MOF材料在水環境污染物去除方面的應用現狀及發展趨勢（II）

黃祎萌; 曹曉強; 尹繼潔; 李廣; 張迪; 李明真; 孟娜; 陳平; 由曉芳; 陳明; 顏炳琪; 李琳; 王鵬; 呂憲俊

doi:10.13374/j.issn2095-9389.2019.12.08.003

MOF材料在水環境污染物去除方面的應用現狀及發展趨勢（II）

doi: 10.13374/j.issn2095-9389.2019.12.08.003

黃祎萌¹,
曹曉強^1, ,,
尹繼潔¹,
李廣¹,
張迪¹,
李明真¹,
孟娜¹,
陳平¹,
由曉芳²,
陳明³,
顏炳琪⁴,
李琳²,
王鵬²,
呂憲俊²

1.
山東科技大學安全與環境工程學院，青島 266590
2.
山東科技大學化學與生物工程學院，青島 266590
3.
牛津大學工程科學系，牛津 OX1 3PJ
4.
清華蘇州環境創新研究院，蘇州 215163

基金項目: 國家自然科學基金資助項目（51674161，51774200，51904174）；山東省重點研發資助項目（2019GGX103035）；山東省研究生導師指導能力提高計劃資助項目（SDYY18080）；山東科技大學訪問學者支持計劃資助項目；山東科技大學“群星”計劃資助項目（QX2018M43）；2019煤炭加工與高效潔凈利用教育部重點實驗室開放基金資助項目；2019國家級大學生創新創業訓練計劃資助項目（201910424019）

詳細信息

通訊作者:
E-mail: caoxiaoqiang@sdust.edu.cn

中圖分類號: X-1; X506; O641.4
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出版歷程
- 收稿日期: 2019-12-08
- 刊出日期: 2020-06-01

Review on the application of MOF materials for removal of pollutants from the water (II)

1.
College of Safety and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China
2.
College of Chemical and Biological Engineering, Shandong University of Science and Technology, Qingdao 266590, China
3.
Department of Engineering Science, University of Oxford, Oxford OX1 3PJ, UK
4.
Research Institute for Environmental Innovation (Suzhou) Tsinghua, Suzhou 215163, China

More Information

Corresponding author: E-mail: caoxiaoqiang@sdust.edu.cn

摘要

摘要: 對近年來MOF材料去除水環境中重金屬、有機物的相關研究進行了總結與評述。本篇是該主題的第2篇，主要對MOF材料去除水中有機污染物的相關研究進行總結和論述。研究表明，MOF材料含有大量開放性金屬位點、路易斯酸堿位以及官能團，因而對染料、抗生素、農藥、持久性有機污染物等均具有較高的吸附性能。氫鍵、π?π作用、疏水作用和靜電引力是其吸附有機污染物的主要機制，部分MOF材料中較大的孔道結構也有利于大分子有機污染物的吸附；另外，部分MOF材料還具有優異的催化性能，能夠作為類Fenton催化，光催化以及過硫酸鹽活化的催化劑實現對有機污染物的催化降解，其中光催化反應中污染物的降解主要源于·O^2?、·OH和h⁺的貢獻；而在過硫酸鹽體系中，·O^2?、·OH、SO₄^·?和¹O₂是導致有機污染物分解的主要活性氧化物種。基于對先前研究的回顧，相信未來的研究領域包括但不限于以下方面：（1）進一步提高MOF在去除有機污染物方面的性能，并提高其可回收性；（2）開展新型MOF催化材料的制備及催化反應機理的研究；（3）研究MOF缺陷結構的調控，以開發具有更高吸附和催化性能的新型MOF材料；（4）研究新的框架材料，例如共價有機骨架（COFs）材料，并將其應用于污染物凈化領域。
- 金屬有機骨架（MOFs） /
- 有機污染物 /
- 藥品和個人護理產品 /
- 吸附 /
- 催化降解 /
- 缺陷結構
Abstract: Metal–organic frameworks (MOFs) are a class of organic–inorganic hybrid functional materials generally formed via self-assembly of metal ions or metal clusters and rigid organic ligands with nitrogen and oxygen atoms. The wide range of potential applications of MOF materials includes gas storage and separation, catalysis, sensing, and drug transportation and release, which can be attributed to their versatile designable structures, modifiable chemical functionality, low-density framework, large specific surface area, and functional and permanent pore space. MOF and its composite materials have also been employed to remove various contaminants from the environment in the recent decade. To present the remarkable research progress and outcomes of MOF materials in the removal of pollutants from the water environment, the related studies on the removal of heavy metals and organic pollutants from the water environment were reviewed in this paper. This was the second paper on the topic that mainly introduced the research progress of MOF materials in the removal of organic pollutants in aqueous solution. The previous studies have shown that MOF materials have open metal sites and Lewis acid–base sites; thus, they exhibit a high adsorption performance for dyes, antibiotics, pesticides, and persistent organic pollutants. Hydrogen bonding, π–π interaction, hydrophobic interaction, and electrostatic attraction are the main mechanisms for their adsorption of organic pollutants. In addition, the large pore structure of some MOF materials is conducive to the adsorption of macromolecular organic pollutants. Moreover, some MOF materials that can be used as catalysts for Fenton-like reactions, photocatalytic reactions, and persulfate activation to degrade organic pollutants, exhibit excellent catalytic performance. The degradation of pollutants in photocatalytic reactions can be mainly attributed to the contributions of ·O^2?, ·OH, and h⁺. In the persulfate system, ·O^2?, ·OH, SO₄^·?, and ¹O₂ are the main reactive oxide species that cause the decomposition of organic pollutants. Based on the review of previous studies, it is believed that future research will include but will not be limited to the following: (1) the improvement of the performance of MOF in removing organic pollutants and its recyclability; (2) the preparation of new MOF catalytic materials and investigation of catalytic reaction mechanisms; (3) the regulation of the defect structure of MOF to develop new MOF materials with high adsorption and catalytic efficiency; and (4) the analysis of new framework materials, e.g., covalent organic framework materials, and their applications in the field of pollutant purification.
- metal organic frameworks (MOFs) /
- organic pollutants /
- pharmaceutical and personal care products (PPCPs) /
- adsorption /
- catalytic degradation /
- defect structure

