CN115109419A - Metal organic framework gel for hazardous chemical decontamination and preparation method thereof - Google Patents
Metal organic framework gel for hazardous chemical decontamination and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a metal organic framework gel for hazardous chemical decontamination and a preparation method thereof, wherein the gel comprises a mixed metal organic framework material and a thermosensitive gel material, and the thermosensitive gel material is prepared from triethylamine, sodium hydride, bentonite, alpha-cyclodextrin, nanocellulose, glycine ethyl ester hydrochloride, polydichlorophosphazene, polyethylene glycol and carboxymethyl cellulose; the mixed metal organic framework material is prepared from a zeolite imidazole ester framework material ZIF-8, a zirconium-based metal organic framework material UiO-66 and an iron-based metal organic framework material MIL-100 (Fe). The preparation method comprises the following steps: the mixed metal organic frame material is premixed with nano-cellulose, and then carboxymethyl cellulose is added to form a cross-linked cluster, so that the mixed metal organic frame gel is obtained. The preparation process is simple, the equipment and material cost is low, and the obtained metal organic framework gel can inhibit secondary disasters such as combustion, explosion and the like in the hazardous chemical decontamination treatment process.
Description
Technical Field
The invention relates to a gel material for hazardous chemical decontamination and a preparation method thereof, in particular to a metal organic framework gel for hazardous chemical decontamination and a preparation method thereof, belonging to the technical field of fire fighting.
Background
With the rapid development of chemical industry in China, the types of dangerous chemical varieties used as raw materials and products in chemical production are increasing continuously, so the probability of various dangerous chemical leakage accidents in the processes of production, transportation and storage is also increased rapidly. Once chemical accidents such as hazardous chemical leakage occur, a large amount of toxic and harmful substances can pollute air, water, soil and the like, the ecological environment is seriously damaged due to long-term pollution, and even in some cases, the hazardous chemical directly threatens the personal safety.
The decontamination of hazardous chemicals is the key point of chemical accident treatment work, is a main link for preventing secondary disasters caused by chemical disaster accidents, and is directly related to the life safety of fire fighters and the protection of ecological environment. The main current decontamination methods comprise a physical decontamination method and a chemical decontamination method, wherein the physical decontamination method mainly utilizes natural conditions to lead poisons to be automatically evaporated and degraded or to be sealed and buried, and most importantly, an adsorbent is utilized to adsorb toxic and harmful chemical substances; the chemical decontamination method is to utilize the chemical reaction between a decontamination agent and a toxic substance to generate a nontoxic or slightly toxic substance.
Most common dangerous chemicals belong to flammable and explosive substances, and if the substances are not properly treated, serious casualties and economic losses are caused due to the fact that serious accidents such as fire disasters and explosions are easily caused. The existing decontamination agents such as oxidation chlorination decontamination agents, acid decontamination agents, alkaline decontamination agents, complex decontamination agents, physical decontamination agents and the like only consider the detoxification and pollution removal of hazardous chemicals, and do not consider the inhibition of secondary accidents such as fire, explosion and the like in the decontamination process. How to realize the prevention and treatment of thermal dynamic disasters such as fire, explosion and the like of hazardous chemicals in the decontamination treatment process of the hazardous chemicals and avoid the malignant accidents are problems to be solved urgently.
Disclosure of Invention
The invention aims to provide a metal organic framework gel for hazardous chemical decontamination and a preparation method thereof, the preparation process is simple, the equipment and material cost is low, the prepared metal organic framework gel can inhibit secondary disasters such as combustion, explosion and the like in the hazardous chemical decontamination treatment process, and is particularly suitable for hazardous chemical decontamination treatment under flammable and explosive conditions.
In order to achieve the purpose, the invention provides a metal-organic framework gel for hazardous chemical decontamination, which comprises a mixed metal-organic framework material and a heat-sensitive gel material, wherein the heat-sensitive gel material is composed of the following raw materials in percentage by weight: 0.1-0.2% of triethylamine, 3-6% of sodium hydride, 5-10% of bentonite, 5-8% of alpha-cyclodextrin, 15-20% of nanocellulose, 8-10% of glycine ethyl ester hydrochloride, 10-15% of polydichlorophosphazene, 15-22% of polyethylene glycol and 20-30% of carboxymethyl cellulose; the mixed metal organic framework material is composed of the following raw materials in percentage by weight: 20-30% of zeolite imidazole ester framework material ZIF-8, 20-40% of zirconium-based metal organic framework material UiO-66 and 40-60% of iron-based metal organic framework material MIL-100 (Fe).
