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Preparation of Polyoxometalates@Metal-Organic Frameworks Materials and Their Application in Wastewater Treatment

Hao Hu , Yunpeng He , Shuijin Yang

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (6) : 1026 -1034.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (6) : 1026-1034 DOI: 10.7536/PC200662
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Preparation of Polyoxometalates@Metal-Organic Frameworks Materials and Their Application in Wastewater Treatment
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Abstract

The pollutants in the wastewater are hazardous to human health due to their complex composition, high biological toxicity and difficult degradation. Therefore, finding and developing some adsorbents that can effectively remove highly toxic and refractory pollutants in wastewater have become an urgent problem to be solved. Metal-organic frameworks(MOFs) materials have the characteristics of orderly and diverse structure, rich topology, ultra-high porosity, large specific surface area, stable framework structure and easy doping with other components, which have attracted wide attention in the field of adsorption. Compared with pure MOFs, the new hybrid materials POMs@MOFs are created by incorporating polyoxometalates(POMs) onto metal-organic frameworks(MOFs). They not only have their unique set of properties, but also combine the strong acidity, oxygen-rich surface, and redox capability of POMs. At the same time, they have overcome shortcomings of POMs and MOFs, such as difficult handling, low surface area, and high solubility. In recent years, researchers have discovered that the composites of POMs and MOFs have excellent performance as adsorbents in the field of wastewater treatment. In this paper, the synthesis and preparation of POMs@MOFs, especially the advantages and disadvantages of various preparation methods, are summarized and analyzed based on the reported researches and the works of our group. This article focuses on the application and development of POMs@MOFs in wastewater treatment. Finally, the development direction and research prospect of POMs@MOFs composite materials are also proposed.

Contents

1 Introduction

2 Preparation of POMs@MOFs materials

2.1 The method of one-pot synthesis

2.2 The method of impregnation synthesis

2.3 The method of mechanical grinding synthesis

3 Application of POMs@MOFs materials in wastewater treatment

3.1 Application of MOFs materials in wastewater treatment

3.2 Application of POMs materials in wastewater treatment

3.3 Application of POMs@MOFs materials in wastewater treatment

4 Conclusion and outlook

Graphical abstract

Keywords

polyoxometalates / metal-organic framework / synthesis / removal / wastewater treatment

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Hao Hu, Yunpeng He, Shuijin Yang. Preparation of Polyoxometalates@Metal-Organic Frameworks Materials and Their Application in Wastewater Treatment. Progress in Chemistry, 2021, 33(6): 1026-1034 DOI:10.7536/PC200662

