Oxygen carrying material for oxygenation treatment of water body as well as preparation method and application of oxygen carrying material

Abstract

The invention provides an oxygen-carrying material for oxygenation treatment of a water body and a preparation method and application of the oxygen-carrying material. The oxygen-carrying material for oxygenation treatment of the water body, provided by the invention, is a granular porous composite material formed by loading calixarene and / or an inclusion compound thereof on a self-assembled metal organic framework (MOF) material, the porous structure of a self-assembled ZIF-8 matrix material of the porous composite material and polar functional groups (such as hydroxyl, carboxyl, sulfonic acid groups, bridging sulfur atoms and the like) carried by sulfonated thiacalix [4] arene (TCAS) loaded on the surface of the self-assembled ZIF-8 matrix material and / or an inclusion compound of the TCAS and oxygen gas molecules generated in a water body are utilized to interact with each other; efficient loading and controllable release of the oxygen nano bubbles are realized, and sustainable recovery of an anoxic fresh water system is realized; the preparation process is rapid, and large-scale production is easy.

Description

Technical Field

[0001] The invention belongs to the technical field of environmental protection, and in particular relates to an oxygen-carrying material for water body oxygenation treatment, and a preparation method and application thereof. Background Art

[0002] With the intensification of human activities, the excessive input of nutrients (such as nitrogen and phosphorus) has led to increasingly serious eutrophication of water bodies, which in turn has intensified the oxygen consumption process in water bodies. This phenomenon is particularly significant in freshwater ecosystems. Freshwater systems including rivers and lakes have generally shown a long-term downward trend in dissolved oxygen (DO) levels. As a key parameter for maintaining the health of aquatic ecosystems, the reduction in dissolved oxygen concentration will not only lead to the degradation of the ecological functions of water bodies, but may also trigger the generation of harmful substances (such as hydrogen sulfide, methane, etc.) under anaerobic conditions, seriously threatening water quality safety and human health. Therefore, how to effectively restore the dissolved oxygen level of anoxic water bodies has become an important issue that needs to be urgently addressed in the field of global environmental science.

[0003] Traditional water oxygenation technology, such as using oxygen-generating equipment to directly aerate the water to increase the oxygen content in the water, is very inefficient, with oxygen utilization rates of only 5-30%.

[0004] Although traditional water oxygenation technology can increase the concentration of dissolved oxygen to a certain extent, it often has limitations such as high energy consumption, poor sustainability, and large disturbance to the ecosystem. Moreover, when using traditional aeration technology to oxygenate water, macroscopic bubbles that can be observed by the naked eye are generally produced in the water. Since macroscopic bubbles rise quickly in the water, they become larger and reach the water surface and burst during the rising process. Oxygen enters the air instead of the water, which reduces the gas-liquid mass transfer efficiency and has a poor effect on water oxygenation.

[0005] In recent years, oxygen nanobubbles (ONBs) transport technology based on porous materials has attracted widespread attention due to its advantages of high efficiency, low consumption, and environmental friendliness. Natural minerals (such as zeolite, diatomaceous earth, muscovite, and sericite) are usually used as carrier particles of oxygen nanobubbles. These porous materials produce nanoscale bubbles through their unique pore structure and surface characteristics. These bubbles have a larger specific surface area and higher mass transfer efficiency, which can effectively input oxygen into the water body and stably transport oxygen nanobubbles to the target hypoxic area, thereby achieving local oxygenation of the water body.

[0006] However, the sustainable restoration of anoxic water bodies not only relies on oxygenation through physical and chemical means, but more importantly, it relies on the degradation of organic pollutants and the self-repair of the ecosystem through the metabolic activities of in situ microbial communities. Therefore, the development of new green oxygen-carrying materials and the revealing of their microbial mechanisms for the restoration of anoxic water bodies have important scientific significance and application value. Summary of the invention

[0007] In view of the defects of the prior art, the object of the present invention is to provide an oxygen-carrying material for water oxygenation treatment and a preparation method thereof.

[0008] Another object of the present invention is to provide an application of the oxygen-carrying material as described above for water oxygenation treatment, utilizing the pore structure of the porous composite material of the oxygen-carrying material and the interaction between the surface polar functional groups and the gas molecules to achieve efficient loading of oxygen nanobubbles and regulation of oxygen adsorption and slow-release performance.