Preferably, the mass ratio of the thermosensitive gel material to the mixed metal organic framework material is 1: (1-4).
Preferably, the nanocellulose is a phosphorylated modified nanocellulose.
Preferably, the polyethylene glycol is one or more of PEG-1500, PEG-2000, PEG-4000, PEG-6000 and PEG-8000.
The invention also provides a preparation method of the metal organic framework gel for hazardous chemical decontamination, which comprises the following steps:
s1, dissolving polydichlorophosphazene in anhydrous tetrahydrofuran to obtain a polymer solution with the mass concentration of 8.0-12.0 g/L; dissolving polyethylene glycol and sodium hydride in anhydrous tetrahydrofuran, and stirring at room temperature for 10-12 h to obtain a brown solution, wherein the mass concentration of the polyethylene glycol in the brown solution is 8.0-11.0 g/L, and the mass concentration of the sodium hydride in the brown solution is 2.0-3.0 g/L; dropwise adding the brown solution into the polymer solution, and reacting at room temperature for 20-24 h to obtain a partially substituted polymer;
s2, dissolving glycine ethyl ester hydrochloride and triethylamine in anhydrous tetrahydrofuran, and stirring at room temperature for 6-8 hours to obtain a mixed solution, wherein the mass concentration of the glycine ethyl ester hydrochloride in the mixed solution is 8-10 g/L, and the mass concentration of the triethylamine is 0.1-0.2 g/L; adding the mixed solution into the partially substituted polymer prepared in the step S1, and stirring and reacting for 12-15 hours at room temperature to obtain a hydrogel precursor mixture;
s3, dissolving the hydrogel precursor mixture prepared in the step S2 in deionized water, wherein the mass ratio of the hydrogel precursor mixture to the deionized water is 1: (10-12), mixing the mixture with an alpha-cyclodextrin water solution with the mass concentration of 10% at room temperature, adding nano-cellulose serving as a cross-linking agent and bentonite serving as a fire extinguishing agent, and uniformly stirring to form a stable hydrogel suspension;
s4, uniformly mixing a zeolite imidazole ester framework material ZIF-8, a zirconium-based metal organic framework material UiO-66 and an iron-based metal organic framework material MIL-100(Fe) according to a ratio to obtain a mixed metal organic framework material, adding the mixed metal organic framework material into the hydrogel suspension obtained in the step S3 to obtain a suspension, mixing the obtained suspension with a 1% carboxymethyl cellulose aqueous solution by mass concentration, reacting for 5-10 min to form a cross-linked cluster, and standing for 10-20 min to obtain the final mixed metal organic framework gel.
Further, in step S4, after the suspension is subjected to ultrasonic treatment for 15 to 20min by using a probe, the obtained suspension is mixed with a carboxymethyl cellulose aqueous solution with a mass concentration of 1% by using a vortex mixer to react for 5 to 10min to form a cross-linked cluster.
In the gel material prepared by the invention, the mixed metal organic framework material is mainly used for absorbing toxic and harmful substances such as heavy metals, organic pollutants and the like in hazardous chemicals; the heat-sensitive gel material further improves the adsorption capacity of the mixed metal organic framework material, and can control the state of gel according to the change of environmental temperature; when the environmental temperature exceeds the phase-change critical temperature of the thermosensitive gel material, the thermosensitive gel material is quickly changed from gel to sol to cover the surface of the hazardous chemical substance, further reaction is prevented by isolating oxygen, and secondary disasters such as combustion, explosion and the like are inhibited; when the environmental temperature is reduced to be lower than the phase-change critical temperature of the thermosensitive gel material, the gel is converted from the sol into the gel, and toxic and harmful substances such as heavy metals, organic pollutants and the like in the hazardous chemical substances are continuously absorbed, so that decontamination operation is completed, and secondary disasters such as combustion, explosion and the like are simultaneously inhibited in the decontamination treatment process of the hazardous chemical substances.
