MOF材料在水環境污染物去除方面的應用現狀及發展趨勢（I）

鄒星云; 陳明; 曹曉強; 王璇; 賈榮暢; 黃祎萌; 李廣; 顏炳琪; 王鵬; 李琳; 胡術剛; 呂憲俊

doi:10.13374/j.issn2095-9389.2019.11.05.003

MOF材料在水環境污染物去除方面的應用現狀及發展趨勢（I）

doi: 10.13374/j.issn2095-9389.2019.11.05.003

1.
山東科技大學化學與環境工程學院，青島 266590
2.
牛津大學工程科學系，英國牛津，OX1 3PJ
3.
青島科技大學山東化工研究院，濟南 250014
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)；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；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: 2019-11-05
- 刊出日期: 2020-03-01

Review of application of MOF materials for removal of environmental pollutants from water (I)

1.
College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China
2.
Department of Engineering Science, University of Oxford, Oxford OX1 3PJ, UK
3.
Chemical Technology Academy of Shandong Province, Qingdao University of Science and Technology, Jinan 250014, China
4.
Research Institute for Environmental Innovation (Suzhou), Tsinghua University, Suzhou 215163, China

More Information

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

摘要

摘要: 金屬有機骨架（Metal-organic frameworks，MOFs）是一類有機?無機雜化材料，通常是指金屬離子或金屬簇與含氮、氧剛性有機配體通過自組裝過程形成的功能性多孔材料。MOF材料具有豐富的可設計的結構類型、可調控的化學功能、低密度的骨架、超高的比表面積，以及可功能化的永久的孔空間，在氣體存儲與分離、催化、傳感、藥物運輸與緩釋等領域都有廣泛的應用潛力。近年來，MOF及其復合材料已經被應用于多種污染物的去除。本文對近年來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。本篇是該主題的第一篇，主要針對MOF材料在水體重金屬污染物去除方面的研究進行論述。通過對以往的研究分析可知，MOF材料對常見重金屬Pb²⁺、Cu²⁺、Cd²⁺、Co²⁺、Ag⁺、Cs⁺、Sr²⁺、Hg(II)以及$ {\rm{TcO}}_4^ - $、Se(VI)、As(III)、As(V)均具有高效吸附性能，甚至部分MOF材料的吸附性能遠高于傳統吸附材料。主要的吸附機理包括：靜電引力、配位/螯合作用、離子交換作用、孔道吸附（物理吸附）等。最后，基于以往的研究成果對未來的研究趨勢進行了展望。
- 金屬有機骨架（MOFs）材料 /
- 重金屬 /
- 去除特性 /
- 機理
Abstract: Metal-organic frameworks (MOFs) are a class of organic–inorganic hybrid functional materials that are generally formed via the self-assembly of metal ions or metal clusters and rigid organic ligands with nitrogen and oxygen atoms. A wide range of potential applications for MOF materials includes gas storage and separation, catalysis, sensing, and drug transportation and release, which is attributable to their versatile designable structures, modifiable chemical functionality, low-density frameworks, large specific surface areas, and functional and permanent pore space. In the past decade, MOFs and their composite materials have also been employed to remove various contaminants from the environment. This paper presented the significant research progress and outcomes achieved using MOF materials in the removal of environmental pollutants from water, based on a review of related studies regarding the removal of heavy metals and organic pollutants from water environments. This represented the first part of a larger paper in which the progress of MOF materials research was presented with respect to the removal of heavy metals from aqueous solution. The presence of heavy metals in water is a global environmental issue that has been receiving considerable attention worldwide. According to previous research reports, MOF materials have high adsorption capacities for common heavy metals, such as Pb²⁺, Cu²⁺, Cd²⁺, Co²⁺, Ag⁺, Cs⁺, Sr²⁺, Hg(II), $ {\rm{TcO}}_4^ - $, Se(VI), As(III), and As(V). Some MOF materials have even higher adsorption capacities than conventional adsorbent materials. The adsorption mechanism mainly involves electrostatic attraction, coordination/chelation, ion exchange, and pore adsorption (physical adsorption). Based on a review of previous studies, it is believed that the future research field includes but is not limited to the following: (1) the structure–activity relationship between the MOF structure and heavy-metal removal, (2) the functionalization, surface modification, and pore size adjustment technology of MOF, or the preparation of composite MOF materials, (3) further study of the regulation of the defect structures of MOFs to develop new MOF materials with higher adsorption efficiency, (4) improving the recyclability of MOF materials, and (5) developing new MOF materials with high structural stability, high adsorption capacities, high selectivity, low cost, and which are easily reused.
- metal organic framework materials (MOFs) /
- heavy metals /
- removal characteristics /
- mechanism