[0009] To achieve the above purpose, the solution adopted by the present invention is as follows:

[0010] In a first aspect, the present invention provides an oxygen-carrying material for oxygenation treatment of water bodies, which is a granular porous composite material in which calixarene and / or its inclusion compound is loaded on a self-assembled metal organic framework (MOF) material; preferably, the mass ratio of the calixarene and / or its inclusion compound to the self-assembled metal organic framework (MOF) material is (10-50):100, preferably (10-30):100; preferably, the specific surface area of ​​the oxygen-carrying material is 1000-1200m 2 / g.

[0011] Preferably, the calixarene is selected from any one of calix[3]arene, calix[4]arene, calix[5]arene, calix[6]arene, calix[7]arene and calix[8]arene, preferably calix[4]arene.

[0012] Preferably, the calixarene is a sulfonated thiacalixarene, preferably a sulfonated thiacalix[4]arene.

[0013] Preferably, the inclusion complex of calixarene comprises an inclusion complex of sulfonated thiacalix[4]arene and a coordinated metal ion, wherein the metal ion is selected from Fe 3+ 、Ni 2+ 、Al 3+ , Pb 2+ 、Cd 2+ 、Co 2+ , Cu 2+ and Ag + One or more of, preferably Co 2+ ; The molar ratio of sulfonated thiacalix[4]arene to coordinated metal ion is 1:(5-8), preferably 1:(6-7).

[0014] Preferably, the inclusion complex of calixarene also includes an inclusion complex of sulfonated thiacalix[4]arene and an electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB); the molar ratio of sulfonated thiacalix[4]arene to the electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) is 1:(20-25), preferably 1:(21-23).

[0015] Preferably, the self-assembled metal organic framework (MOF) material is a zeolite-imidazole framework material ZIF, preferably ZIF-8.

[0016] In a second aspect, the present invention also provides a method for preparing an oxygen-carrying material for water oxygenation treatment as described above, comprising the following steps: dissolving calixarene and / or its inclusion complex in a mixed solvent, then adding a self-assembled metal organic framework (MOF) material, and then grinding the mixture in a mortar. After the grinding is completed, washing the solid product with a washing solvent, collecting it by centrifugation, and finally drying it.

[0017] Preferably, the calixarene is a sulfonated thiacalixarene, preferably a sulfonated thiacalix[4]arene; the inclusion complex of the calixarene comprises an inclusion complex of the sulfonated thiacalix[4]arene and a coordinated metal ion, wherein the metal ion is selected from Fe 3+ 、Ni 2 + 、Al 3+ , Pb 2+ 、Cd 2+ 、Co 2+ , Cu 2+ and Ag + One or more of, preferably Co 2+ , the molar ratio of sulfonated thiacalix[4]arene to the coordinated metal ion is 1:(5-8), preferably 1:(6-7); the inclusion complex of calixarene also includes the inclusion complex of sulfonated thiacalix[4]arene and the electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB), the inclusion complex of sulfonated thiacalix[4]arene and the electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) The molar ratio of TATB to 3TATB is 1:(20-25), preferably 1:(21-23); the particle size of the calixarene inclusion compound is 10-50 μm, preferably 30-50 μm; the self-assembled metal organic framework (MOF) material is a zeolite-imidazole framework material ZIF, preferably ZIF-8, prepared by coprecipitation method, with a particle size of 100-400 nm and a specific surface area of ​​1000-1500 m 2 / g; the particle size of the obtained oxygen-carrying material is 150-450nm, and the specific surface area is 1000-1200m 2 / g.

[0018] Preferably, the mixed solvent is a mixture of methanol and dimethylformamide, the volume ratio of methanol to dimethylformamide is (3-5):1; the grinding rate is 150-250rpm, and the grinding time is 5-10 minutes; the washing solvent is a mixture of DMF and methanol, washed 3 times, and the drying temperature is 50-70°C.