The metal organic framework gel material for hazardous chemical decontamination prepared by the invention is green, safe, pollution-free and high in biodegradability. The preparation process is simple, the equipment and material cost is low, the prepared metal organic framework gel can inhibit secondary disasters such as combustion, explosion and the like in the hazardous chemical decontamination treatment process, and is particularly suitable for decontamination treatment of hazardous chemicals under flammable and explosive conditions.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A metal organic framework gel for hazardous chemical decontamination comprises a mixed metal organic framework material and a thermosensitive gel material, wherein the thermosensitive gel material is prepared from the following raw materials in percentage by weight: 0.1% of triethylamine, 4% of sodium hydride, 5% of bentonite, 5.9% of alpha-cyclodextrin, 15% of nanocellulose, 10% of glycine ethyl ester hydrochloride, 10% of polydichlorophosphazene, 20% of polyethylene glycol and 30% of carboxymethyl cellulose; the mixed metal organic framework material is composed of the following raw materials in percentage by weight: 20% of zeolite imidazolate framework material ZIF-8, 20% of zirconium-based metal organic framework material UiO-66 and 60% of iron-based metal organic framework material MIL-100 (Fe); the mass ratio of the thermosensitive gel material to the mixed metal organic framework material is 1: 1.25.
the mixed metal organic framework material selected in this example was zeolite imidazolate framework material ZIF-8 (1.0 g), zirconium-based metal organic framework material UiO-66 (1.0 g), and iron-based metal organic framework material MIL-100(Fe) (3.0 g); the selected thermosensitive gel materials comprise 0.004g of triethylamine, 0.16g of sodium hydride, 0.2g of bentonite, 0.236g of alpha-cyclodextrin, 0.6g of nanocellulose, 0.4g of glycine ethyl ester hydrochloride, 0.4g of polydichlorophosphazene, 0.3g of PEG-1500, 0.5g of PEG-2000 and 1.2g of carboxymethyl cellulose.
The preparation method of the metal organic framework gel for hazardous chemical decontamination comprises the following steps:
s1, dissolving 0.4g of polydichlorophosphazene in 50mL of anhydrous tetrahydrofuran to obtain a polymer solution with the mass concentration of 8.0 g/L; dissolving 0.3g of PEG-1500, 0.5g of PEG-2000 and 0.16g of sodium hydride in 80mL of anhydrous tetrahydrofuran, and stirring at room temperature for 10 hours to obtain a brown solution, wherein the mass concentration of the polyethylene glycol in the brown solution is 10.0g/L, and the mass concentration of the sodium hydride is 2.0 g/L; dropwise adding the brown solution into the polymer solution, and reacting at room temperature for 20h to obtain a partially substituted polymer;
s2, dissolving 0.4g of glycine ethyl ester hydrochloride and 0.004g of triethylamine in 40mL of anhydrous tetrahydrofuran, and stirring at room temperature for 8 hours to obtain a mixed solution, wherein the mass concentration of the glycine ethyl ester hydrochloride in the mixed solution is 10g/L, and the mass concentration of the triethylamine is 0.1 g/L; adding the mixed solution into the partially substituted polymer prepared in the step S1, and stirring and reacting for 12 hours at room temperature to obtain a hydrogel precursor mixture;
s3, dissolving the hydrogel precursor mixture prepared in the step S2 in deionized water, wherein the mass ratio of the hydrogel precursor mixture to the deionized water is 1: 10, then mixing the mixture with 2.36g of alpha-cyclodextrin water solution with the mass concentration of 10% at room temperature, adding 0.6g of nano-cellulose serving as a cross-linking agent and 0.2g of bentonite serving as a fire extinguishing agent, and uniformly stirring to form stable hydrogel suspension;
s4, uniformly mixing 1.0g of zeolite imidazole ester framework material ZIF-8, 1.0g of zirconium-based metal organic framework material UiO-66 and 3.0g of iron-based metal organic framework material MIL-100(Fe) to obtain a mixed metal organic framework material, adding the mixed metal organic framework material into the hydrogel suspension obtained in the step S3, performing ultrasonic treatment for 15min by using a probe to uniformly suspend the mixed metal organic framework material in the hydrogel suspension, mixing the obtained suspension with 120g of carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using a vortex mixer, reacting for 5min to form a cross-linked cluster, and standing for 10min to obtain the final mixed metal organic framework gel.