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1 Introduction

Water pollution has become one of the most serious problems at present[1]. Contaminated water often contains heavy metal salts or organic contaminants[2,3]. Residual organic dyes in water not only cause damage to the water ecosystem, but also endanger human health[4⇓~6]. However, the heavy metal ions in sewage often contain arsenic (As), lead (Pb), mercury (Hg), cadmium (Cd) and chromium (Cr), which can be enriched into organisms through the food chain and cause harm to human beings and the ecological environment, so it is very important to develop some technologies for wastewater treatment[7,8]. Several common technologies, such as ion exchange, membrane separation, chemical oxidation, advanced oxidation and biological treatment, can be used to treat pollutants[9,10]. However, these methods have the disadvantages of high operation cost and large amount of waste. Comparatively speaking, adsorption and catalysis methods have the advantages of green, energy saving, simple and efficient, and can effectively remove toxic and refractory pollutants in wastewater without secondary pollution, so they have become one of the preferred methods for wastewater treatment[11]. The traditional adsorbents mainly include activated carbon, carbon nanotubes, slag, graphene and metal oxides, which generally have the problems of low adsorption capacity and no selectivity[12⇓⇓⇓~16]. Therefore, researchers have been committed to finding and developing new materials with low cost, high adsorption capacity and high selectivity.
Metal-organic frameworks (MOFs) are inorganic-organic hybrid crystalline materials formed by the self-assembly of metal ions or clusters and organic ligands through coordination bonds[17,18]. These materials have attracted great interest in recent years because of their large surface area, adjustable pore size and designable function[19⇓~21]. It has a wide range of applications in gas storage and separation, proton conduction, pollutant analysis, sensing, drug delivery and so on[22⇓⇓⇓⇓⇓~28]. Among them, MOFs have shown excellent performance in adsorbing and separating pollutants from aqueous solutions as adsorbents[29]. Haque et al. First used PED-MIL-101 (Cr) to adsorb and remove methyl orange (MO) in aqueous solution, and Ke et al. First used HKUST-1 to adsorb and remove Hg2+ in aqueous solution[30][31]. However, in the actual treatment of wastewater, because most of MOFs have no free functional groups, and their stability in aqueous solution is relatively low, lack of flexibility and fragility, their adsorption performance is generally low and their adsorption selectivity is poor, which hinders their potential application value[32,33]. When MOFs are used as loading hosts, they can selectively bind different functional guest molecules, thus optimizing the structure of MOFs and making them have better specific adsorption performance. Among them, the introduction of polyoxometalates (POMs) as active guest molecules into the mesopores of MOFs has become an effective way to construct novel POMs @ MOFs functionalized porous materials. POM is an important metal oxide cluster with high negative charge, rich topological structure, strong acidity and rich surface oxygen[34⇓⇓⇓⇓⇓~40]. Has potential application value in the fields of catalytic adsorption, analytical chemistry, ion exchange, biochemistry, medicine and the like[41⇓⇓⇓⇓⇓~47]. However, there are still some disadvantages in the application of POMs, such as small specific surface area (1~10 m2/g), solubility in polar solvents, easy loss, difficult recovery, corrosion of equipment and so on[48,49]. Some groups have proposed to immobilize POMs in porous materials to overcome these shortcomings and obtain adsorbents with high performance, such as titanium dioxide, ion exchange resins, zeolites and metal-organic frameworks[50⇓⇓~53].
POMs @ MOFs composites not only combine their respective advantages, but also overcome their respective defects to achieve the maximum functionality of materials in many fields. At present, domestic and foreign research groups have reported the application of POMs @ MOFs in many fields, including gas storage and separation, catalysis, heavy metal/organic pollutant adsorption, sensing, proton conduction and electrochemistry[54⇓⇓⇓~58]. In this paper, the preparation methods of POMs @ MOFs and their applications in the field of heavy metal/organic pollutant adsorption and catalysis are reviewed, and several common preparation methods and their advantages and disadvantages are introduced.The adsorption mechanism and application of different POMs @ MOFs composite materials were discussed, and the future development direction and problems in the field of water purification were prospected.

2 Preparation of POMs @ MOFs

Due to the rapid development of science and technology, the research on the preparation and application of POMs @ MOFs materials is rapidly rising. In this kind of composite structure, POMs are either part of the framework or encapsulated inside the cavity of MOFs as guest molecules. The most common preparation methods of POMs @ MOFs are mainly divided into three categories: one-pot synthesis, impregnation synthesis and mechanical grinding synthesis[59⇓⇓~62]. In this paper, the advantages and disadvantages of these three methods will be introduced in detail.

