石墨烯-有机物复合光催化材料及其应用

刘洋洋; 易敏; 陈涛; 董舒宇

doi:10.13801/j.cnki.fhclxb.20220628.003

石墨烯-有机物复合光催化材料及其应用

doi: 10.13801/j.cnki.fhclxb.20220628.003

刘洋洋^{1, 2, ,},
易敏^{1, 2},
陈涛^{1, 2},
董舒宇¹

1.
首钢集团有限公司技术研究院，北京 100043
2.
绿色可循环钢铁流程北京市重点实验室，北京 100043

详细信息

通讯作者:
刘洋洋，硕士，工程师，研究方向为石墨烯及相关复合材料　E-mail: m15210570625@163.com

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2022-04-25
- 修回日期: 2022-05-31
- 录用日期: 2022-06-18
- 网络出版日期: 2022-06-29
- 刊出日期: 2023-04-15

Applications of graphene-organic compound photocatalytic materials

LIU Yangyang^{1, 2
, ,},
YI Min^{1, 2},
CHEN Tao^{1, 2},
DONG Shuyu¹

1.
Shougang Research Institute of Technology, Beijing 100043, China
2.
Beijing Key Laboratory of Green Recyclable Process for Iron and Steel Production Technology, Beijing 100043, China

摘要

摘要: 光催化技术以其绿色安全的特点在能源和环境领域显示出巨大的应用潜力。近年来，有机物光催化剂以其可见光响应及成本较低等优势逐渐进入人们的视野，但也存在一些不足，而石墨烯材料的大比表面积、高载流子迁移率等性质，在催化剂构建领域具有天然优势。本文针对石墨烯-有机物半导体光催化材料，在总结石墨烯在材料中的基本作用的基础上，介绍了石墨烯/共轭聚合物、石墨烯/金属有机骨架、石墨烯/染料3种典型的石墨烯-有机物光催化材料及多种合成方法。进一步阐述了此类材料在能源和环境领域，包括光解水析氢、CO₂还原、有机物降解、重金属离子还原及细菌灭活等领域的应用。最后对石墨烯-有机物复合光催化材料的未来发展提出了建议。
- 石墨烯 /
- 有机物 /
- 光催化 /
- 能源与环境 /
- 金属有机骨架
Abstract: The great application potential of photocatalysis technology with green and safe characteristics has been shown on the field of energy and environment. Over recent years, the organic photocatalysts have been familiar with their advantages of visible light response, low cost and also some shortcomings. Graphene materials which surface area was large and high carrier mobility have natural advantages in the field of catalyst construction. The graphene-organic semiconductor as an photocatalysis materials, this work introduced three typical graphene-organic photocatalysis materials: Graphene/conjugated polymer, graphene/metal organic framework and graphene/dye and various synthesis methods. This work have discussed some application fields of energy and environment, including photocatalysis of water for hydrogen evolution, CO₂ reduction, organic matter degradation, heavy metal ion reduction and bacterial inactivation etc. Some suggestions for future development of the graphene materials with organic compound photocatalyst are given.
- graphene /
- organic /
- photocatalysis /
- energy and environment /
- metal organic framework

HTML全文

图 1 石墨烯(G)-有机物复合光催化材料的种类、制备及应用情况

Figure 1. Types, preparation and application of graphene (G)-organic compound photocatalytic materials

GO—Graphene oxide; X—Dopant atoms

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图 2 暴露在联氨蒸气下氧化石墨烯(GO)的带隙逐渐减小^[21]

Figure 2. Gradual decrease in optical band gap of GO upon exposure to hydrazine vapors^[21]

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图 3 光电流响应图^[24]

Figure 3. Photocurrent responses spectra^[24]

TPA—Triphenylamine

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图 4 可见光下材料的光电流对比^[27]

Figure 4. Photocurrent action spectra of the materials^[27]

RGO—Reduced graphene oxide; ZnP—Porphyrin; NPs—Nanoparticles

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图 5 多孔g-C₃N₄(PCN)/AgBr/RGO复合材料制备示意图^[34]

Figure 5. Schematic diagrams of preparation process of the porous g-C₃N₄(PCN)/AgBr/RGO nanocomposite^[34]

CTAB—Cetyltrimethyl ammonium bromide

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图 6 太阳光照射下BiOCl/RGO/质子化g-C₃N₄ (PTCN)光催化剂中光诱导载流子分离和传输示意图^[36]