[0019] In a third aspect, the present invention also provides an application of the oxygen-carrying material for water oxygenation treatment as described above, wherein the oxygen-carrying material is directly thrown into anoxic water, and the oxygen-carrying material in powdery granular form is in full contact with the water to generate oxygen nanobubbles. The pore structure of the porous composite material of the oxygen-carrying material and the interaction between the surface polar functional groups and the gas molecules are utilized to achieve efficient loading of the oxygen nanobubbles and regulation of oxygen adsorption and sustained-release performance.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The oxygen-carrying material for water oxygenation treatment prepared by the present invention utilizes the pore structure of the self-assembled ZIF-8 matrix material of the porous composite material and the interaction between the polar functional groups (such as hydroxyl, carboxyl, sulfonic acid, bridging sulfur atoms, etc.) carried by the sulfonated thiacalix[4]arene (TCAS) and / or its inclusion complex loaded on the surface thereof and the oxygen gas molecules generated in the water body, thereby realizing the efficient loading and controllable release of oxygen nanobubbles and realizing the sustainable recovery of the anoxic freshwater system; the preparation process is fast and easy to mass produce. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a scanning electron microscope (SEM) image of the granular porous composite material (ZIF-8@PCC) prepared in an example of the present invention.

[0023] Figure 2 This is a chart of the oxygen carrying capacity of the granular porous composite material (ZIF-8@PCC) prepared in the embodiment of the present invention and the control sample (ZIF-8, PCC).

[0024] Figure 3 This is a DO kinetic chart of the granular porous composite material (ZIF-8@PCC) prepared in the embodiment of the present invention and the control samples (ZIF-8, PCC) in the overlying water during a 10-day experiment.

[0025] Figure 4DO diagram of the granular porous composite material (ZIF-8@PCC) prepared in the embodiment of the present invention and the control sample (ZIF-8, control) during 28 days. DETAILED DESCRIPTION

[0026] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and specific implementation methods.

[0027] The invention provides an oxygen-carrying material for water body oxygenation treatment, which is a granular porous composite material in which calixarene and / or its inclusion compound is loaded on a self-assembled metal organic framework (MOF) material.

[0028] According to the scheme of the present invention, in the oxygen-carrying material for water oxygenation treatment provided by the present invention, the self-assembled metal organic framework (MOF) material used in the present invention is the matrix material of the oxygen-carrying material of the present invention, which is an organic-inorganic hybrid material with intramolecular pores formed by self-assembly of organic ligands and inorganic metal ions or clusters through coordination bonds. It can be divided into network metal organic framework materials IRMOF, zeolite-imidazole framework materials ZIF, Levahill organic framework materials MIL and channel framework materials PCN, etc. According to the type, zeolite-imidazole framework materials ZIF are preferably used as the matrix material of the oxygen-carrying material of the present invention, such as ZIF-8 and ZIF-67.

[0029] In an embodiment of the present invention, ZIF-8 is taken as an example as a self-assembled metal organic framework (MOF) material. The ZIF-8 material is a metal organic framework material with high crystallinity and porosity, composed of metal ions (such as zinc ions) and organic ligands (such as 2-methylimidazole), with high specific surface area and high porosity, and can be used as carrier particles of oxygen nanobubbles. Its unique porous pore structure and surface properties can produce nanoscale bubbles in water.

[0030] The ZIF-8 material can be prepared by conventional preparation methods such as hydrothermal method or coprecipitation method. In the present invention, the ZIF-8 material prepared by the coprecipitation method which can prepare a smaller particle size range and a larger specific surface area is preferably used. The preparation process comprises the following steps: firstly dissolving a metal salt (such as zinc nitrate hexahydrate) and an organic ligand (such as 2-methylimidazole) in a methanol solvent respectively, then mixing the two solutions, stirring and mixing at room temperature, after the reaction is completed, obtaining a white precipitate by centrifugation, then washing with a methanol solvent for multiple times, and finally drying at 60°C to obtain a ZIF-8 material. The obtained ZIF-8 material has a particle size of 100-400nm and a specific surface area of ​​1000-1500m 2 / g, the pore size of ZIF-8 material can also be changed by adjusting the synthesis conditions according to specific needs.

[0031] According to the scheme of the present invention, in the present invention, zeolite-imidazole framework material ZIF-8 material is preferentially used as the matrix material of the oxygen-carrying material of the present invention, which can realize the generation of nano-scale bubbles in the water body. Its pore structure is not only conducive to the adsorption of oxygen gas, but also conducive to the regulation of the slow-release performance of oxygen adsorption, thereby achieving the purpose of efficient local oxygenation and sustainable restoration of hypoxic water bodies.