The metal organic frame gel prepared in this example was subjected to performance testing, and the results were as follows:
when the temperature is increased to 46 ℃, the prepared mixed metal organic framework gel begins to gradually change from gel to sol, and when the temperature exceeds 51 ℃, all mixed metal organic framework gels are completely changed into sol. When the temperature is gradually reduced to below 46 ℃, the mixed metal organic framework is changed from sol to gel again, and the expected effect is achieved.
Example 2
A metal organic framework gel for hazardous chemical decontamination comprises a mixed metal organic framework material and a thermosensitive gel material, wherein the thermosensitive gel material is prepared from the following raw materials in percentage by weight: 0.105% of triethylamine, 3.0% of sodium hydride, 5.895% of bentonite, 5% of alpha-cyclodextrin, 18% of nanocellulose, 10% of glycine ethyl ester hydrochloride, 12% of polydichlorophosphazene, 22% of polyethylene glycol and 24% of carboxymethyl cellulose; the mixed metal organic framework material is composed of the following raw materials in percentage by weight: 20% of zeolite imidazolate framework material ZIF-8, 30% of zirconium-based metal organic framework material UiO-66 and 50% of iron-based metal organic framework material MIL-100 (Fe); the mass ratio of the thermosensitive gel material to the mixed metal organic framework material is 1: 1.5.
the mixed metal organic framework material selected in this example was zeolite imidazolate framework material ZIF-8 (1.2 g), zirconium-based metal organic framework material UiO-66 (1.8 g), and iron-based metal organic framework material MIL-100(Fe) (3.0 g); the selected thermosensitive gel materials comprise 0.0042g of triethylamine, 0.12g of sodium hydride, 0.2358g of bentonite, 0.2g of alpha-cyclodextrin, 0.72g of nanocellulose, 0.4g of glycine ethyl ester hydrochloride, 0.48g of polydichlorophosphazene, 0.32g of PEG-2000, 0.56g of PEG-4000 and 0.96g of carboxymethyl cellulose.
The preparation method of the metal organic framework gel for hazardous chemical decontamination comprises the following steps:
s1, dissolving 0.48g of polydichlorophosphazene in 50mL of anhydrous tetrahydrofuran to obtain a polymer solution with the mass concentration of 9.6 g/L; dissolving 0.32g of PEG-2000, 0.56g of PEG-4000 and 0.12g of sodium hydride in 80mL of anhydrous tetrahydrofuran, and stirring at room temperature for 11 hours to obtain a brown solution, wherein the mass concentration of the polyethylene glycol in the brown solution is 11.0g/L, and the mass concentration of the sodium hydride is 1.5 g/L; dropwise adding the brown solution into the polymer solution, and reacting at room temperature for 23h to obtain a partially substituted polymer;
s2, dissolving 0.4g of glycine ethyl ester hydrochloride and 0.0042g of triethylamine in 40mL of anhydrous tetrahydrofuran, and stirring at room temperature for 8 hours to obtain a mixed solution, wherein the mass concentration of the glycine ethyl ester hydrochloride in the mixed solution is 10g/L, and the mass concentration of the triethylamine is 0.105 g/L; adding the mixed solution into the partially substituted polymer prepared in the step S1, and stirring and reacting for 14 hours at room temperature to obtain a hydrogel precursor mixture;
s3, dissolving the hydrogel precursor mixture prepared in the step S2 in deionized water, wherein the mass ratio of the hydrogel precursor mixture to the deionized water is 1: 11, mixing the mixture with 2.0g of an alpha-cyclodextrin water solution with the mass concentration of 10% at room temperature, adding 0.72g of nano-cellulose serving as a cross-linking agent and 0.2358g of bentonite serving as a fire extinguishing agent, and uniformly stirring to form a stable hydrogel suspension;
s4, uniformly mixing 1.2g of zeolite imidazole ester framework material ZIF-8, 1.8g of zirconium-based metal organic framework material UiO-66 and 3.0g of iron-based metal organic framework material MIL-100(Fe) to obtain a mixed metal organic framework material, adding the mixed metal organic framework material into the hydrogel suspension obtained in the step S3, performing ultrasonic treatment for 18min by using a probe to uniformly suspend the mixed metal organic framework material in the hydrogel suspension, mixing the obtained suspension with 96g of carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using a vortex mixer, reacting for 8min to form a cross-linked cluster, and standing for 18min to obtain the final mixed metal organic framework gel.
