阅读说明：本技术 离子交换树脂基复合材料及其制备方法 (Ion exchange resin-based composite material and preparation method thereof ) 是由 王章忠 巴志新 张泽武 卜小海 杨金涛 于 2020-07-10 设计创作，主要内容包括：本发明提供一种离子交换树脂基复合材料及其制备方法,首先将含氮杂环芳香族羧酸化合物作为有机配体加入到分散液中,超声分散0.5～2h,加入铈源,分散均匀后转移至反应釜中,在40～180℃下反应12～36h,冷却至室温,离心,再用乙醇洗涤,70～90℃下真空干燥8～12h,得Ce-MOF；将Ce-MOF置于管式炉中,通入惰性气体,升温至550～900℃,焙烧碳化2～6h,得碳氮材料-氧化铈复合物；将强酸性苯乙烯系离子交换树脂分散于去离子水中,加入碳氮材料-氧化铈复合物作为活性负载物,超声分散0.5～2h,得到离子交换树脂基复合材料。本发明制备的离子交换树脂基复合材料不仅可以提高酸性离子交换树脂的阳离子交换能力,并赋予离子交换树脂良好的有机污染物吸附处理能力,同时该复合材料还具备优异的光电响应特性,该材料在光催化有机污染物降解、光电催化水分解等反应中具有优异的催化性能。(The invention provides an ion exchange resin matrix composite material and a preparation method thereof, wherein an azacyclo-aromatic carboxylic acid compound is added into a dispersion liquid as an organic ligand, ultrasonically dispersed for 0.5-2 h, added with a cerium source, uniformly dispersed, transferred to a reaction kettle, reacted for 12-36 h at 40-180 ℃, cooled to room temperature, centrifuged, washed with ethanol, and vacuum-dried for 8-12 h at 70-90 ℃ to obtain Ce-MOF; placing the Ce-MOF into a tube furnace, introducing inert gas, heating to 550-900 ℃, roasting and carbonizing for 2-6 h to obtain a carbon-nitrogen material-cerium oxide compound; dispersing strong-acid styrene ion exchange resin in deionized water, adding a carbon-nitrogen material-cerium oxide compound as an active load, and performing ultrasonic dispersion for 0.5-2 h to obtain the ion exchange resin matrix composite. The ion exchange resin-based composite material prepared by the invention can improve the cation exchange capacity of acidic ion exchange resin, endow the ion exchange resin with good organic pollutant adsorption treatment capacity, and has excellent photoelectric response characteristics, and the material has excellent catalytic performance in photocatalytic organic pollutant degradation, photoelectric catalytic water decomposition and other reactions.)

1. The preparation method of the ion exchange resin-based composite material is characterized by comprising the following steps of:

step S1, adding an azacyclo-aromatic carboxylic acid-containing compound serving as an organic ligand into the dispersion liquid, ultrasonically dispersing for 0.5-2 h, adding a cerium source, uniformly dispersing, transferring into a reaction kettle, reacting for 12-36 h at 40-180 ℃, cooling to room temperature, centrifuging, washing with ethanol, and vacuum drying for 8-12 h at 70-90 ℃ to obtain Ce-MOF;

s2, placing the Ce-MOF into a tube furnace, introducing inert gas, heating to 550-900 ℃, and roasting and carbonizing for 2-6 h to obtain a carbon-nitrogen material-cerium oxide compound;

and S3, dispersing the strong-acid styrene ion exchange resin in deionized water, adding a carbon-nitrogen material-cerium oxide compound as an active load, and performing ultrasonic dispersion for 0.5-2 hours to obtain the ion exchange resin matrix composite.

2. The method for preparing an ion exchange resin-based composite material according to claim 1, wherein the nitrogen-containing heterocyclic aromatic carboxylic acid compound is at least one of pyrrole-2, 3, 5-tricarboxylic acid, pyridine-2, 4, 6-tricarboxylic acid, pyrazine-2, 3, 5-tricarboxylic acid.

3. The method for preparing an ion exchange resin-based composite material according to claim 1, wherein the dispersion is at least one of N, N-dimethylformamide, petroleum ether, and methanol.

4. The method for preparing an ion exchange resin-based composite material according to claim 1, wherein the cerium source is cerium nitrate hexahydrate, cerium chloride or cerium sulfate.