[0032] In order to further improve the gas adsorption and sustained release performance of the matrix material ZIF-8, the present invention also loads container-shaped (or cage-shaped) calixarene and / or its inclusion complex on the pore surface of the matrix material ZIF-8 material. According to the scheme of the present invention, the calixarene used in the present invention is a type of macrocyclic oligomer connected by phenol units through methylene, because its tetramer conformation is similar to the Greek Holy Grail, and it is an aromatic molecule composed of multiple benzene rings, with a cavity composed of cyclically arranged hydroxyl groups and benzene rings connected by methylene, ethylene or oxypropylidene groups, the upper edge of the cavity is a hydrophobic tert-butyl group connected to the benzene ring, and the lower edge of the cavity is a hydrophilic hydroxyl group and other groups, the size of the cavity can be adjusted, and neutral molecules or ions can be identified and included.

[0033] According to the number of benzene rings in the cup-shaped cavity of calixarene, it can be divided into calix[3]arene, calix[4]arene, calix[5]arene, calix[6]arene, calix[7]arene or calix[8]arene. In the present invention, the more commonly used calix[4]arene is preferably used. In order to improve the reaction activity, the present invention more preferably uses sulfonated thiacalix[4]arene (TCAS for short) as shown in the following formula (I).

[0034]

[0035] According to the scheme of the present invention, in the sulfonated thiacalix [4]arene (TCAS) used in the present invention, the lower edge of the cavity is replaced by the heteroatom S to replace the bridge chain methylene, which greatly improves the rigidity and polarity of the aromatic macrocyclic structure of the calixarene; the tert-butyl group on the upper edge of the cavity is replaced by the sodium sulfonyl salt, which can further improve the water solubility and biocompatibility of the calixarene, and the sulfonate ion also enhances the electronegativity of the calixarene cavity, providing it with additional electrostatic binding sites, so that the sulfonated thiacalix [4]arene (TCAS) exhibits a strong bonding ability to organic cations in the aqueous phase, as shown in formula (II). In the oxygen-carrying material for water oxygenation treatment of the present invention, these surface polar functional groups (such as hydroxyl, carboxyl, etc.) and hydrogen bonding, electrostatic bonding and other bonding abilities can be used to increase the interaction with the oxygen gas molecules generated in the water body, enhance the stability of the oxygen nanobubbles, and promote the interaction between the interface of the oxygen nanobubbles and the microbial community in the water body, so as to achieve efficient loading and controllable release of the oxygen nanobubbles.

[0036]

[0037] According to the scheme of the present invention, in the sulfonated thiacalix[4]arene (TCAS) used in the present invention, a pair of lone pairs of electrons generated by the bridging sulfur atom can participate in the binding and recognition of metal cations, and can enhance the recognition and binding of the inclusion complex and the matrix ZIF-8 material, for example, the metal ion Fe 3+ 、Ni 2+ 、Al 3+ , Pb 2+ 、Cd 2+ 、Co 2+ , Cu 2+ and Ag + Therefore, in the present invention, the inclusion compound of calixarene used in the present invention comprises sulfonated thiacalix[4]arene and coordinated metal ion Fe 3+ 、Ni 2+ 、Al 3+ , Pb 2+ 、Cd 2+ 、Co 2+ , Cu 2+ and Ag + In the embodiment of the present invention, Co 2+ The embodiment of the present invention is described as a preferred example of the coordinated metal ion. In the present invention, the molar ratio of the sulfonated thiacalix[4]arene to the coordinated metal ion is 1:(5-8), preferably 1:(6-7).

[0038] According to the solution of the present invention, the inclusion complex of calixarene used in the present invention also includes the inclusion complex of sulfonated thiacalix[4]arene and electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB). Among them, 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) can enhance the binding with the matrix ZIF-8 material through the dipole-dipole effect or weak coordination bond of the nitrogen atom in its molecular formula, and promote the binding and adsorption with the oxygen gas molecules generated in the water body. In the present invention, the molar ratio of sulfonated thiacalix[4]arene to the electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) is 1:(20-25), preferably 1:(21-23).