Figure 6. Schematic diagram for photoinduced charge carrier separation and transportation in BiOCl/RGO/protonation g-C₃N₄ (PTCN) photocatalyst under simulated solar light irradiation^[36]

SHE—Standard hydrogen electrode; VB—Valence band; CB—Conduction band; TC—Tetracycline

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图 7 Co-金属有机物层(MOL)@GO的合成过程示意图^[52]

Figure 7. Schematic diagrams of preparation process of Co-metal-organic layers(MOL)@GO^[52]

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图 8 g-C₃N₄/RGO/MoS₂三元2D纳米结(a)和2D-0D (b)光催化剂示意图^[43]

Figure 8. Schematic diagrams of g-C₃N₄/RGO/MoS₂ ternary 2D nanojunction photocatalysts (a) and 2D-0D photocatalysts (b)^[43]

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图 9 吸附一个氢原子(a)、一个氢分子(b)和多个不同界面氢分子(c)的石墨烯(G)-C₃N₄-G三明治结构的优化布局^[42]

Figure 9. Optimized configurations of the G-C₃N₄-G sandwich adsorbed with one H atom (a), one H₂ molecule (b) and many H₂ molecules (c) with different interfacial spaces^[42]

d—Interfacial spaces

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图 10 GO/g-C₃N₄/聚丙烯腈(PAN)纤维((a)~(c))及GO (d)的透射电镜图^[40]

Figure 10. TEM images of GO/g-C₃N₄/polyacrylonitrile (PAN) fiber ((a)-(c)) and GO (d)^[40]

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图 11 可见光驱动光催化细菌灭活机制：g-C₃N₄(CN)-RGO-环辛硫(S₈) (a)、RGO-CN-S₈ (b)有氧环境下；CN-RGO-S₈ (c)、RGO-CN-S₈ (d)无氧环境下^[48]

Figure 11. Schematic illustration of the visible light driven photocatalytic bacterial inactivation mechanisms: g-C₃N₄(CN)-RGO-S₈ (a), RGO-CN-S₈ (b) in aerobic condition; CN-RGO-S₈ (c), RGO-CN-S₈ (d) in anaerobic condition^[48]

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表 1 石墨烯-共轭聚合物复合材料的制备方法及光催化效果

Table 1. Preparation method and photocatalytic effects of graphene-conjugated polymer composites

Composites	Preparation	Application	Effects	Role of graphene	Ref.
PCN/AgBr/RGO	Ultrasonic hydrothermal	Degradation of organics	Tetracycline: Degradation rate 78.4% in 90 min	Conduction of electrons and holes between the two catalysts	[34]
CNNP/GO	Acid ultrasonic	Degradation of organics	Methylene blue: Degradation rate 67% in 3 h	Changing the band gap and promoting the separation of photogenerated carriers	[35]
BiOCl/RGO/PTCN	Ultrasonic hydrothermal	Degradation of organics	Tetracycline: k=1.58×10⁻² min⁻¹	Conduction of electrons between the two catalysts	[36]
MCN/RGOA	Ultrasonic	Degradation of organics	Rhodamine B: k=3.78×10⁻² min⁻¹	Accelerating electron conduction and organic matter adsorption	[37]
RGO-CNDs	Ultrasonic hydrothermal	Degradation of organics	Methylene blue: Degradation rate 90% in 1 h	Changing the band gap, promoting the separation of photogenerated carriers and organic matter adsorption	[38]
NG@g-C₃N₄	Ultrasonic	Degradation of organics	Methyl orange: k=2.76×10⁻² min⁻¹	Promoting the separation of photogenerated carriers	[39]
GO/g-C₃N₄	Spinning	Degradation of organics	Rhodamine B: degradation rate 91.1% in 100 min	Broaden the available light range	[40]
GO-Ln-DPDPP	Ultrasonic	Hydrogen production	549 μmol·h⁻¹·g⁻¹	Photocatalyst	[41]
G_F-C_xN_y	Simulation calculation	Hydrogen production	—	Photocatalyst	[42]
g-C₃N₄/ RGO/MoS₂	Calcination hydrothermal	Hydrogen production	317 µmol·h⁻¹·g⁻¹	Promoting the separation of photogenerated carriers	[43]
aza-CMP^*/RGO/C₂N	Calcination	Hydrogen production	10 µmol·h⁻¹	Promoting the separation of photogenerated carriers	[44]
g-C₃N₄/GA	Ultrasonic hydrothermal	CO₂ reduction	3833 μmol·h⁻¹·g⁻¹	Accelerating electron conduction and organic matter adsorption	[45]
g-C₃N₄@PPy-RGO	In situ synthesis	Heavy metal reduction	Cr(VI) degradation rate 100% in 150 min	Changing the band gap, accelerating electron conduction and organic matter adsorption	[46]
PDCN/GO	Ultrasonic	Bacterial inactivation	Escherichia coli: Inactivation rate 98% in 7 h	Promoting the separation of photogenerated carriers	[47]
RGO-CN-S₈ and CN-RGO-S₈	Illumination	Bacterial inactivation	Escherichia coli: Inactivation rate 100% in 4 h	Promoting the separation of photogenerated carriers	[48]
Notes: aza-CMP^*—aza fused π conjugated microporous polymer; CNNP—g-C₃N₄ nanoparticles; MCN—Mesoporous g-C₃N₄; A—Aerogel; CNDs—g-C₃N₄ nanodots; NG—N-doped graphene; DPDPP—Diphenylporphyrin; PDCN—P-doped g-C₃N₄; G_F—Graphene layers modifified by functional groups; GA—Graphene aerogel; PPy—Polypyrrole; S₈—Cyclooctene sulfur; k—Reaction rate constant.