HTML全文

圖 1 不同的NH₂-MIL-125(Ti)的掃描電鏡圖^[22]。（a）吸附前；（b）第1次循環后；（c）第2次循環后；（d）第3次循環后

Figure 1. SEM images of different NH₂-MIL-125(Ti)^[22]: (a) before adsorption; (b) first cycle; (c) second cycle; (d) third cycle

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圖 2 BUT結構以及不同BUT樣品的粉末X射線衍射圖譜。（a）合成的BUT-12以及采取不同處理手段后得到的樣品的粉末X射線衍射圖譜；（b）BUT-12結構；（c）BUT-13以及采取不同處理手段后得到的樣品的粉末X射線衍射圖譜；（d）BUT-13結構^[36]

Figure 2. BUT structure and powder X-ray diffraction (PXRD) patterns of different BUT samples: (a) PXRD patterns of BUT-12 upon treatment using different methods; (b) structures of BUT-12; (c) PXRD patterns of BUT-13 upon treatment using different methods; (d) structures of BUT-13^[36]

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圖 3 PCN-222結構示意圖。（a）PCN-222的孔結構；（b）組成PCN-222的無機簇Zr₆(μ-OH)₈(OH)₈(CO₂)₈（顏色：Zr藍色；C灰色；O紅色；H白色）^[38]

Figure 3. Structure diagram of PCN-222: (a) pore structure; (b) inorganic clusters Zr₆(μ-OH)₈(OH)₈(CO₂)₈ of PCN-222 (color code: blue, Zr; grey, C; red, O; white, H)^[38]

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圖 4 NKU-101的晶體結構。（a）四足籠型Zn₄₈(BTC-1)₁₂(BTC)₈(PyC)₆；（b）四足籠的堆疊方式；（c）沿a、b和c方向延伸的3D通道網絡^[47]

Figure 4. Crystal structure of NKU-101: (a) tetrapodal cage Zn₄₈(BTC-1)₁₂(BTC)₈(PyC)₆; (b) packing of tetrapodal cages; (c) 3D channel net running along the a, b, and c directions^[47]

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圖 5 不同樣品的UV–vis DRS譜（a）以及不同光催化劑的四環素去除性能（b）^[65]

Figure 5. UV–vis DRS spectra of different samples (a) and the removal of tetracycline using different photocatalysts (b)^[65]

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圖 6 ZIF?8/NF?TiO₂光電極的制備及其催化降解SMT機理^[74]

Figure 6. Fabrication of ZIF?8/NF?TiO₂ photoelectrode and catalytic mechanism of SMT degradation^[74]

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圖 7 不同催化劑的電鏡照片及污染物降解機理。Co₃O₄（a）和Co₃O₄@MOF-5（b）的透射電鏡圖像；（c）Co₃O₄@MOF-5的掃描電鏡圖像；（d）可能的降解機理^[82]

Figure 7. Electron micrographs of different catalysts and degradation mechanism of pollutants: TEM images of Co₃O₄ (a) and Co₃O₄@MOFs (b); (c) SEM image of Co₃O₄@MOF-5; (d) possible mechanism of degradation^[82]

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圖 8 AQS?NH?MIL?101(Fe)催化降解BPA機理（a）及不同條件下BPA的去除效率（b）^[83]

Figure 8. Mechanism of AQS?NH?MIL?101(Fe) catalytic degradation of BPA (a) and removal of BPA under different catalytic conditions (b)^[83]

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圖 9 MOF中的缺陷結構^[84]

Figure 9. Defect structures in MOF^[84]

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