The metal organic frame gel prepared in this example was subjected to performance testing, and the results were as follows:
when the temperature is raised to 51 ℃, the prepared mixed metal organic framework gel begins to gradually change from gel to sol, and when the temperature exceeds 55 ℃, all mixed metal organic framework gels are completely changed into sol. When the temperature is gradually reduced to below 51 ℃, the mixed metal organic framework is changed from sol to gel again, and the expected effect is achieved.
Example 3
A metal organic framework gel for hazardous chemical decontamination comprises a mixed metal organic framework material and a thermosensitive gel material, wherein the thermosensitive gel material is prepared from the following raw materials in percentage by weight: 0.2% of triethylamine, 6% of sodium hydride, 10% of bentonite, 8% of alpha-cyclodextrin, 15.8% of nanocellulose, 8% of glycine ethyl ester hydrochloride, 15% of polydichlorophosphazene, 16% of polyethylene glycol and 21% of carboxymethyl cellulose; the mixed metal organic framework material is composed of the following raw materials in percentage by weight: 30% of zeolite imidazolate framework material ZIF-8, 35% of zirconium-based metal organic framework material UiO-66 and 35% of iron-based metal organic framework material MIL-100 (Fe); the mass ratio of the thermosensitive gel material to the mixed metal organic framework material is 1: 2.
the mixed metal organic framework material selected in this example was 2.4g of zeolitic imidazolate framework material ZIF-8, 2.8g of zirconium-based metal organic framework material UiO-66, 2.8g of iron-based metal organic framework material MIL-100 (Fe); the selected thermosensitive gel materials comprise 0.008g of triethylamine, 0.24g of sodium hydride, 0.4g of bentonite, 0.32g of alpha-cyclodextrin, 0.632g of nanocellulose, 0.32g of glycine ethyl ester hydrochloride, 0.6g of polydichlorophosphazene, 0.27g of PEG-4000, 0.37g of PEG-8000 and 0.84g of carboxymethyl cellulose.
The preparation method of the metal organic framework gel for hazardous chemical decontamination comprises the following steps:
s1, dissolving 0.6g of polydichlorophosphazene in 50mL of anhydrous tetrahydrofuran to obtain a polymer solution with the mass concentration of 12 g/L; dissolving 0.27g of PEG-4000, 0.37g of PEG-8000 and 0.24g of sodium hydride in 80mL of anhydrous tetrahydrofuran, and stirring at room temperature for 12 hours to obtain a brown solution, wherein the mass concentration of the polyethylene glycol in the brown solution is 8.0g/L, and the mass concentration of the sodium hydride is 3.0 g/L; dropwise adding the brown solution into the polymer solution, and reacting at room temperature for 24h to obtain a partially substituted polymer;
s2, dissolving 0.32g of glycine ethyl ester hydrochloride and 0.008g of triethylamine in 40mL of anhydrous tetrahydrofuran, and stirring at room temperature for 6 hours to obtain a mixed solution, wherein the mass concentration of the glycine ethyl ester hydrochloride in the mixed solution is 8g/L, and the mass concentration of the triethylamine is 0.2 g/L; adding the mixed solution into the partially substituted polymer prepared in the step S1, and stirring and reacting for 15 hours at room temperature to obtain a hydrogel precursor mixture;
s3, dissolving the hydrogel precursor mixture prepared in the step S2 in deionized water, wherein the mass ratio of the hydrogel precursor mixture to the deionized water is 1: 10, then mixing the mixture with 3.2g of alpha-cyclodextrin water solution with the mass concentration of 10% at room temperature, adding 0.632g of nano-cellulose serving as a cross-linking agent and 0.4g of bentonite serving as a fire extinguishing agent, and uniformly stirring to form stable hydrogel suspension;
s4, uniformly mixing 2.4g of zeolite imidazole ester framework material ZIF-8, 2.8g of zirconium-based metal organic framework material UiO-66 and 2.8g of iron-based metal organic framework material MIL-100(Fe) to obtain a mixed metal organic framework material, adding the mixed metal organic framework material into the hydrogel suspension obtained in the step S3, performing ultrasonic treatment for 20min by using a probe to enable the mixed metal organic framework nano material to be suspended in the hydrogel suspension, mixing the obtained suspension with 84g of carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using a vortex mixer, reacting for 10min to form a cross-linked cluster, and standing for 20min to obtain the final mixed metal organic framework gel.
