阅读说明：本技术 一种多重响应性有机无机复合Janus笼状材料及其制备与应用 (Multi-responsiveness organic-inorganic composite Janus cage-shaped material and preparation and application thereof ) 是由 杨振忠 斯炎 梁福鑫 于 2019-04-26 设计创作，主要内容包括：本发明提供一种多重响应性有机无机复合Janus笼状材料及其制备方法与其在燃油污染物处理中的应用。通过不完全刻蚀磁性介孔二氧化硅颗粒的磁性内核,保留磁性并释放内表面新鲜硅羟基,外侧修饰离子液体赋予其催化性能,内侧接枝响应性聚合物,得到可催化氧化燃油中硫化物污染物并可富集且可控释放催化氧化后产物的磁性Janus笼状材料。本发明能够实现批量化制备组成可调控的具有催化性能和多重响应性的Janus材料,此材料结合了离子液体、响应性聚合物和磁性介孔纳米粒子的优异性能,在尾气处理、水体净化和药物运输等领域中具有重要的意义。(The invention provides a multi-responsiveness organic-inorganic composite Janus cage-shaped material, a preparation method thereof and application thereof in fuel pollutant treatment. The magnetic Janus cage-shaped material which can catalyze and oxidize sulfide pollutants in fuel oil and enrich and controllably release products after catalytic oxidation is obtained by incompletely etching the magnetic core of the magnetic mesoporous silica particles, retaining magnetism and releasing fresh silicon hydroxyl on the inner surface, modifying ionic liquid on the outer side to endow the catalytic performance with the ionic liquid, and grafting responsive polymers on the inner side. The invention can realize the batch preparation of the Janus material with adjustable composition, catalytic performance and multiple responsiveness, combines the excellent performances of the ionic liquid, the responsive polymer and the magnetic mesoporous nano particles, and has important significance in the fields of tail gas treatment, water purification, drug transportation and the like.)

1. An organic-inorganic composite Janus cage-shaped material is as follows: the magnetic Janus cage-shaped material is obtained by incompletely etching the magnetic core of the magnetic mesoporous silica particle, retaining magnetism, releasing silicon hydroxyl on the inner surface, modifying ionic liquid on the outer side to endow the catalytic performance of the magnetic mesoporous silica particle with the ionic liquid, and grafting a responsive polymer on the inner side;

wherein the chemical composition of the inner and outer sides is adjustable; the thickness of the shell layer is controllable;

the organic-inorganic composite Janus cage-shaped material is a nano particle with the size of 100-300 nm.

2. A method of preparing the organic-inorganic composite Janus cage material of claim 1, comprising the steps of:

1) preparing magnetic nano particles, taking a surfactant as a pore-forming agent, and coating a layer of mesoporous silica on the surfaces of the magnetic nano particles to obtain magnetic mesoporous silica particles;

2) Modifying imidazoline groups on the surfaces of the magnetic mesoporous silica particles obtained in the step 1) and further reacting the imidazoline groups with halogenated hydrocarbons to obtain magnetic mesoporous silica particles of which the outer surfaces are modified with ionic liquid taking halogen as anions;

3) removing the pore-forming agent from the magnetic mesoporous silica particles of which the outer surfaces are modified with the ionic liquid taking halogen as anions obtained in the step 2), and then carrying out incomplete etching by using dilute hydrochloric acid to release partial cavities to obtain particles with a yolk-eggshell structure;

4) modifying double bonds on the inner surface of the yolk-eggshell structure particles obtained in the step 3) to obtain yolk-eggshell structure particles modified with double bonds on the inner surface;

5) under the action of an initiator, carrying out free radical polymerization on the monomer and the modified double bond on the inner surface to obtain Janus particles with the inner surface grafted with a responsive polymer;

6) leading the Janus particles with the inner surface grafted with the responsive polymer obtained in the step 5) to react with phosphotungstic acid, and obtaining the product with the outer surface with anions of PW₁₂O₄₀ ^3-The inner surface of the ionic liquid is Janus cage-shaped material modified by responsive polymer.

3. The method of claim 2, wherein: in the step 1), the magnetic nanoparticles are Fe ₃O₄A nanoparticle;

the surfactant is cetyl trimethyl ammonium bromide;

the coating of the mesoporous silica layer on the surface of the magnetic nano-particles is realized by the following operations: in the presence of a surfactant serving as a pore-foaming agent, tetraethoxysilane is hydrolyzed under an alkaline condition to obtain mesoporous silicon dioxide.