2.1 One-pot Synthesis

The one-pot synthesis method generally refers to POMs precursors, metal ions and organic ligands as initial raw materials, and then the composite materials are prepared by a conventional water/solvent/electrothermal method, and the main operation is to add the POMs precursors in the process of synthesizing the MOFs[63,64]. The method has the advantages of simple operation and good repeatability, and is suitable for preparing the POMs with the pore size smaller than that of the MOFs. However, the synthesis conditions of some MOFs are difficult, and the reaction needs to be carried out under high temperature and high pressure, which may lead to the instability of POMs structure. Therefore, it is necessary to select POMs with stable structure as templates to prepare POMs @ MOFs materials for the treatment of dye wastewater.
Sun et al. Compounded heteropolyacid with Cu3(BTC)2 and prepared H3PMo12O40@Cu3(BTC)2 composite material by solvothermal method. They characterized by X-ray powder diffraction (XRD), Fourier-infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller specific surface area method (BET) and so on, and came to a conclusion that heteropolyacid exists in the octahedral cage of Cu3(BTC)2 as a guest molecule[65]. The catalytic activity of the composite was evaluated by catalyzing excess ethyl acetate. The experimental results showed that the POMs supported on MOFs could enhance the catalytic activity, which was attributed to the good dispersion of polymethyl esters in the MOFs at the molecular level during the preparation of the composite, which prevented the agglomeration of POMs, and the POMs were fixed in the composite to avoid the deactivation of the catalyst. In addition, in 2011, they reported that a new structural material H3[(Cu4Cl)3(BTC)8]2[PW12O40]3(C4H12N)6·3H2O, referred to as NENU-11, was formed in the H3PW12O40·nH2O of Cu3(BTC)2 packaging, as shown in Figure 1[66]. The results showed that the adsorption and degradation ability of the composite material for dimethyl methylphosphonate was improved. They confirmed by elemental analysis and atomic absorption spectroscopy that there are six (CH3)4N+ around each [PW12O40]3- in the composite crystal structure. In addition, the solvothermal composite NENU-11 shows good stability due to the good matching of the shape (approximately spherical) and size (~ 10.44 Å) of the Keggin-type POMs with the bulk MOFs in symmetry (Td). Yan et al. Prepared POM@MIL-101(POM=K4PW11V O 4 0, H3PW12O40,K4SiW12O40) composites by one-pot method by mixing various POMs into the precursor solution of MIL-101[67]. Their research shows that the absorption capacity of MIL-101 for organic pollutants in aqueous solution can be significantly improved by immobilizing hydrophilic POMs in the framework of MIL-101. Li et al. Synthesized POMs @ MOFs compounds by hydrothermal method[68]. In 2019, Marandi et al. Synthesized Co-POM @ MIL-101 (Cr) composite without HF by one-pot method (as shown in Figure 1). They characterized the composite by XRD, transmission electron microscope (TEM), scanning electron microscope (SEM), etc., and proved that Co-POM was encapsulated in the skeleton of MIL-101 (Cr)[69]. As shown in Fig. 1, Hoseini et al. prepared a novel inorganic-organic yolk shell microsphere with P5W30@MIL-101(Cr) by hydrothermal synthesis method, using Preyssler-type heteropolytungstic acid (K12.5Na1.5[NaP5W30O110]), chromium nitrate nonahydrate (Cr(NO3)3·9H2O) and terephthalic acid (H2BDC) as raw materials, placing at 200 ℃ for 24 H under hydrothermal conditions, and doping Preyssler-type NaP5W30O11014- polyoxometalate into three-dimensional porous MIL-101 (Cr) metal-organic framework[70].
From the POMs @ MOFs composite prepared by the above one-pot synthesis method, Keggin-type POMs are mainly used as guest molecules, and secondly, the size of POMs must be larger than the pore window of MOFs to prevent the leaching of POMs. In addition, the one-pot synthesis method is not suitable for all MOFs structures.