The metal organic frame gel prepared in this example was subjected to performance testing, and the results were as follows:
when the temperature is increased to 55 ℃, the prepared mixed metal organic framework gel begins to gradually change from gel to sol, and when the temperature exceeds 60 ℃, all mixed metal organic framework gels are completely changed into sol. When the temperature is gradually reduced to be below 55 ℃, the mixed metal organic framework is changed from sol to gel, and the expected effect is achieved.
Example 4
A metal organic framework gel for hazardous chemical decontamination comprises a mixed metal organic framework material and a thermosensitive gel material, wherein the thermosensitive gel material is prepared from the following raw materials in percentage by weight: 0.12% of triethylamine, 4.8% of sodium hydride, 7% of bentonite, 5.88% of alpha-cyclodextrin, 20% of nanocellulose, 10% of glycine ethyl ester hydrochloride, 10.2% of polydichlorophosphazene, 22% of polyethylene glycol and 20% of carboxymethyl cellulose; the mixed metal organic framework material is composed of the following raw materials in percentage by weight: 20% of zeolite imidazolate framework material ZIF-8, 40% of zirconium-based metal organic framework material UiO-66 and 40% of iron-based metal organic framework material MIL-100 (Fe); the mass ratio of the thermosensitive gel material to the mixed metal organic framework material is 1: 2.5.
the mixed metal organic framework material selected in this example was 2.0g of zeolitic imidazolate framework material ZIF-8, 4.0g of zirconium-based metal organic framework material UiO-66, 4.0g of iron-based metal organic framework material MIL-100 (Fe); the selected thermosensitive gel materials comprise 0.0048g of triethylamine, 0.192g of sodium hydride, 0.28g of bentonite, 0.2352g of alpha-cyclodextrin, 0.8g of phosphorylation modified nano-cellulose, 0.4g of glycine ethyl ester hydrochloride, 0.408g of polydichlorophosphazene, 0.4g of PEG-6000, 0.48g of PEG-8000 and 0.8g of carboxymethyl cellulose.
The preparation method of the metal organic framework gel for hazardous chemical decontamination comprises the following steps:
s1, dissolving 0.408g of polydichlorophosphazene in 50mL of anhydrous tetrahydrofuran to obtain a polymer solution with the mass concentration of 8.16 g/L; dissolving 0.4g of PEG-6000, 0.48g of PEG-8000 and 0.192g of sodium hydride in 80mL of anhydrous tetrahydrofuran, and stirring at room temperature for 10 hours to obtain a brown solution, wherein the mass concentration of the polyethylene glycol in the brown solution is 11.0g/L, and the mass concentration of the sodium hydride is 2.4 g/L; dropwise adding the brown solution into the polymer solution, and reacting at room temperature for 22h to obtain a partially substituted polymer;
s2, dissolving 0.4g of glycine ethyl ester hydrochloride and 0.0048g of triethylamine in 40mL of anhydrous tetrahydrofuran, and stirring at room temperature for 8 hours to obtain a mixed solution, wherein the mass concentration of the glycine ethyl ester hydrochloride in the mixed solution is 10g/L, and the mass concentration of the triethylamine is 0.12 g/L; adding the mixed solution into the partially substituted polymer prepared in the step S1, and stirring and reacting for 13 hours at room temperature to obtain a hydrogel precursor mixture;
s3, dissolving the hydrogel precursor mixture prepared in the step S2 in deionized water, wherein the mass ratio of the hydrogel precursor mixture to the deionized water is 1: 12, mixing the mixture with 2.352g of an alpha-cyclodextrin water solution with the mass concentration of 10% at room temperature, adding 0.8g of phosphorylation modified nano-cellulose serving as a cross-linking agent and 0.28g of bentonite serving as a fire extinguishing agent, and uniformly stirring to form a stable hydrogel suspension;
s4, uniformly mixing 2.0g of zeolite imidazole ester framework material ZIF-8, 4.0g of zirconium-based metal organic framework material UiO-66 and 4.0g of iron-based metal organic framework material MIL-100(Fe) to obtain a mixed metal organic framework material, adding the mixed metal organic framework material into the hydrogel suspension obtained in the step S3, performing ultrasonic treatment for 16min by using a probe to uniformly suspend the mixed metal organic framework material in the hydrogel suspension, mixing the obtained suspension with 80g of carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using a vortex mixer, reacting for 6min to form a cross-linked cluster, and standing for 15min to obtain the final mixed metal organic framework gel.