[0039] According to the scheme of the present invention, the present invention combines sulfonated thiacalix[4]arene with metal ion Co 2+The inclusion complex with 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) can also play a role in adjusting the pore size of the ZIF-8 material, which not only makes the oxygen-carrying material of the present invention better fit the oxygen size range, but also makes the size of the matrix material ZIF-8 material and the container-shaped (or cage-shaped) sulfonated thiacalix[4]arene (TCAS) and / or its inclusion complex loaded on its surface closely matched. The matrix material and the surface regulator material synergistically enhance the adsorption of oxygen by the porous composite material, and the sustained release performance is significantly improved.

[0040] According to the scheme of the present invention, as a specific embodiment, the present invention also provides a method for preparing the above-mentioned calixarene and / or its inclusion compound, comprising the following steps:

[0041] Step (1), preparation of sulfonated thiacalix[4]arene (TCAS): dissolve calixarene in dichloromethane solvent, slowly drop chlorosulfonic acid into the calixarene solution under ice-water bath conditions, control the dropping speed to avoid violent heat release, after the dropwise addition is completed, slowly pour the reaction mixture into ice water, then adjust the pH value to 7.0 with sodium hydroxide solution (10% w / v), and obtain a crude product by filtration or centrifugation, then dissolve the crude product in deionized water, heat to about 60° C. to completely dissolve it, cool to room temperature, add ethanol to induce crystallization, collect the crystalline product, wash with methanol to remove impurities, and finally vacuum dry at about 60° C. to obtain;

[0042] Step (2), preparation of the inclusion complex of sulfonated thiacalix[4]arene (TCAS): suspend cobalt chloride hexahydrate, 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) and sulfonated thiacalix[4]arene (TCAS) in methanol, and then heat the mixture in an oven at about 85°C for 12 hours. After cooling to room temperature, collect the generated large purple crystals and wash them with methanol to obtain the product.

[0043] In step (2) of the above preparation method, the sulfonated thiacalix[4]arene is reacted with the coordinated metal ion Co 2+ The molar ratio of sulfonated thiacalix[4]arene to electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) is 1:(20-25), preferably 1:(21-23); the particle size of the obtained inclusion complex of sulfonated thiacalix[4]arene (TCAS) is 10-50 μm, preferably 30-50 μm.

[0044] As mentioned above, in order to further improve the gas adsorption and sustained release performance of the matrix material ZIF-8, the present invention also loads container-shaped (or cage-shaped) calixarene and / or its inclusion complex on the pore surface of the matrix material ZIF-8, for example, loading the sulfonated thiacalix[4]arene (TCAS) and / or its inclusion complex as described above, thereby obtaining a granular porous composite material as the oxygen-carrying material for water oxygenation treatment of the present invention.

[0045] According to the scheme of the present invention, the present invention further provides a method for preparing the above-mentioned oxygen-carrying material for water oxygenation treatment, comprising the following steps: dissolving the sulfonated thiacalix[4]arene (TCAS) and / or its inclusion complex as described above in a mixed solvent, then adding the self-assembled ZIF-8 matrix material, and then placing the mixture in a mortar for grinding. After the grinding is completed, washing the solid product with a washing solvent, collecting it by centrifugation, and finally drying it to obtain the product.

[0046] In the above preparation method, the mixed solvent is a mixture of methanol and dimethylformamide, and the volume ratio of methanol to dimethylformamide is (3-5):1; the grinding rate is 150-250rpm, and the grinding time is 5-10 minutes; the washing solvent is a mixture of DMF and methanol, washing is performed 3 times, and the drying temperature is 50-70°C.

[0047] The particle size of the granular porous composite material obtained by the above preparation method is 150-450nm, and the specific surface area is 1000-1200m 2 / g.

[0048] The granular porous composite material obtained by the above preparation method is used as the oxygen-carrying material for water oxygenation treatment of the present invention. The present invention adopts a solvent-assisted grinding method (the solvent is a mixed system of methanol and dimethylformamide). The grinding process only takes 5 minutes (mechanical grinding) or 10 minutes (manual grinding), which is much shorter than the reaction time of several hours or even dozens of hours required by the traditional impregnation method, significantly improving the preparation efficiency and facilitating large-scale production.