5. The method for preparing an ion exchange resin-based composite material according to claim 1, wherein in the step S1, the mass ratio of the nitrogen-containing heterocyclic aromatic carboxylic acid compound to the cerium source is 0.2: 1-2: 1.

6. the method for preparing an ion exchange resin-based composite material according to claim 1, wherein in the step S3, the loading amount of the carbon nitrogen material-cerium oxide compound is 2-20% by mass of the components of the composite material.

7. The method for preparing an ion exchange resin-based composite material according to claim 1, wherein in the step S2, the inert gas is one of nitrogen, argon or helium.

8. An ion exchange resin-based composite material prepared according to the preparation method of any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of ion exchange resin-based composite materials, in particular to an ion exchange resin-based composite material and a preparation method thereof.

Background

The ion exchange resin is widely used in a plurality of fields of food, medicine and health, petrochemical industry, electronics, metallurgy, energy, environmental protection and the like. The most prominent field is water treatment, which can be used for industrial water treatment and drinking water purification treatment, and can also be used in energy industry.

The ion exchange resin is used for removing impurity ions in water, has certain organic pollution resistance, has high organic matter removal rate, can be recycled, can overcome the defect that the adsorption capacity of activated carbon cannot be recovered after the activated carbon is saturated with adsorbed impurities, and thus, replaces the conventional activated carbon to play a role in removing the organic matters in the water. Meanwhile, the unique absorption effect of the ion exchange resin on visible light can also improve the photoelectrocatalysis response efficiency of the composite material.

Disclosure of Invention

The invention aims to provide a preparation method of an ion exchange resin-based composite material, the ion exchange resin composite material prepared by the method can improve the cation exchange capacity of acidic ion exchange resin and endow the ion exchange resin with good organic pollutant adsorption treatment capacity, and meanwhile, the composite material also has excellent photoelectric response characteristics, and has excellent catalytic performance in photocatalytic organic pollutant degradation, photoelectric catalytic water decomposition and other reactions.

According to a first aspect of the above object of the present invention, there is provided a method for preparing an ion exchange resin-based composite material, comprising the steps of:

step S1, adding an azacyclo-aromatic carboxylic acid-containing compound serving as an organic ligand into the dispersion liquid, ultrasonically dispersing for 0.5-2 h, adding a cerium source, uniformly dispersing, transferring into a reaction kettle, reacting for 12-36 h at 40-180 ℃, cooling to room temperature, centrifuging, washing with ethanol, and vacuum drying for 8-12 h at 70-90 ℃ to obtain Ce-MOF;

s2, placing the Ce-MOF into a tube furnace, introducing inert gas, heating to 550-900 ℃, and roasting and carbonizing for 2-6 h to obtain a carbon-nitrogen material-cerium oxide compound;

and S3, dispersing the strong-acid styrene ion exchange resin in deionized water, adding a carbon-nitrogen material-cerium oxide compound as an active load, and performing ultrasonic dispersion for 0.5-2 hours to obtain the ion exchange resin matrix composite.

Preferably, the nitrogen-containing heterocyclic aromatic carboxylic acid compound is at least one of pyrrole-2, 3, 5-tricarboxylic acid, pyridine-2, 4, 6-tricarboxylic acid and pyrazine-2, 3, 5-tricarboxylic acid.

Preferably, the dispersion is at least one of N, N-dimethylformamide, petroleum ether and methanol.

Preferably, the cerium source is cerium nitrate hexahydrate, cerium chloride or cerium sulfate.

Preferably, in the step S1, the mass ratio of the azacyclic aromatic carboxylic acid-containing compound to the cerium source is 0.2: 1-2: 1.

preferably, in the step S3, the carbon-nitrogen material-cerium oxide composite is loaded in an amount of 2% to 20% by mass of the composite components.

Preferably, in step S2, the inert gas is one of nitrogen, argon or helium.

According to a second aspect of the above object of the present invention, there is provided an ion exchange resin-based composite material prepared according to the above method, wherein the carrier of the composite material is a strongly acidic styrene-based ion exchange resin, and the active support is a porous carbon nitride material-cerium oxide composite, wherein the carbon nitride material-cerium oxide composite is obtained by calcining and carbonizing a cerium-based metal organic framework, and the organic ligand of the cerium-based metal organic framework is a nitrogen-containing heterocyclic aromatic carboxylic acid compound.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention realizes oxygen-enriched vacancy CeO by constructing a cerium-based metal organic framework and roasting and carbonizing the cerium-based metal organic framework₂The specific surface area of the ion exchange resin is increased by synchronously constructing the porous carbon-nitrogen material;