4. A method according to claim 2 or 3, characterized in that: in the step 2), the operation of modifying the imidazoline group on the surface of the magnetic mesoporous silica particle is as follows: dispersing the magnetic mesoporous silica particles into a solvent, adding an imidazoline silane coupling agent, and reacting to obtain imidazoline group modified magnetic mesoporous silica particles;

wherein, the imidazoline silane coupling agent can be triethoxy-3- (2-imidazole-1-linyl) propane silane;

the reaction temperature is 60-80 ℃ and the reaction time is 10-16 h.

5. The method according to any one of claims 2-4, wherein: the halogenated hydrocarbon for the reaction with the imidazolinyl group is: at least one of bromoethane, bromo-n-propane, bromo-n-butane, bromo-n-pentane, 1-bromohexane, n-bromododecane, chloroethane, chloro-n-propane, chloro-n-butane, chloro-n-pentane, and 1-chlorohexane;

The reaction temperature of the reaction of the imidazoline group and the halogenated hydrocarbon is 110-120 ℃, and the reaction time is 10-15 h.

6. The method according to any one of claims 2-5, wherein: in the step 3), the operation of removing the pore-forming agent is as follows: placing the magnetic mesoporous silica modified by the ionic liquid in a Soxhlet extractor, and extracting for three days by using acetone;

the operation of using dilute hydrochloric acid to carry out incomplete etching is as follows: dispersing the magnetic mesoporous silica modified by the ionic liquid in ethanol, adding hydrochloric acid, and reacting;

the reaction temperature is 65-75 ℃, and the reaction time is 1.5-2.5 hours;

the operation of the step 4) is as follows: dispersing the particles with the yolk-eggshell structure obtained in the step 3) into a solvent, adding 3- (methacryloyloxy) propyl trimethoxy silane, and reacting;

the ratio of the particles with the yolk-eggshell structure to the 3- (methacryloyloxy) propyl trimethoxy silane is as follows: 1 mg: 1-1.2 uL;

the reaction temperature is 65-75 ℃ and the reaction time is 10-14 hours.

7. The method according to any one of claims 2-6, wherein: in the step 5), the monomers which can be used for carrying out free radical polymerization with the double bond of the inner surface modification comprise a responsive monomer and an alkene monomer;

The responsive monomer is selected from N-isopropyl acrylamide and diethylaminoethyl methacrylate;

the vinyl monomer is selected from one or any combination of acrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, butadiene, isoprene and chloroprene;

the initiator for the free radical polymerization reaction is an oil-soluble free radical initiator:

the oil-soluble free radical initiator comprises azo compound initiators; also comprises a peroxide oil-soluble initiator;

the addition amount of the initiator accounts for 0.05 to 5 percent of the total mass of the monomers;

in the free radical polymerization, the reaction temperature is as follows: the reaction time is as follows at 60-90 deg.C: 8-14 h.

8. The method according to any one of claims 2-7, wherein: in the step 6), the mass ratio of the Janus particles with the inner surface grafted with the responsive polymer to the phosphotungstic acid is as follows: 1: 2.8-3.5;

the reaction with phosphotungstic acid is carried out at room temperature for 1-2 h.

9. The organic-inorganic composite Janus cage-shaped material of claim 1 or the organic-inorganic composite Janus cage-shaped material prepared by the method of any one of claims 2-8 is applied to the treatment of fuel oil sulfide pollutants;

The application specifically can be as follows: the sulfide pollutants in the fuel oil are catalyzed and oxidized, the products after catalytic oxidation are enriched, and the products after catalytic oxidation are released controllably.

10. A method for treating fuel oil sulfide pollutants by using the organic-inorganic composite Janus cage material of claim 1 or the organic-inorganic composite Janus cage material prepared by the method of any one of claims 2-8, comprising the following steps: in the presence of an organic-inorganic composite Janus cage-shaped material, enabling a fuel oil sulfide pollutant to be treated to contact with an oxidant to generate a catalytic oxidation reaction, adding water to extract a treated product, and enabling an aqueous solution in which the treated product is dissolved to be adsorbed into a Janus cage cavity, so as to realize separation and enrichment of the treated product from a catalytic system;

the temperature of the catalytic oxidation reaction is 20-25 ℃.

11. The method of claim 10, wherein: the method further comprises: heating the Janus material adsorbed with the water solution of the treated product to release the treated product;

the heating temperature is 40-45 ℃.