[0049] The granular porous composite material obtained by the above preparation method is used as the oxygen-carrying material for water oxygenation treatment of the present invention. The present invention uses a self-assembled ZIF-8 material as a matrix material, and uses sulfonated thiacalix[4]arene (TCAS) and / or its inclusion compound as a surface regulator and surface capping agent of the matrix material. The sulfonated thiacalix[4]arene (TCAS) and / or its inclusion compound has a porous coordination cage characteristic of intrinsic pores and pore sizes, thereby improving the gas adsorption and sustained release performance of the matrix material self-assembled ZIF-8 material. Conventional surface capping agents (such as polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG), etc.) may partially block the porosity of the matrix framework material when functionalizing the ZIF-8 surface, so it is necessary to additionally screen suitable ligands and optimize the modification conditions. In contrast, the present invention uses sulfonated thiacalix[4]arene (TCAS) and / or its inclusion compound as a surface regulator and surface capping agent of the matrix material, and can synthesize a porous composite material with substantially retained porosity, thereby avoiding additional optimization or screening steps.

[0050] The granular porous composite material obtained by the above preparation method is used as the oxygen-carrying material for water oxygenation treatment of the present invention. The pore structure of the self-assembled ZIF-8 matrix material of the porous composite material and the interaction between the polar functional groups (such as hydroxyl, carboxyl, sulfonic acid, bridging sulfur atoms, etc.) carried by the sulfonated thiacalix[4]arene (TCAS) and / or its inclusion complex loaded on its surface and the oxygen gas molecules generated in the water body are utilized to achieve efficient loading and controllable release of oxygen nanobubbles, and realize sustainable recovery of the anoxic freshwater system.

[0051] Specifically, the multi-level pore structure of the composite material not only provides a stable storage space for oxygen nanobubbles, but also optimizes the release dynamics of the bubbles by regulating the pore size and surface chemical properties. In addition, the polar functional groups on the surface of the material (such as hydroxyl, carboxyl, sulfonic acid, bridging sulfur atoms, etc.) enhance the stability of oxygen nanobubbles through hydrogen bonds, electrostatic interactions and other mechanisms, and promote their interfacial interactions with microbial communities in water bodies. At the same time, by adjusting the pore / window aperture size exposed on the crystal surface of the calixarene and / or its inclusion complex nanoparticles and the surface-modified polar functional groups such as sulfonic acid, hydroxyl, and carboxyl, the adsorption of oxygen is further improved, and it has a sustained release effect.

[0052] The granular porous composite material obtained by the above preparation method is used as the oxygen-carrying material for water oxygenation treatment of the present invention. The present invention adopts a mechanochemical synthesis method to quickly and easily prepare the above porous composite material, and the sizes of the matrix material ZIF-8 material and the container-shaped (or cage-shaped) sulfonated thiacalix[4]arene (TCAS) and / or its inclusion complex loaded on the surface thereof are closely matched, and the matrix material and the surface conditioning agent material synergistically enhance the adsorption of oxygen by the porous composite material, and the sustained release performance is significantly improved. The mechanochemical synthesis method is not only widely applicable, but also provides a potential design principle for the development of hybrid porous materials with enhanced oxygen adsorption and sustained release performance, and shows broad application prospects in the fields of water pollution control.

[0053] The present invention is further described below in conjunction with examples, the purpose of which is to better understand the content of the present invention and reflect the essential characteristics of the present invention, so the examples cited should not be regarded as limiting the scope of protection of the present invention. It is also particularly pointed out here that the specific experimental methods and equipment involved in the examples are conventional methods or implemented under the conditions recommended by the manufacturer's instructions unless otherwise specified, and the reagents involved are commercially available unless otherwise specified.

[0054] Example:

[0055] An oxygen-carrying material for water oxygenation treatment is a granular porous composite material in which calixarene and / or its inclusion compound is loaded on a self-assembled metal organic framework (MOF) material, specifically a granular porous composite material in which sulfonated thiacalix[4]arene (TCAS) and / or its inclusion compound is loaded on a self-assembled ZIF-8 matrix material. The preparation method thereof comprises the following steps:

[0056] Step S1: Preparation of self-assembled ZIF-8 matrix material: Zn(NO3)2·6H2O (5.95 g, 0.02 mol) and 2-methylimidazole (6.16 g, 0.075 mol) were dissolved in 150 mL of methanol (MeOH) to form two clear solutions. Subsequently, the 2-methylimidazole solution was poured into the Zn(NO3)2·6H2O solution and stirred at room temperature for 24 hours. After the reaction, a white precipitate was obtained by centrifugation, washed with methanol several times, and finally dried at 60°C to obtain ZIF-8 (specific surface area 1250 m 2 / g);