(2) in the process that the carbon-nitrogen material-cerium oxide compound is loaded on the strongly acidic styrene ion exchange resin, the effective immobilization of the carbon-nitrogen material-cerium oxide compound on the strongly acidic styrene ion exchange resin can be realized by utilizing the bonding effect between the carbon-nitrogen material and groups on the skeleton of the strongly acidic styrene ion exchange resin, the synergistic effect of the carbon-nitrogen material-cerium oxide compound is improved, and the excellent photoelectrocatalysis effect is endowed to the catalyst;

(3) the introduction of the carbon-nitrogen material-cerium oxide compound does not affect the exchange capacity of the strong-acid ion exchange resin, and simultaneously realizes the adsorption of organic pollutants by utilizing the directional enrichment effect of the porous carbon-nitrogen material, and simultaneously realizes the degradation of low-content organic matters by utilizing the oxygen-rich vacancy characteristic of cerium oxide, thereby achieving the effective removal of the organic pollutants.

It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent. In addition, all combinations of claimed subject matter are considered a part of the presently disclosed subject matter.

The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present invention, such as features and/or advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of specific embodiments in accordance with the teachings of the present invention.

Drawings

The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:

FIG. 1 is a schematic representation of the oxygen-rich vacancy characteristics of cerium oxide for an ion exchange resin-based composite material prepared in accordance with an embodiment of the present invention.

FIG. 2 is N of an ion exchange resin-based composite material prepared by an exemplary embodiment of the present invention₂Adsorption-desorption curve.

Detailed Description

In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.

In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways, as the disclosed concepts and embodiments are not limited to any one implementation. In addition, some aspects of the present disclosure may be used alone, or in any suitable combination with other aspects of the present disclosure.

In combination with the disclosed embodiment of the invention, the invention provides an ion exchange resin-based composite material which takes a strong-acid styrene ion exchange resin as a carrier and a porous carbon-nitrogen material-cerium oxide composite as an active load, wherein the carbon-nitrogen material-cerium oxide composite is obtained by roasting and carbonizing a cerium-based metal organic framework, and an organic ligand of the cerium-based metal organic framework is a nitrogen-containing heterocyclic aromatic carboxylic acid compound.

In an alternative embodiment, the present invention prepares the above-described ion exchange resin-based composite material by the following preparation process.

Step S1, adding an azacyclo-aromatic carboxylic acid-containing compound serving as an organic ligand into the dispersion liquid, ultrasonically dispersing for 0.5-2 h, adding a cerium source, uniformly dispersing, transferring into a reaction kettle, reacting for 12-36 h at 40-180 ℃, cooling to room temperature, centrifuging, washing with ethanol, and vacuum drying for 8-12 h at 70-90 ℃ to obtain Ce-MOF;

s2, placing the Ce-MOF into a tube furnace, introducing inert gas, heating to 550-900 ℃, and roasting and carbonizing for 2-6 h to obtain a carbon-nitrogen material-cerium oxide compound;

and S3, dispersing the strong-acid styrene ion exchange resin in deionized water, adding a carbon-nitrogen material-cerium oxide compound as an active load, and performing ultrasonic dispersion for 0.5-2 hours to obtain the ion exchange resin matrix composite.

Preferably, the nitrogen-containing heterocyclic aromatic carboxylic acid compound is at least one of pyrrole-2, 3, 5-tricarboxylic acid, pyridine-2, 4, 6-tricarboxylic acid and pyrazine-2, 3, 5-tricarboxylic acid.

Preferably, the dispersion is at least one of N, N-dimethylformamide, petroleum ether and methanol.

Preferably, the cerium source is cerium nitrate hexahydrate, cerium chloride or cerium sulfate.

Preferably, in the step S1, the mass ratio of the azacyclic aromatic carboxylic acid-containing compound to the cerium source is 0.2: 1-2: 1.

preferably, in the step S3, the carbon-nitrogen material-cerium oxide composite is loaded in an amount of 2% to 20% by mass of the composite components.

Exemplary implementations of the above steps are described in more detail below with reference to specific embodiments.

