MOF基的光解水制氢催化剂研究进展

陈柏瑜; 胡天丁; 陕绍云; 支云飞; 张楚茹; 吴琪

doi:10.13801/j.cnki.fhclxb.20211011.001

MOF基的光解水制氢催化剂研究进展

doi: 10.13801/j.cnki.fhclxb.20211011.001

昆明理工大学化学工程学院，昆明 650500

基金项目: 国家自然科学基金 (21766016)；云南省“万人计划”基金 (YNWR-QNBJ-2018-198)；昆明市科学技术局科技计划基金 (2019-1-G-25318000003480)；倪永浩院士工作站 (2019IC002)；云南省基础研究计划青年项目 (202001AU070023)；昆明市科学技术局科技创新要素聚集计划重点项目 (2019-1-A-24657)；云南省科技厅重大科技专项计划 (202002AB080002)

详细信息

通讯作者:
胡天丁，博士，副教授，硕士生导师，研究方向为金属-有机框架材料（MOFs）的合成与催化反应机理的DFT计算研究　E-mail: teddyhu1991@163.com

陕绍云，博士，教授，博士生导师，研究方向为多孔环保材料 E-mail：shansy411@163.com

中图分类号: TQ032
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出版历程
- 收稿日期: 2021-08-19
- 修回日期: 2021-09-19
- 录用日期: 2021-09-27
- 网络出版日期: 2021-10-18
- 刊出日期: 2022-03-23

Research advances of MOF-based catalyst for photohydrolysis for hydrogen production

Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China

摘要

摘要: 随着能源枯竭和环境污染问题日益严重，人们不得不将目光转向更加清洁环保的氢能源。光解水制氢技术是一种获取氢能源经济且清洁的理想方式，通过光催化手段将太阳能转化为化学能也是一种很有前景的技术手段。然而如何选取高效、经济的光催化剂是制氢最关键的环节。金属-有机框架(Metal-organic frameworks, MOFs)由于比表面积大、孔尺寸可调节、结构易于修饰及活性位点丰富等特点，使其成为光解水制氢理想的光催化剂候选材料。国内外学者就MOFs光解水制氢开展了大量的研究，并且取得了丰硕的成果。本论文综述了MOF基材料作为催化剂在光解水制氢领域的研究进展，总结了MOFs作为催化剂的优点和局限性，并对MOFs及其相关材料在光催化水解制氢领域的发展前景提出展望，以期对未来研究提供参考。
- 金属-有机框架 /
- 光催化 /
- 催化剂 /
- 水解 /
- 制氢
Abstract: The increasingly serious energy exhaustion and environmental pollution accelerates the development of clean hydrogen energy. Water splitting via photocatalysis technology provides an economical and clean way for the hydrogen production, converting solar energy into chemical energy through photocatalytic means is also a promising technical means. The rational selection of photocatalyst is the critical step for obtaining hydrogen energy in an efficient and economical way. Featuring the traits of large specific surface area, adjustable pore size, easy structure modification and abundant active sites, metal-organic frameworks (MOFs) are ideal candidates for photocatalytic hydrogen production scientists from domestic and foreign have carried out numerous researches on the water splitting with MOF-based photocatalysts. Currently, fruitful progresses have been achieved. In this paper, the state-of-the-art advances for the MOF-based materials as catalysts in the field of hydrogen production from splitting water was reviewed, and the advantages and limitations of MOFs as catalysts were summarized. The development prospect of MOFs and related materials in the field of photocatalytic hydrogen production was proposed, providing a valuable guideline for developing future photocatalysts.
- metal-organic frameworks /
- photocatalysis /
- catalyst /
- water splitting /
- hydrogen production

HTML全文

图 1 金属-有机框架(MOFs)适用于催化的结构特征^[19]

Figure 1. Structural characteristics of metal-organic frameworks (MOFs) apply to catalytic^[19]

PSM—Post-synthetic modification

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图 2 MOFs应用于光催化的种类

Figure 2. Types of MOFs used in photocatalysis

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图 3 Al₃(OH)₃(HTCS)₂(AlTCS-1)在水和三乙醇胺(TEOA)混合溶剂中光催化裂解水的机制^[24]

Figure 3. Mechanism of the photocatalytic water splitting process of Al₃(OH)₃(HTCS)₂(AlTCS-1) in mixed solvents of H₂O and triethanolamine (TEOA)^[24]

NHE—Normal hydrogen electrode; TCS—Tetrakis (4-oxycarbonylphenyl) silane; CB—Conduction band; VB—Valence band; E_g—Energy gap

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图 4 (a) 金属有机框架-808-乙二胺四乙酸 (MOF-808-EDTA) 模型图；(b) 封装单原子Pt的MOF-808-EDTA模型图^[32]

Figure 4. (a) Metal-organic frameworks-808-ethylenediaminetetraacetic acid (MOF-808-EDTA) model diagram; (b) Model diagram of MOF-808-EDTA encapsulating a single atomic Pt^[32]

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图 5 Al-TCPP-Pt光催化制氢机制图^[31]

Figure 5. Schematic illustration showing the synthesis of Al-TCPP-Pt for photocatalytic hydrogen production^[31]

Al-TCPP—(AlOH)₂H₂TCPP (H₂TCPP = 4, 4′, 4″, 4″-(Porphyrin-5, 10, 15, 20-tetrayl)tetrabenzoate)