Technical Field

The invention relates to the technical field of materials, in particular to a multiple-responsiveness organic-inorganic composite Janus cage-shaped material, a preparation method thereof and application thereof in fuel oil pollutant treatment.

Background

Janus originated from the goddess of ancient Roman mystery, in 1991, the famous French scientist De Gennes first proposed Janus to describe particles with dual properties in structure or organization (De Gennes.; P.G. SoftMatter. science.1992,256(5056), 495-497). Janus materials with dual properties are novel materials with unique microstructures and functionalitiesHas important application prospect in multiple fields and becomes a research hotspot in the field of new material science. Wherein, the material with Yolk-eggshell (Yolk-Shell) structure has a Shell layer with better transmittance, and the inner cavity endows the material with excellent loading capacity, so that the material can be used in drug delivery (Zhang L, Wang T, Li L, Wang C, SuZ, Li J, Multifunctional fluorescent-magnetic polyethylene functionalized Fe)₃O₄-mesoporous silica yolk–shell nanocapsules for siRNA deliver”[J],Chem.Commun.2012,48,8706-8708)，(Fang X,Zhao X,Fang W,Chen C,Zheng N,Self-templating synthesis of hollow mesoporous silica and their applications incatalysis and drug delivery[J]Nanoscale2013,5,2205-2218) and the field of catalysis (Fang X, Liu Z, Hsieh M F, Chen M, Liu P, Chen C, Zheng N, Hollow Mesoporous alumina spheres with Perpendicular Pore Channels as Catalytic nanoreacts [ J],ACSNano 2012,6,4434-4444.)，(Lee J,Park J C,Bang J U,Song H,Precise Tuning ofPorosity and Surface Functionality in [email protected]₂Nanoreactors for High CatalyticEfficiency[J]Chem. Mater.2008,20,5839- ₂Catalysts[J],Angew.Chem.Int.Ed.2011,50,10208-10211.)，(Li W,Deng Y,Wu Z,Qian X,Yang J,Wang Y,Gu D,Zhang F,Tu B,Zhao D,Hydrothermal EtchingAssisted Crystallization:A Facile Route to Functional Yolk-Shell TitanateMicrospheres with Ultrathin Nanosheets-Assembled Double Shells[J]J.Am.chem.Soc.2011,133, 15830-15833.). Nowadays, the popularization of automobiles brings great convenience to the life of people, and meanwhile, the environmental problem caused by the increase of exhaust emission is more and more serious. Among them, sulfides in fuel such as Thiophene (T), Benzothiophene (BT), Dibenzothiophene (DBT), etc. are a common type of pollutants. Since thiophene sulfides generally have a large steric hindrance, they are difficult to remove by the reduction method which is generally used in industry. Catalytic oxidation desulfurization generally has higher removal rates for thiophenic sulfides (Otsuki S, Nonaka T, Takashima N, Qian W,Ishihara A,Imai T,Kabe T,Energy&fuels2000,14,1232.), but during the reaction, polar solvents are often required to extract the sulfones produced by the reaction, which also increases the cost of the process.

Therefore, how to construct a more efficient and 'green' catalytic system to treat the sulfide in the fuel oil is a problem which needs to be further researched and solved urgently.

Disclosure of Invention

Based on the problems of sulfide treatment in automobile exhaust in the industry, the invention aims to provide an organic-inorganic composite Janus cage-shaped material which has catalytic oxidation performance on sulfide, enrichment and responsive release on reaction products and a preparation method thereof.

The organic-inorganic composite Janus cage-shaped material provided by the invention comprises the following components in parts by weight: by incompletely etching the magnetic core of the magnetic mesoporous silica particles, retaining magnetism and releasing fresh silicon hydroxyl on the inner surface, modifying ionic liquid on the outer side to endow the magnetic mesoporous silica particles with catalytic performance, grafting responsive polymers on the inner side to obtain the magnetic Janus cage-shaped material which can catalyze and oxidize sulfide pollutants in fuel oil and enrich and controllably release products after catalytic oxidation,

wherein the chemical composition of the inner and outer sides is adjustable; the thickness of the shell layer is controllable;

the organic-inorganic composite Janus cage-shaped material is a nanoparticle with the size of 100-300nm (specifically, 150-250 nm).

