na2SO4 | 1.20 | 1.40 |
Fig.5 Ti?MOF derived heterophase TiO2 photoanode(A)[94] and Co?MOF derived BiVO4@Co3O4 photoanode(B)[95](A) Copyright 2020, Elsevier; (B) Copyright 2019, Elsevier.
MOFs precursor | MOFs?based photoelectrode | Light source | Electrolyte | Potential/V (vs. RHE) | Photocurrent density/ (mA·cm-2) |
---|---|---|---|---|---|
NH2?MIL?125 | MoS2 coupled dual?phase TiO2[ | AM 1.5G | 0.35 mol/L Na2S and 0.25 mol/L Na2SO3 | 1.2 | 1.2 |
TixFe1-xOy@Fe2O3[ | AM 1.5G | 1 mol/L NaOH | 1.23 | 0.724 | |
M?TiO2/CdSe[ | AM 1.5G | 0.25 mol/L Na2S and 0.35 mol/L Na2SO3 | 0.9 | 7.55 | |
ZIF?67 | Co3O4/BiVO4[ | Xenon lamp | 0.5 mol/L K2H2PO4 with Na2SO3 | 1.23 | 2.35 |
Co3O4/TiO2[ | Xenon lamp | 1 mol/L NaOH | 1.23 | 1.04 | |
Co3C/TiO2[ | ― | 1 mol/L NaOH | 1.23 | 2.6 | |
ZIF?8/ZIF?67 | Zn0.4Co0.6O4/BiVO4[ | AM 1.5G | 0.5 mol/L K2H2PO4 | 1.23 | 3.55 |
MIL?88B | Fe2O3@C photoanode[ | AM 1.5G | Neutral aqueous | 1.65 | 2.5 |
FeP@C photocathode[ | AM 1.5G | -0.07 | 10 | ||
HKUST?1 | FeOOH/Cu2O/Ce?Fe2O3[ | AM 1.5G | 1 mol/L KOH | 1.23 | 4.2 |
Table 2 Performance of reported MOFs-derived photoelectrodes
MOFs precursor | MOFs?based photoelectrode | Light source | Electrolyte | Potential/V (vs. RHE) | Photocurrent density/ (mA·cm-2) |
---|---|---|---|---|---|
NH2?MIL?125 | MoS2 coupled dual?phase TiO2[ | AM 1.5G | 0.35 mol/L Na2S and 0.25 mol/L Na2SO3 | 1.2 | 1.2 |
TixFe1-xOy@Fe2O3[ | AM 1.5G | 1 mol/L NaOH | 1.23 | 0.724 | |
M?TiO2/CdSe[ | AM 1.5G | 0.25 mol/L Na2S and 0.35 mol/L Na2SO3 | 0.9 | 7.55 | |
ZIF?67 | Co3O4/BiVO4[ | Xenon lamp | 0.5 mol/L K2H2PO4 with Na2SO3 | 1.23 | 2.35 |
Co3O4/TiO2[ | Xenon lamp | 1 mol/L NaOH | 1.23 | 1.04 | |
Co3C/TiO2[ | ― | 1 mol/L NaOH | 1.23 | 2.6 | |
ZIF?8/ZIF?67 | Zn0.4Co0.6O4/BiVO4[ | AM 1.5G | 0.5 mol/L K2H2PO4 | 1.23 | 3.55 |
MIL?88B | Fe2O3@C photoanode[ | AM 1.5G | Neutral aqueous | 1.65 | 2.5 |
FeP@C photocathode[ | AM 1.5G | -0.07 | 10 | ||
HKUST?1 | FeOOH/Cu2O/Ce?Fe2O3[ | AM 1.5G | 1 mol/L KOH | 1.23 | 4.2 |
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