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表 2 石墨烯-金属有机骨架复合材料的制备方法及光催化效果

Table 2. Preparation method and photocatalytic effect of graphene-MOFs composites

Composites	Preparation	Application	Effects	Role of graphene	Ref.
ZnO/GO+(Cu-BTC)	Electrostatic self-assembly	Hydrogen production	191 µmol·h⁻¹·g⁻¹	Accelerating electron conduction	[50]
NH₂-MIL-125(Ti)/PPy-RGO	Electrostatic self-assembly	Hydrogen production	91 µmol·h⁻¹·g⁻¹	Promoting the separation of photogenerated carriers	[53]
G wrapped ZIF-8	Electrostatic self-assembly	Hydrogen production	41.4 mmol·h⁻¹·g⁻¹	Promoting the separation of photogenerated carriers	[54]
MIL-53(Fe)-RGO	Electrostatic self-assembly hydrothermal	Heavy metal reduction	Cr(VI) degradation rate 100% in 80 min	Broaden the available light range	[55]
G/MIL-53(Fe)	Hydrothermal	Degradation of organics	Rhodamine B: k=7.77×10⁻² min⁻¹	Accelerating electron conduction, broaden the available light range	[51]
RMZ	Microwave	Degradation of organics	Methylene blue degradation rate 82% in 2 h	Accelerating electron conduction and organic matter adsorption	[56]

M88/GO	Ultrasonic hydrothermal	Degradation of organics	Rhodamine B: k=6.45×10⁻² min⁻¹	Changing the band gap and increasing the active sites	[57]
Co-MOL@GO	Hydrothermal growth	CO₂ reduction	CO productivity 18.02 mmol·g⁻¹·h⁻¹	Reducing surface energy and accelerating electron conduction	[52]
UIO-66-NH₂/G	Microwave digestion	CO₂ reduction	Reduction rate 532 μmol·h⁻¹·g⁻¹	Accelerating electron conduction, broaden the available light range	[58]
2D/2D RGO/MOF	Ultrasonic	CO₂ reduction	CO productivity 34.5 mmol·h⁻¹·g⁻¹	Accelerating electron conduction, broaden the available light range	[59]
Notes: BTC—2-methylimidazole zinc salt; NH₂-MIL-125(Ti)—Coordination metal Ti ligand, C₄₈H₃₄N₆O₃₆Ti₈; ZIF-8—2-methylimidazole zinc salt; MIL-53(Fe)—Coordination metal Fe ligand terephthalic acid, C₈H₅FeO₅; RMZ—Reduced graphene oxide incorporated MOF derived ZnO composites; M88—Coordination metal Fe ligand fumaric acid, C₁₂H₆O₁₃Fe₃; UIO-66-NH₂—Amino functionalized organometallic framework, G—Graphene.

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