2.2 Dipping synthesis method

The impregnation synthesis method comprises the following steps of: dissolving the POMs to be loaded in deionized water or an organic solvent in advance to prepare a polyacid solution, adding a certain amount of MOFs carriers, stirring at a certain temperature, standing, and loading the POMs into the pore canals of the MOFs through electrostatic adsorption and intermolecular diffusion of the MOFs. Since most POMs are well soluble in polar solvents, the impregnation method is a simple and straightforward method for their preparation.
F Férey et al. Synthesized KPW11O40·nH2O@MIL-101(Cr) composite materials by loading KPW11O40·nH2O on MIL-101 (Cr) by impregnation method, which opened up a way for the application of heterogeneous catalysis[71]. Maksimchuk et al. reported for the first time that two transition metal-substituted heteropolyacids, H5PW11CoO39 and H5PW11TiO40, were supported on MIL-101 (Cr), and H5PW11CoO39@MIL-101(Cr) and H5PW11TiO40@MIL-101(Cr)2 nanocomposites were synthesized by impregnation method.They used X-ray photoelectron spectroscopy (XPS), XRD, Brunauer-Emmett-Teller surface area method (BET) and other characterization methods to confirm that H5PW11CoO39 and H5PW11TiO40 exist in the pores of MIL-101 (Cr) (as shown in Figure 2), and that heteropolyacid and MIL-101 (Cr) are bound together by electrostatic interaction[72].
In 2015, Buru et al. dissolved the H3PW12O40 in an aqueous solution, and then added it to the NU-1000 material prepared in advance. After ultrasonic treatment for 1 min, it was allowed to stand at room temperature, filtered, washed, and dried to obtain the PW12@NU-1000 composite material prepared by the impregnation method[73]. In 2018, Stuckart et al. Added the pre-prepared ZIF-67 to methanol solution containing H3PMo12O20 by dipping method, and heated the ZIF-67 skeleton to partially dissociate and form defects, which opened the smaller window, and then loaded the H3PMo12O20 into the ZIF- 67 skeleton to obtain the H3PMo12O20@ZIF-67 material[74]. Chen et al. prepared the metal-organic framework ZIF-67 in advance, and then heated it in methanol solution containing H3PMo12O20, so that the mesoporous framework of ZIF-67 was partially dissociated to form defects, and the H3PMo12O20 successfully entered the framework of ZIF- 67 in the form of guest molecules. The H3PMo12O20@ZIF-67 material was synthesized by impregnation method, and calcined under the protection of N2 to further obtain the particle MoxCoxC, as shown in Figure 2[75]. In 2012, Jeon et al. Added the pre-prepared ZIF-8 material into the aqueous solution dissolved with H3PW12O40 for ultrasonic treatment, stirred at room temperature, centrifuged, washed and dried to obtain the H3PW12O40@ZIF-8 composite material with core-shell nanostructure prepared by impregnation method[76]. Buru et al. prepared PV2Mo10@NU-1000 by loading polyoxometalate H5PV2Mo10O40 into metal-organic framework NU-1000 material by impregnation method, and further synthesized PV2Mo10@NU-1000-scCO2 material activated by supercritical CO2[77].
In the above studies, the reaction conditions required by the impregnation synthesis method are relatively mild, the preparation conditions are simple, and the POMs in the prepared composites are relatively uniformly dispersed. However, the impregnation synthesis method needs to select MOFs with well-matched pore structure according to the size of POMs.

2.3 Mechanical Abrasion Synthesis

Mechanical grinding synthesis is a synthesis method that converts the mechanical energy of mechanical grinding into chemical energy and makes it react rapidly in solid phase without solvent (pure solid phase) or with the assistance of trace solvent. Its advantages are simple operation, short reaction time, green and energy-saving, but its disadvantages are that the mechanical method has serious damage to the structure, it is difficult to obtain materials with specific morphology, and its scope of application is limited.
As shown in Figure 3, in 2014, Li et al. loaded three polyoxometalate H3PW12O40, H4SiW12O40 and H3PMo12O40 into the ZIF-8 nanocrystalline material by a simple mechanical ball milling method. They characterized the composite material by XRD, UV-Vis, FT-IR, SEM and TEM[78]. The experimental results show that the polyoxometalate molecules are loaded into the ZIF-8 framework, and the structure of the composite is stable. In addition, the obtained composite material has good adsorption performance for methylene blue solution. In 2018, Zhong et al. Encapsulated H3PW12O40 into MOFs material HKUST-1 through a simple liquid-assisted grinding method to obtain H3PW12O40@HKUST-1 nanocrystal composite (NENU-3N), which was used as a catalyst for phenol degradation[79]. This is the first time that liquid-assisted milling has been used to prepare nanocrystalline POMs @ MOFs hybrids. At 35 ℃, phenol was degraded by 97% and mineralized by 88% by Cu2+ in POMs and MOFs, respectively. In addition, the comparative experiments showed that the size reduction of NENU-3N catalyst was helpful to enhance its catalytic performance. Finally, the NENU-3N catalyst has good stability and is easy to be recycled and reused, and the catalyst is not easy to be deactivated. In 2012, Li et al. used phosphotungstic acid (H3PW12O40), indium nitrate (In(NO3)3·5H2O) and 3,3 ', 5,5' -biphenyltetracarboxylic acid (H4BPTC) as raw materials by grinding and solvent-free in-situ hot pressing.The H3PW12O40 (denoted as the PW12) was rapidly incorporated into the metal-organic framework MFM-300 (In) In a short period of time, resulting in a novel PW12@MFM-300(In) composite with the structure shown in fig. 3[80]. This solvent-free preparation process is not only environmentally friendly, but also saves energy and time. The inclusion of PW12 In MFM-300 (In) was demonstrated by different physical and chemical characterizations. The composites showed high crystallinity and stability, and no PW12 agglomeration was observed on the surface of MOFs, which indicated that PW12 had good dispersion in MOFs.