The organic-inorganic composite Janus cage-shaped material provided by the invention is prepared by the following steps:

1) preparing magnetic nano particles, taking a surfactant as a pore-forming agent, and coating a layer of mesoporous silica on the surfaces of the magnetic nano particles to obtain magnetic mesoporous silica particles;

2) modifying imidazoline groups on the surfaces of the magnetic mesoporous silica particles obtained in the step 1) and further reacting the imidazoline groups with halogenated hydrocarbons to obtain magnetic mesoporous silica particles of which the outer surfaces are modified with ionic liquid taking halogen as anions;

3) Removing the pore-forming agent from the magnetic mesoporous silica particles with the outer surfaces modified with the ionic liquid taking halogen as anions obtained in the step 2), and then carrying out incomplete etching by using dilute hydrochloric acid to release partial cavities to obtain particles with a yolk-eggshell structure;

4) modifying double bonds on the inner surface of the yolk-eggshell structure particles obtained in the step 3) to obtain yolk-eggshell structure particles modified with double bonds on the inner surface;

5) under the action of an initiator, carrying out free radical polymerization on the monomer and the modified double bond on the inner surface to obtain Janus particles with the inner surface grafted with a responsive polymer;

6) leading the Janus particles with the inner surface grafted with the responsive polymer obtained in the step 5) to react with phosphotungstic acid, and obtaining the product with the outer surface with anions of PW₁₂O₄₀ ^3-The inner surface of the ionic liquid is Janus cage-shaped material modified by responsive polymer.

In step 1) of the above method, the magnetic nanoparticles may be Fe₃O₄And (3) nanoparticles.

The magnetic nanoparticles can be prepared by a solvothermal method.

The surfactant may specifically be cetyltrimethylammonium bromide.

The coating of the mesoporous silica layer on the surface of the magnetic nano-particles can be realized by the following operations: in the presence of a surfactant serving as a pore-foaming agent, hydrolyzing ethyl orthosilicate under an alkaline condition to obtain mesoporous silicon dioxide;

The magnetic mesoporous silica particles can be specifically represented as: fe₃O₄@mSiO₂And (3) granules.

In step 2), the operation of modifying the imidazoline group on the surface of the magnetic mesoporous silica particle is as follows: and dispersing the magnetic mesoporous silica particles into a solvent, adding an imidazoline silane coupling agent, and reacting to obtain the imidazoline group modified magnetic mesoporous silica particles.

The imidazoline silane coupling agent can be triethoxy-3- (2-imidazole-1-linyl) propane silane.

The proportion of the magnetic mesoporous silica particles to the triethoxy-3- (2-imidazole-1-linyl) propane silane can be 100 mg: 100 μ L.

Wherein the reaction temperature can be 60-80 ℃, particularly 70 ℃, and the reaction time can be 10-16h, particularly 12 h.

The halogenated hydrocarbons useful for reacting with the imidazolinyl group include, but are not limited to: bromoethane, bromo-n-propane, bromo-n-butane, bromo-n-pentane, 1-bromohexane, n-bromododecane, chloroethane, chloro-n-propane, chloro-n-butane, chloro-n-pentane, 1-chlorohexane, and the like.

The imidazolinyl group Fe₃O₄@mSiO₂The ratio of particles to halogenated hydrocarbon may be: 100 mg: 1 mL.

The reaction temperature of the reaction of the imidazoline group and the halogenated hydrocarbon can be 110-120 ℃, specifically 115 ℃, and the reaction time can be 10-15h, specifically 12 h.

In step 3), the specific operation of removing the pore-forming agent is as follows: placing the magnetic mesoporous silica modified by the ionic liquid in a Soxhlet extractor, and extracting for three days by using acetone;

the operation of using dilute hydrochloric acid to carry out incomplete etching is as follows: dispersing the magnetic mesoporous silica modified by the ionic liquid in ethanol, adding hydrochloric acid, and reacting;

wherein, the hydrochloric acid can be hydrochloric acid solution with the concentration of 2M;

the proportion of the ionic liquid modified magnetic mesoporous silica to the hydrochloric acid solution with the concentration of 2M can be as follows: 100 mg: 1-1.2ml, specifically 100 mg: 1 ml.

The reaction temperature may be 65 to 75 ℃, specifically 70 ℃, and the reaction time may be 1.5 to 2.5 hours, specifically 2 hours.