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圖 1 Cu₃(BTC)₂-SO₃H MOF吸附Cd(II) 機理^[38]

Figure 1. Adsorption mechanism of Cd(II) onto Cu₃(BTC)₂-SO₃H MOF^[38]

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圖 2 三聚氰胺?MOF對Pb(II)的吸附. （a）MOF和三聚氰胺?MOF的Zeta電位隨pH值的變化；（b）不同pH值條件下三聚氰胺?MOF的吸附容量變化；（c）三聚氰胺?MOF吸附Pb(II)的機理^[40]

Figure 2. Adsorption of Pb (II) by melamine?MOF: (a) changes in Zeta potential with pH values of MOFs and melamine–MOFs; (b) changes in adsorption capacities of melamine–MOFs at various pH values; (c) mechanism of Pb(II) adsorption onto melamine–MOFs^[40]

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圖 3 SCU-100的結構. （a）沿c軸觀察的SCU-100-Re透視堆砌結構；（b）SCU-100-Re的單一網絡晶體結構；（c）SCU-100-Re的晶體結構不對稱單元；（d）SCU-100-Re中氫鍵網絡^[58]

Figure 3. Structure of the SCU-100: (a) perspective of packing structure of SCU-100-Re viewed along c–axis; (b) single-network crystal structure of SCU-100-Re; (c) crystal asymmetric structure unit of SCU-100-Re; (d) hydrogen bond networks in SCU-100-Re^[58]

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圖 4 （a）與SCU-100進行陰離子交換過程中的${\rm{TcO}}_4^{ - 1}$水溶液紫外可見吸收光譜；（b）${\rm{TcO}}_4^{ - 1}$和${\rm{ReO}}_4^{ - 1}$去除率隨吸附時間的變化；（c）不同材料對${\rm{ReO}}_4^{ - 1}$的吸附動力學曲線對比；（d）不同材料對應的${\rm{ReO}}_4^{ - 1}$吸附等溫線對比^[58]

Figure 4. (a) UV-Vis spectra of aqueous ${\rm{TcO}}_4^{ - 1}$ solution during the anion exchange by SCU-100; (b) removal of ${\rm{TcO}}_4^{ - 1}$ and ${\rm{ReO}}_4^{ - 1}$ by SCU-100 as a function of contact time; (c) comparison of the sorption kinetics of ${\rm{ReO}}_4^{ - 1}$ by different materials; (d) adsorption isotherms of ${\rm{ReO}}_4^{ - 1}$ by cationic SCU-100, compared with other materials^[58]

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圖 5 SCU-8的晶體結構圖. （a）Th⁴⁺的配位幾何結構；（b）作為二級構筑單元（SBU）的[Th₃(COO)₉O(H₂O)_3.78]⁺陽離子簇；（c）結構中的六角形管狀通道；（d）沿c軸的陽離子介孔骨架結構圖（無序的羧基（O₃，O₄）、配位水（O₆）和bptc^3-（H₃bptc=[1,1′-biphenyl]-3,4′,5-tricarboxylicacid）配體僅顯示主要構象）^[59]

Figure 5. Crystal structure of SCU-8: (a) coordination geometry of Th⁴⁺; (b) cationic cluster of [Th₃(COO)₉O(H₂O)_3.78]⁺ as the SBU; (c) hexagonal tubular channels in the structure; (d) cationic mesoporous framework structure along c-axis (only the major conformations are shown, including the disordered carboxylate group (O₃, O₄), coordinating water (O₆), and bptc^3? ligand)^[59]

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圖 6 含有結構缺陷的Zr₆?MOF及其吸附${\rm{SeO}}_4^{2 - }$的機理^[60]

Figure 6. Zr₆?MOF with defective structure and the mechanism of ${\rm{SeO}}_4^{2 - }$adsorption^[60]

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圖 7 ZJU-101對${\rm{C}}{{\rm{r}}_{\rm{2}}}{\rm{O}}_7^{2 - }$的等溫吸附曲線及機理. （a）ZJU-101與${\rm{C}}{{\rm{r}}_{\rm{2}}}{\rm{O}}_7^{2 - }$的離子交換過程；（b）MOF-867和ZJU-101的N₂吸附等溫線；（c）正配體和負${\rm{C}}{{\rm{r}}_{\rm{2}}}{\rm{O}}_7^{2 - }$之間的庫侖吸引力示意圖^[62]

Figure 7. Isothermal adsorption curves and mechanism of ZJU-101 for ${\rm{C}}{{\rm{r}}_{\rm{2}}}{\rm{O}}_7^{2 - }$: (a) ion exchange process of ${\rm{C}}{{\rm{r}}_{\rm{2}}}{\rm{O}}_7^{2 - }$ with ZJU-101; (b) N₂ adsorption isotherms of MOF-867 and ZJU-101; (c) schematic illustration of electrostatic interaction between positive ligand and negative ${\rm{C}}{{\rm{r}}_{\rm{2}}}{\rm{O}}_7^{2 - }$^[62]