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图 6 MOFs复合材料种类

Figure 6. Types of MOFs composites

COFs—Covalent organic frameworks; POMs—Polyoxometalates; QDs—Quantum dots

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图 7 [Ru(cod)(cot)]_3.5@MOF-5模型^[47]

Figure 7. Model of [Ru(cod)(cot)]_3.5@MOF-5^[47]

cod—1, 5-Cyclochloro ethane; cot—1, 3, 5-Cyclochlorine ethane

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图 8 基于连接簇电荷转移 (LCCT) 机制的Pt负载Ti-MOF-NH₂光催化制氢反应机制图^[55]

Figure 8. A schematic illustration of photocatalytic hydrogen production reaction over Pt-supported Ti-MOF-NH₂ on the basis of the ligand-to-cluster charge transfer (LCCT) mechanism^[55]

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图 9 结晶多氧钛簇/CdS/MIL-101 (PTC/CdS/MIL-101) 催化水裂解制氢示意图^[63]

Figure 9. Schematic diagram of polyoxo-titanium clusters/CdS/MIL-101 (PTC/CdS/MIL-101) catalytic water cracking for hydrogen production^[63]

MIL-101—Materials of institute lavoisier-101

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图 10 NH₂-UiO-66/TpPa-1-共价有机框架 (NH₂-UiO-66/TpPa-1-COF) (4:6)杂化材料制氢机制示意图^[66]

Figure 10. Mechanism schematic of hybrid material NH₂-UiO-66/TpPa-1-covalent organic framework (NH₂-UiO-66/TpPa-1-COF) (4:6) for photocatalytic hydrogen production^[66]

SA—Sodium ascorbate; E—Electrode potential

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图 11 掺Fe的TiO₂用于可见光下催化产氢^[70]

Figure 11. Fe-loaded TiO₂ catalyzes hydrogen production under visible light^[70]

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图 12 ZnIn₂S₄-In₂O₃异质结构用于产生H₂的电荷分离和转移的示意图^[74]

Figure 12. Schematic illustration of the charge separation and transfer in the ZnIn₂S₄-In₂O₃heterostructure for H₂ evolution^[74]

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图 13 Cu₃P@CoP的曙红Y (EY) 敏化剂p-n异质结在可见光照射下水分解制氢过程机制图^[78]

Figure 13. Mechanism diagram of the hydrogen production process by water decomposition of Eosin Y (EY) sensitizer p-n heterojunction of Cu₃P@CoP under visible light irradiation^[78]

SCE—Saturated calomel electrode; E_f—Fermi level; ISC—Inter system crossing

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表 1 有关MOF/纳米颗粒复合材料作为可见光照射下的光催化析氢反应的催化剂

Table 1. MOF/nanoparticle composites as catalysts for photocatalytic hydrogen evolution under visible light irradiation

Photocatalyst	Bandgap E_g/eV	Sacrificial agents	Co-catalysts	H₂ Production rate/(mmol·h⁻¹ ·g⁻¹)	Recycled times	Solution stability/h	Ref.
TiO₂@ZIF-8	3.28	Methanol	—	0.25	4	24	[56]
MOF-199/Ni	—	Triethanolamine	Pt	24.40	3	9	[57]
Ru-Pt-UiO-67	—	N, N-Dimethylacetamide	—	34.00	3	30	[58]
Pt@MIL-125/Au	—	Triethanolamine	—	1.74	3	6	[59]
Calix-3/Pt@UiO-66-NH₂	—	Methanol	—	1.53	3	9	[60]
Ni-MOF-74-CdS/Co₃O₄	1.97	Lactic acid	—	0.58	4	20	[61]
ZIF-9/Zn_0.8Cd_0.2S	—	Triethanolamine	—	6.42	—	—	[62]

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表 2 部分用于可见光催化析氢反应的MOFs衍生物

Table 2. Some MOFs derivatives used in visible light catalytic hydrogen evolution reaction

Photocatalyst	MOF precursors	Bandgap E_g/eV	Sacrificial agents	Co-catalysts	H₂ Production rate/(mmol·h⁻¹·g⁻¹)	Recycled times	Solution stability/h
Cu_0.9Co_2.1S₄@MoS₂	ZIF-67(Cu/Co)	—	Triethanolamine	—	40.16	3	30
FeO_3.3C_0.2H_1.0	MIL-101(Fe)	1.61	—	—	125.00	4	24
Pt-Zn₃P₂-CoP	ZnCoZIF-8	—	Methanol	—	9.15	4	24
Co-Zn_0.5Cd_0.5S	ZnCoZIF-8	—	$ {\mathrm{S}\mathrm{O}}_{3}^{2-} $/$ {\mathrm{S}}^{2-} $	—	17.36	6	30
Hollow Cu-TiO₂/C	SiO₂@HKUST-1	—	Methanol	Pt	14.05	3	18
Hollow CdS nanoboxes	Cd-MOF-74	2.30	Lactic acid	Pt	21.65	4	16
Co/NGC@ZnIn₂S₄	ZIF-8@ZIF-67	2.10	Triethanolamine	—	11.27	5	20
Notes: NGC—N-Doped graphitic carbon; HKUST-1—Hong Kong University of Science and Technology-1.

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