[ example 1 ]

Adding 1.99g of 2,3, 5-pyrrole tricarboxylate into methanol, ultrasonically dispersing for 1h, adding 8.27g of cerium nitrate hexahydrate under the condition of a water bath at a certain temperature, transferring the mixture into a reaction kettle after the mixture is uniformly dispersed, adjusting the reaction temperature to 160 ℃, standing and cooling to room temperature after reacting for 12h, centrifuging, washing with ethanol, and placing the mixture into a very empty oven to perform vacuum drying at 75 ℃ for 12h to obtain 2.64g of Ce-MOF;

and (3) placing the Ce-MOF into a tubular furnace, introducing argon, adjusting the temperature in the tubular furnace to 800 ℃, and roasting and carbonizing for 6h to obtain the carbon-nitrogen material-cerium oxide compound, wherein the loading amount of the carbon-nitrogen material-cerium oxide compound is 7%. (ii) a

Dispersing strong-acid styrene ion exchange resin in deionized water, adding a carbon-nitrogen material-cerium oxide compound, and performing ultrasonic dispersion for 2 hours to obtain the ion exchange resin-based composite material.

The cerium oxide in the ion exchange resin matrix composite material has obvious oxygen-rich vacancy characteristic (see figure 1), and the specific surface area of the material is 269.8m²The material has a typical hierarchical pore structure, and when the material is applied to a reaction for degrading rhodamine B by visible light catalysis, the rhodamine B can be completely carbonized within 15 min.

[ example 2 ]

Adding 1.99g of 2,3, 5-pyrrole tricarboxylate into a mixed solution of methanol and petroleum ether, ultrasonically dispersing for 2h, adding 6.2g of cerium nitrate hexahydrate under the condition of a water bath at a certain temperature, transferring the mixture into a reaction kettle after the mixture is uniformly dispersed, adjusting the reaction temperature to 180 ℃, reacting for 24h, standing and cooling to room temperature, centrifuging, washing with ethanol, and placing the mixture into a very empty oven to perform vacuum drying for 12h at 90 ℃ to obtain 1. 41g of Ce-MOF;

and (3) placing the Ce-MOF into a tubular furnace, introducing argon, adjusting the temperature in the tubular furnace to 900 ℃, and roasting and carbonizing for 6h to obtain the carbon-nitrogen material-cerium oxide compound, wherein the loading capacity of the compound is 15%. (ii) a

Dispersing strong-acid styrene ion exchange resin in deionized water, adding a carbon-nitrogen material-cerium oxide compound, and performing ultrasonic dispersion for 2 hours to obtain the ion exchange resin-based composite material.

With the combination of the figures 1 and 2, the cerium oxide of the ion exchange resin matrix composite material has the characteristic of obvious oxygen-rich vacancy, and the specific surface area of the material is 311.9m²The material has a typical hierarchical pore structure, and methylene blue can be completely carbonized within 10min when the material is applied to the reaction of degrading rhodamine B through visible light catalysis. The material is applied to the hydrogen production reaction by visible light catalytic water decomposition, and the hydrogen production efficiency of the composite material reaches 24000 mu mol h^-1g^-1。

[ example 3 ]

Adding 2.01g of pyridine-2, 4, 6-tricarboxylic acid into N, N-dimethylformamide, ultrasonically dispersing for 1h, adding 10g of cerium nitrate hexahydrate under the condition of a water bath at a certain temperature, transferring the mixture into a reaction kettle after the mixture is uniformly dispersed, adjusting the reaction temperature to 150 ℃, reacting for 12h, standing and cooling to room temperature, centrifuging, washing with ethanol, and placing the mixture into a very empty oven to perform vacuum drying at 90 ℃ for 12h to obtain 2.66g of Ce-MOF;

and (3) placing the Ce-MOF into a tubular furnace, introducing argon, adjusting the temperature in the tubular furnace to 700 ℃, and roasting and carbonizing for 4h to obtain the carbon-nitrogen material-cerium oxide compound, wherein the loading amount of the carbon-nitrogen material-cerium oxide compound is 12%. (ii) a

Dispersing strong-acid styrene ion exchange resin in deionized water, adding a carbon-nitrogen material-cerium oxide compound, and performing ultrasonic dispersion for 2 hours to obtain the ion exchange resin-based composite material.

The cerium oxide of the ion exchange resin-based composite material has the characteristic of obvious oxygen-rich vacancy, and the specific surface area of the material is 272.5m²G, typical hierarchical pore structure, and application of the material in visible light photocatalytic degradationIn the reaction of rhodamine B, the mixture of methylene blue and rhodamine B can be completely carbonized within 12 min.

Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.