[0057] Step S2: Preparation of sulfonated thiacalix[4]arene (TCAS) sodium salt: Weigh calixarene (1.00 g, 1.47 mmol) and dissolve it in dichloromethane (50 mL) to form a uniform solution. Slowly add chlorosulfonic acid (2.5 mL, 37.5 mmol) to the calixarene solution under ice-water bath conditions, and control the drop rate to avoid violent heat release. After the dropwise addition is completed, the reaction mixture is warmed to room temperature and stirred for 6 hours to ensure that the sulfonation reaction is complete. The reaction mixture is slowly poured into ice water (100 mL) and stirred for 30 minutes. Use sodium hydroxide solution (10% w / v) to adjust the pH to 7.0, and obtain the crude product by filtration or centrifugation. The crude product is dissolved in deionized water (50 mL) and heated to 60°C to completely dissolve it. After slowly cooling to room temperature, ethanol (100 mL) is added to induce crystallization. The crystalline product is collected and washed with methanol (20 mL×3 times) to remove impurities. Finally, the product was dried under vacuum at 60 °C for 12 h to obtain pure sulfonated thiacalix[4]arene (TCAS) sodium salt (PCC);

[0058] Step S3: Preparation of inclusion complex of sulfonated thiacalix[4]arene (TCAS): Cobalt chloride hexahydrate (23.7 mg, 0.1 mmol), 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) (14.5 mg, 0.33 mmol) and sulfonated thiacalix[4]arene (TCAS) sodium salt (18 mg, 0.015 mmol) were suspended in 2 mL of methanol, and then the mixture was heated in an oven at about 85° C. for 12 hours. After cooling to room temperature, the generated large purple crystals were collected and washed with methanol;

[0059] Step S4: 15 mg PCCs was dissolved in 1.5 mL of a mixed solvent (methanol: dimethylformamide = 4:1, volume ratio), and then 100 mg ZIF-8 was dispersed in the PCC solution. The mixture was placed in a mortar and ground at 200 rpm for 5 minutes, or manually ground for 10 minutes. After grinding, the solid product was washed three times with DMF and methanol, respectively, to remove free PCC, and the solid product was collected by centrifugation. Finally, the obtained solid was air-dried at 60 ° C to obtain ZIF-8@PCC (specific surface area 1120 m 2 / g).

[0060] Performance test: The static gas adsorption equilibrium test was performed on a BSD-660S-0005 instrument. Before the test, the sample was vacuum activated at 120°C for 12 hours. The activated sample was tested for N2 adsorption isotherm at 77K. The test temperature for O2 adsorption isotherm was 273K.

[0061] The scanning electron microscopy image of the prepared granular porous composite material (ZIF-8@PCC) is shown in Figure 1 shown.

[0062] The oxygen carrying capacity of the prepared granular porous composite material (ZIF-8@PCC) and the control sample (ZIF-8, PCC) is shown in Figure 2 shown.

[0063] The DO dynamics of the prepared granular porous composite material (ZIF-8@PCC) and the control samples (ZIF-8, PCC) in the overlying water during the 10-day experiment are shown in Figure 2. Figure 3 shown.

[0064] The DO graphs of the prepared granular porous composite material (ZIF-8@PCC) and the control sample (ZIF-8, PCC) during 28 days are shown in Figure 2. Figure 4 As shown, in Figure 4 In the figure, “control” refers to the blank control group, that is, the DO curve when no sample is added.

[0065] from Figure 2 , Figure 3 and Figure 4 It can be seen that compared with the ZIF-8 material itself or sulfonated thiacalix[4]arene (TCAS) sodium salt (PCC), the granular porous composite material (ZIF-8@PCC) prepared by the present invention has a greatly improved adsorption capacity for oxygen and has a sustained release effect.

[0066] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An oxygen-carrying material for water oxygenation treatment, characterized in that: The invention is a granular porous composite material in which calixarene and / or its inclusion compound is supported on a self-assembled metal organic framework (MOF) material; preferably, the mass ratio of the calixarene and / or its inclusion compound to the self-assembled metal organic framework (MOF) material is (10-50):100, preferably (10-30):100; preferably, the specific surface area of ​​the oxygen-carrying material is 1000-1200m 2 / g.