3 Application of POMs @ MOFs in Wastewater Treatment

3.1 Application of MOFs in Wastewater Treatment

In recent years, the application of MOFs in the field of adsorption/separation has been widely reported due to its rich topological structure, high porosity, adjustable pore size, large specific surface area, stable framework structure, easy to dope other components and easy to modify the inner surface[19⇓~21]. When used as a single catalyst, MOFs have catalytic adsorption effect on organic dyes and other pollutants.
In 2011, Haque et al. Synthesized MOFs material MOF-235, which showed the adsorption capacity for anionic dye methyl orange (MO) and cationic dye methylene blue (MB), and the adsorption mechanism was mainly due to electrostatic attraction and π-π conjugation between dye molecules and MOFs skeleton[81]. In 2013, Tong et al. Prepared MOFs material MIL-100 (Fe, Cr), and found that MIL-100 (Fe) showed a very good adsorption performance for MO and MB, but ML-100 (Cr) could only adsorb MB from the MO-MB mixture[82]. Next, Lin et al synthesized MOFs material Cu-BTC, and studied the possible mechanism and adsorption behavior of Cu-BTC adsorbing MB[83]. In addition to adsorption, MOFs can also be used as photocatalysts for the degradation of dye macromolecules in water. The MOFs material UiO-66 was prepared by hydrothermal method in our group, and it was found that the single UiO-66 had a certain degradation performance for rhodamine B (RhB)[84]. In 2011, Du et Al synthesized MOFs material MIL-53 (M) (M = Fe, Cr, Al), and introduced the degradation efficiency and degradation mechanism of MIL-53 (Fe) for MB in detail, which confirmed that MOFs will be a promising material in the field of photocatalysis[85]. In 2014, Yuan et al. prepared MOFs material MIL-88a, and discussed the degradation performance of MIL-88a on MB. The experimental results showed that under the irradiation of visible light, although the single phase MIL-88A had a certain degradation effect on the dye, the degradation efficiency was low, and only 16% was degraded in 20 minutes[86]. So far, there are quite a lot of reports on the application of MOFs in wastewater treatment. Combined with the above reports, it can be seen that single MOFs material has low adsorption and separation efficiency for dyes, which limits its application in the field of wastewater treatment. Therefore, it is an urgent problem to modify the single phase MOFs to improve their catalytic adsorption properties.

3.2 Application of POMs in Wastewater Treatment

POMs are wide band gap materials with HOMO-LUMO energy gap of 3. 1 ~ 4.6 eV, and the absorption peak is mainly in the ultraviolet region, but the band can be extended to the visible region[87]. Under the irradiation of near ultraviolet light, it has high response activity, electron-hole pair separation occurs, and the degradation of organic matter is achieved through autoxidation and the generation of hydroxyl radicals[88,89]. At present, it has been applied to the degradation of various pollutants.POM-based composite catalyst include H3PW12O40@BiVO4, H3PW12O40@TiO2, H3PMo12O40@ZnO,Ag@AgxH3-xPMo12O40, H3PW12O40@ZrO2, H3PW12O40@In2O3 and other efficient catalysts[90⇓⇓⇓⇓~95]. In these composite catalysts, the addition of POMs greatly improves the adsorption and separation ability of single catalyst for pollutants, in which POMs play a role in delaying the recombination of electron-hole pairs, enhancing the absorption of ultraviolet light by the composite materials, and increasing the light absorption ability of the composite materials in the visible light region.