In the step 4), the operation of modifying the inner surface of the particle with the yolk-eggshell structure with double bonds is as follows: dispersing the particles with the yolk-eggshell structure obtained in the step 3) into a solvent, adding 3- (methacryloyloxy) propyl trimethoxy silane (MPS), and reacting.

The solvent can be ethanol;

wherein the ratio of the particles with the yolk-eggshell structure to the 3- (methacryloyloxy) propyl trimethoxy silane is 1 mg: 1-1.2uL, specifically 1 mg: 1 uL.

The reaction temperature may be 65 to 75 ℃, specifically 70 ℃, and the reaction time may be 10 to 14 hours, specifically 12 hours.

In step 5), the monomers that can be used for radical polymerization with the internal surface modified double bond include responsive monomers and vinyl monomers, and specifically can be responsive monomers;

the responsive monomer can be selected from N-isopropyl acrylamide, diethylaminoethyl methacrylate and the like;

the vinyl monomer can be selected from acrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, butadiene, isoprene, chloroprene or any combination thereof.

The mass ratio of the monomer to the yolk-eggshell structure particles with double bonds modified on the inner surface can be 1-1.2: 1, specifically 1: 1.

The initiator for the free radical polymerization reaction is an oil-soluble free radical initiator:

the oil-soluble free radical initiator comprises azo compounds such as azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate initiator; also can include peroxide oil-soluble initiators such as benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, etc.;

Wherein the addition amount of the initiator accounts for 0.05-5%, preferably 0.3-3%, and more preferably 0.5-1% of the total mass of the monomers.

In the free radical polymerization, the reaction temperature may be: 60-90 ℃, and specifically comprises the following components: the reaction time can be as follows at 70-80 deg.C: 8h-14h, which can be specifically as follows: 10h to 12 h.

The free radical polymerization reaction is carried out in an organic solvent,

the organic solvent can be selected from benzene, toluene and alkane;

the alkane can be one of n-hexane, n-heptane and n-decane or any combination thereof.

In step 6), the mass ratio of the Janus particles with the inner surface grafted with the responsive polymer to the phosphotungstic acid may be: 1: 2.8-3.5, specifically 1: 3.

The temperature for the reaction with the phosphotungstic acid can be room temperature, and the time can be 1-2h, specifically 1 h.

The application of the organic-inorganic composite Janus cage-shaped material in the treatment of fuel oil sulfide pollutants also belongs to the protection scope of the invention.

The fuel oil pollutant may be sulfide in fuel oil, including but not limited to: thiophene (T), Benzothiophene (BT), Dibenzothiophene (DBT), and the like.

The application specifically can be as follows: the sulfide pollutants in the fuel oil are catalyzed and oxidized, the products after catalytic oxidation are enriched, and the products after catalytic oxidation are released controllably.

The invention also provides a method for treating fuel oil sulfide pollutants by using the organic-inorganic composite Janus cage-shaped material.

The method for treating the fuel oil sulfide pollutants provided by the invention comprises the following steps: in the presence of the organic-inorganic composite Janus cage-shaped material, the fuel oil sulfide pollutant to be treated is contacted with an oxidant to generate a catalytic oxidation reaction, water is added to extract the treated product, the water solution in which the treated product is dissolved is adsorbed into a Janus cage cavity, and the separation and enrichment of the treated product from a catalytic system are realized.

In the above method, the oxidant may specifically be H₂O₂。

The temperature of the catalytic oxidation reaction can be 20-25 ℃, and specifically can be 25 ℃.

The above method may further comprise: and (3) heating the Janus material adsorbed with the aqueous solution of the treated product to release the treated product.

The heating temperature may be 40-45 deg.C, specifically 40 deg.C.

The invention can realize the batch preparation of the Janus material with adjustable composition, catalytic performance and multiple responsiveness, combines the excellent performances of the ionic liquid, the responsive polymer and the magnetic mesoporous nano particles, and has important significance in the fields of tail gas treatment, water purification, drug transportation and the like.

Drawings

Fig. 1 is a schematic diagram illustrating a preparation method of a magnetic mesoporous Janus composite cage-shaped material with a core-shell structure, which is prepared according to an embodiment of the present invention.

Fig. 2 shows a transmission electron microscope photograph of the magnetic mesoporous Janus composite cage material with the core-shell structure prepared in the embodiment of the invention.

Fig. 3 shows TGA curves before and after the core-shell structure magnetic mesoporous Janus composite cage material prepared by the embodiment of the invention is grafted with a polymer.

Detailed Description

The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.

The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.