2. The oxygen-carrying material for water oxygenation treatment according to claim 1, characterized in that: The calixarene is selected from any one of calix[3]arene, calix[4]arene, calix[5]arene, calix[6]arene, calix[7]arene and calix[8]arene, preferably calix[4]arene.

3. The oxygen-carrying material for water oxygenation treatment according to claim 2, characterized in that: The calixarene is a sulfonated thiacalixarene, preferably a sulfonated thiacalix[4]arene.

4. The oxygen-carrying material for water oxygenation treatment according to claim 3, characterized in that: The inclusion compound of calixarene comprises an inclusion compound of sulfonated thiacalix[4]arene and a coordinated metal ion, wherein the metal ion is selected from Fe 3+ 、Ni 2+ 、Al 3+ , Pb 2+ 、Cd 2+ 、Co 2+ , Cu 2+ and Ag + One or more of, preferably Co 2+ ; The molar ratio of sulfonated thiacalix[4]arene to coordinated metal ion is 1:(5-8), preferably 1:(6-7).

5. The oxygen-carrying material for water oxygenation treatment according to claim 4, characterized in that: The inclusion complex of calixarene also includes the inclusion complex of sulfonated thiacalix[4]arene and electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB); the molar ratio of sulfonated thiacalix[4]arene to electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) is 1:(20-25), preferably 1: (21-23)。 6. The oxygen-carrying material for water oxygenation treatment according to claim 1, characterized in that: The self-assembled metal organic framework (MOF) material is a zeolite-imidazole framework material ZIF, preferably ZIF-8.

7. A method for preparing an oxygen-carrying material for water oxygenation treatment according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: dissolving calixarene and / or its inclusion complex in a mixed solvent, then adding a self-assembled metal organic framework (MOF) material, and then grinding the mixture in a mortar. After the grinding is completed, washing the solid product with a washing solvent, collecting it by centrifugation, and finally drying it to obtain the product.

8. The preparation method according to claim 7, characterized in that: The calixarene is a sulfonated thiacalixarene, preferably a sulfonated thiacalix[4]arene; the inclusion complex of the calixarene comprises an inclusion complex of the sulfonated thiacalix[4]arene and a coordinated metal ion, wherein the metal ion is selected from Fe 3+ 、Ni 2+ 、Al 3+ , Pb 2+ 、Cd 2+ 、Co 2+ , Cu 2+ and Ag + One or more of, preferably Co 2+ , the molar ratio of sulfonated thiacalix[4]arene to the coordinated metal ion is 1:(5-8), preferably 1:(6-7); the inclusion complex of calixarene also includes the inclusion complex of sulfonated thiacalix[4]arene and the electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB), the inclusion complex of sulfonated thiacalix[4]arene and the electron acceptor 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) The molar ratio of TATB to 3TATB is 1:(20-25), preferably 1:(21-23); the particle size of the calixarene inclusion compound is 10-50 μm, preferably 30-50 μm; the self-assembled metal organic framework (MOF) material is a zeolite-imidazole framework material ZIF, preferably ZIF-8, prepared by coprecipitation method, with a particle size of 100-400 nm and a specific surface area of ​​1000-1500 m 2 / g; the particle size of the obtained oxygen-carrying material is 150-450nm, and the specific surface area is 1000-1200m 2 / g.

9. The preparation method according to claim 7, characterized in that: The mixed solvent is a mixture of methanol and dimethylformamide, and the volume ratio of methanol to dimethylformamide is (3-5):1; the grinding rate is 150-250rpm, and the grinding time is 5-10 minutes; the washing solvent is a mixture of DMF and methanol, washing is performed 3 times, and the drying temperature is 50-70°C.

10. An application of the oxygen-carrying material for water oxygenation treatment according to any one of claims 1 to 6, characterized in that: The oxygen-carrying material is directly thrown into an oxygen-deficient water body, and the oxygen-carrying material in powdered granular form is fully in contact with the water body to generate oxygen nanobubbles. The pore structure of the porous composite material of the oxygen-carrying material and the interaction between the surface polar functional groups and gas molecules are utilized to achieve efficient loading of the oxygen nanobubbles and regulation of oxygen adsorption and slow-release performance.

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