3.3 Application of POMs @ MOFs in Wastewater Treatment

The composite of MOFs and POMs can fully combine the advantages of the two materials, effectively improve the overall performance of the composite and enhance the functionality of MOFs. Finding a simple and feasible way to combine MOFs and POMs materials to improve the adsorption and separation performance of pollutants and expand other functional applications without reducing the stability of MOFs has become an important issue for the application of POMs @ MOFs materials in water pollution treatment.
In 2015, our research group used one-step solvothermal method to prepare H6P2W18O62@Cu3(BTC)2 complex, and systematically discussed its performance as an adsorbent for the removal of methylene blue, and discussed the factors affecting the adsorption performance: initial pH value of the solution, initial concentration, mixing time, system temperature, and finally studied the kinetics and thermodynamics of the adsorption process[96]. The following year, our research group used solvothermal method to prepare and characterize H6P2W18O62@MOF-5 complexes on the basis of previous studies, and simulated wastewater system to study their selective adsorption effect on dyes in mixed wastewater solution.Considering that the actual dye wastewater can not contain only a single component, we chose the mixed solution of MB and MO to simulate the industrial wastewater system to explore the separation and industrial application ability of the complex for mixed dye molecules[97]. Subsequently, our group used solvothermal method to synthesize the H6P2Mo15W3O62@Cu3(BTC)2 composites, and characterized them in detail to study the adsorption properties and mechanism of the composites for dye wastewater[98]. The composite material has fast selective adsorption performance for rhodamine B (RhB), malachite green (MG) and methyl violet (MV). Therefore, the composite has universal applicability to the removal treatment of the cationic dye. At the same time, it was found that the charge of the complex had a great influence on the adsorption of cationic dyes, and the more negative charges, the better the adsorption of cationic dyes. In 2013, Zou et al. added H3PW12O40 into the precursor solution of Cu-BTC with a certain Cu/W molar ratio, and prepared the HKUST-1-MW@H3PW12O40 composite material in situ through microwave reaction. The experiment showed that the composite material had large specific surface area and high-density adsorption sites, and had high adsorption capacity for Pb2+, as well as Cr3+ and Cd2+[99]. In 2014, Ren et al. Compounded POMs and ZIF-8 by mechanical grinding method, and successfully loaded POMs materials into the pore structure of ZIF materials[100]. At the same time, POMs @ ZIF-8 was applied to the adsorption of heavy metal ions for the first time. Compared with single ZIF-8, the adsorption capacity of POMs @ ZIF-8 for heavy metal ions was increased by about one time. Sun et al. Successfully synthesized four new POMs @ MOFs composites by hydrothermal method and used them as adsorbents to remove dyes from aqueous solutions[101]. Experiments show that they can not only remove MB quickly and achieve high adsorption capacity, but also selectively separate MB from dye wastewater mixture (RhB, MB, MO and MB), as shown in Figure 4. In 2018, Zeng et al. prepared K6P2W18O62@UiO-66 composite materials by encapsulating heteropolyacid K6P2W18O62 into the pores of metal organic framework UiO-66 by solvothermal method, and studied the adsorption properties of K6P2W18O62@UiO-66 composite materials for cationic dye and anionic dye Orange G (OG)[102]. The adsorption capacities of RhB, mg and OG on the K6P2W18O62@UiO-66 composite material were 222.6, 190.6 and 40 MG/G, respectively. Compared with the single use of UiO-66 material, the adsorption capacity of the composite material to the dye is greatly improved. In 2016, Liu et al. Prepared two new POMs @ MOFs composite materials by hydrothermal method, namely [Ag7(L1)2·(μ2-OH)4][H3VW12O40[103].
POMs @ MOFs materials can be applied not only in the field of dye adsorption but also in the field of dye degradation. In 2015, Wang et al. synthesized 5 POMs @ MOFs composite materials, in which [Cu3(4-atrz)8(PMo12O40)2(H2O)2]·2H2O material had adsorption and degradation effect on RhB, and [Cu2(4-atrz)6(SiW12O40)(H2O)]·6H2O and [Cu2(4-atrz)4(μ2-OH)(CrMo6(OH)6O18)]·3H2O material had good adsorption and degradation effect on MB[104]. In the same year, Huo et al. Synthesized H3PW12O40@MOFs composite material by hydrothermal method, and the experiment confirmed that the material had good catalytic adsorption performance for organic dye MB[105]. Li et al. Encapsulated H3PW12O40(HPW) into MIL-53 (Fe) by solvothermal method to form HPW @ MIL-53 (Fe) composite. The RhB removal experiment showed that the composite not only had good adsorption for RhB, but also showed excellent photocatalytic activity under visible light irradiation, and the photocatalytic activity of the composite was much higher than that of the single material[106]. This is mainly attributed to the enhanced separation of photogenerated carriers between HPW and MIL-53 (Fe) and the strong adsorption ability of MIL-53 (Fe) itself. Liang et al. mixed H3PMo12O40 into the precursor solution of MIL-100 (Fe) and produced H3PMo12O40@MIL-100(Fe) composite material by one-pot reaction. When the content of H3PMo12O40 was 5 wt%, the composite material could reduce Cr (Ⅵ) 100% after 8 min of visible light irradiation[107]. Yan et al prepared POM-AgCl@NH2-MIL-101(Al) composites by impregnation method[108]. Under the irradiation of visible light, the composite material showed strong photocatalytic activity for RhB degradation. Chen et al. Dispersed the H4SiW12O40 in an aqueous solution, and then added the precursor solution of Cu-MOF to form the H4SiW12O40@Cu-MOF complex through a one-pot reaction[109]. The introduction of H4SiW12O40 enhanced the degradation of RhB by MOFs.