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圖 8 一維MnO₂@ZIF-8材料及其對As(III)的同時氧化和吸附去除. （a）合成后的MnO₂@ZIF-8的掃描電鏡圖像；（b, c）透射電鏡和高分辨透射電鏡圖；（d）不同MnO₂納米線添加量樣品的X射線衍射圖；（e） MnO₂@ZIF-8去除As（III）的過程示意圖(藍色部分代表ZIF-8顆粒，紅色部分代表As（III）離子）；（f）甲醇溶液中形成MnO₂@ZIF-8納米線的可能機制^[73]

Figure 8. One-dimensional MnO₂@ZIF-8 material and its simultaneous oxidation and adsorption removal of As(III): (a) SEM image of the as-synthesized MnO₂@ZIF-8 NWs; (b, c) TEM and HRTEM images, respectively; (d) XRD patterns of the products when controlling different MnO₂ nanowire additions; (e) schematic illustration of the As(III) removal process from MnO₂@ZIF-8 NWs (blue area illustrates ZIF-8 particles and the red particles are As(III) ions); (f) proposed mechanism for the formation of MnO₂@ZIF-8 nanowires in methanol solution^[73]

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表 1 不同MOF材料對陽離子態重金屬的吸附性能及機理對比

Table 1. Comparison of adsorption performance and mechanisms of different MOFs for cationic heavy metals

Adsorbent	Heavy metal	Adsorption capacity /(mg?g^?1)	Adsorption mechanism	References
ZIF-8	Pb²⁺/Cu²⁺	1119.80/454.72	Not reported	[32]
ZIF-67	Pb²⁺/Cu²⁺	1348.42/617.51	Not reported	[32]
ED-MIL-101(Cr)	Pb²⁺	81.09	Coordination	[35]
Zr-MOFs	Pb²⁺/Cd²⁺	166.74/177.35	Coordination	[36]
MOF	Pb²⁺	616.64	Electrostatic attraction，Coordination	[37]
Cu₃(BTC)₂-SO₃H	Cd²⁺	88.7	Chelation	[38]
HKUST-1-MW@H₃PW₁₂O₄₀	Pb²⁺/Cd²⁺	98.18/32.45	Chemisorption	[39]
Melamine–MOFs	Pb²⁺	205	Coordination	[40]
UiO-66@CA	Pb²⁺/Cu²⁺	81.30/31.23	Not reported	[41]
UiO-66-NH₂@CA	Pb²⁺/Cu²⁺	89.40/39.33	Not reported	[41]
MOF(AMOF-1)	Cd²⁺	41	Ion exchange	[42]
HS-mSi@MOF-5	Cd²⁺	98	Coordination	[43]
MOF	Cd²⁺	100	Ion exchange	[44]
UiO-66-Schiff	Co²⁺	256	Coordination	[46]
MIL-53(Al)–MOF	Ag⁺	183	Coordination	[47]
Nd-BTC-MOF	Cs⁺/Sr²⁺	86/58	Physical adsorption	[49]
Ca-MOF	Pb²⁺/Cd²⁺	522/220	Ion exchange	[50]
UiO-66-NHC(S)NHMe	Hg(II)	769	Coordination	[52]
MIL-101-Thymine	Hg(II)	51.27	Coordination	[55]

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表 2 不同MOF材料對陰離子態重金屬的吸附性能及機理對比

Table 2. Comparison of adsorption performances and mechanisms of different MOFs for anion heavy metals

Adsorbents	Heavy metals	Adsorption capacity/(mg?g^?1)	Adsorption mechanism	References
SCU-100	TcO₄^-	541.00	Ion exchange	[58]
Zr₆-MOF	Se(VI)	86.60	Ion exchange	[60]
1-NO₃	Cr(VI)	37.00	Ion exchange	[61]
ZJU-101	Cr(VI)	245.00	Electrostatic attraction，Ion exchange	[62]
MIL-100(Fe)	As(V)	57.71	Coordination	[67]
UiO-66	As(III)/As(V)	10.00/40.00	Coordination	[68]
MIL-53(Fe)	As(V)	21.27	Electrostatic attraction，Coordination	[69]
MIL-100(Fe)	As(V)	110.00	Electrostatic attraction，Coordination	[70]
ZIF-8	As(III)/As(V)	49.49/60.03	Electrostatic attraction，Coordination	[71]
Fe₃O₄@ZIF-8	As(III)	100	Coordination	[72]
MnO₂@ZIF-8	As(III)	140.27	Not reported	[73]

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