4 Conclusion and prospect

The POMs @ MOFs composite material makes up for various defects and deficiencies of a single adsorbent, on the one hand, the adsorption performance of the POMs @ MOFs composite material is enhanced, and on the other hand, the POMs @ MOFs composite material enables the adsorbent to have selective adsorption capability, realizes maximum functionalization of the material in the field of catalytic adsorption, and has great development prospect in the field of catalytic adsorption. With regard to the development of POMs @ MOFs system in the field of catalytic adsorption, there are still some problems to be solved urgently, which need to be studied in depth from the following aspects:
(1) We need to develop composite materials with simple method, low cost, good performance, low energy consumption and multiple utilization, which can improve the utilization value of materials and reduce the production cost of factories; Because the dyes used in the laboratory are all configured, there are differences in concentration, discharge type and ion content between the dyes used in the laboratory and the actual dye wastewater, so it is necessary to carry out practical research on the actual dye wastewater. At the same time, according to the composition of the pollutants in the wastewater or the source of the wastewater, the pollutants in the wastewater can be treated by combining a plurality of technologies or by sequentially carrying out a plurality of technologies. For example, in the treatment of dyes in wastewater, we can first remove the easily degradable pollutants through biodegradation, and then adsorb, photodegrade and volatilize the wastewater in turn, so as to achieve efficient removal of pollutants in water.
(2) Through the study and discussion of the mechanism, the most ideal construction mode of POMs and MOFs materials is found to improve the adsorption performance; Kinetics, thermodynamics and other reaction mechanisms of POMs @ MOFs in the process of selective adsorption still need to be further studied, especially in the specific experimental process, with the continuous change of adsorbent capacity, its physical parameters are also changing in real time, so it is necessary to adopt the integrated research method of calculation and experiment. In the experimental process, it is difficult to obtain the mechanism of POMs and MOFs and what role they play in the adsorption process, which we need to consider in the future. At present, researchers mainly study the adsorption capacity and desorption capacity of POMs @ MOFs, ignoring the kinetic rate of the adsorption and desorption process. However, in practical applications, a material should have both high adsorption/desorption capacity and high adsorption/desorption rate. However, these two factors are often opposite, so it is necessary to consider the synergistic effects of balance and transfer performance.
(3) The size of adsorbents is one of the important factors affecting the adsorption performance of adsorbents, so the study of POMs @ MOFs nanomaterials is the key direction in the future; Considering the introduction of POMs with different functions into MOFs and adding new active sites for the application of MOFs materials will become a new direction of POMs @ MOFs research in the future.

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Funding

National Natural Science Foundation of China(21171053)

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