The metal organic frame gel prepared in this example was subjected to performance testing, and the results were as follows:
when the temperature rises to 57 ℃, the prepared mixed metal organic framework gel begins to gradually change from gel to sol, and when the temperature exceeds 60 ℃, all mixed metal organic framework gels completely change into sol. When the temperature is gradually reduced to be below 57 ℃, the mixed metal organic framework is changed from sol to gel again, and the expected effect is achieved.
In order to test the metal organic framework gels prepared in the above examples 1 to 4, respectively, against toxicityThe absorption performance of harmful substances, namely, the potassium dichromate with the most toxic chromium metal is selected as a representative component in dangerous chemicals. In the test, 1.0cm 3 Examples 1 to 4 the metal organic framework gels prepared respectively were put into 10mL of an aqueous solution containing 10mg/L of potassium dichromate, reacted for 24 hours without any stirring, and then the content of potassium dichromate in the solution was measured.
The test results of examples 1-4 are shown in the following table:
| test items | Gel-sol phase transition temperature/. degree.C | Absorption of potassium dichromate in mg g -1 |
| Example 1 | 46 | 2.92 |
| Example 2 | 51 | 3.16 |
| Example 3 | 55 | 3.55 |
| Example 4 | 57 | 3.68 |
According to the test results shown in the table above, the phase transition temperature of the metal organic framework gel material can be adjusted and controlled by selecting polyethylene glycol with different molecular weights, and the specific expression is that the phase transition temperature gradually rises along with the increase of the molecular weight of polyethylene glycol, and the polyethylene glycol can be reasonably selected according to the actual decontamination environment and safety factor requirements in actual use so as to achieve the best effect. On the other hand, the ratio of the mixed metal organic framework material also affects the absorption effect of the mixed metal organic framework material on hazardous chemical materials, and it can be seen from the embodiments 1 to 4 that the absorption rate of the mixed metal organic framework gel material on potassium dichromate is increased with the increase of the ratio of the zirconium-based metal organic framework material UiO-66. Therefore, in the specific decontamination operation, the reasonable mixture ratio of the mixed metal organic framework material can be selected according to the types and the components of the hazardous chemical substances, and the efficiency of the decontamination operation can be greatly improved.
Claims (6)
1. The metal-organic framework gel for hazardous chemical decontamination is characterized by comprising a mixed metal-organic framework material and a thermosensitive gel material, wherein the thermosensitive gel material is prepared from the following raw materials in percentage by weight: 0.1-0.2% of triethylamine, 3-6% of sodium hydride, 5-10% of bentonite, 5-8% of alpha-cyclodextrin, 15-20% of nanocellulose, 8-10% of glycine ethyl ester hydrochloride, 10-15% of polydichlorophosphazene, 15-22% of polyethylene glycol and 20-30% of carboxymethyl cellulose; the mixed metal organic framework material is composed of the following raw materials in percentage by weight: 20-30% of zeolite imidazole ester framework material ZIF-8, 20-40% of zirconium-based metal organic framework material UiO-66 and 40-60% of iron-based metal organic framework material MIL-100 (Fe).
2. The metal-organic framework gel for hazardous chemical decontamination according to claim 1, wherein the mass ratio of the thermosensitive gel material to the mixed metal-organic framework material is 1: (1-4).
3. The metal-organic framework gel for hazardous chemical decontamination according to claim 1 or 2, wherein the nanocellulose is phosphorylation-modified nanocellulose.
4. The metal-organic framework gel for hazardous chemical decontamination according to claim 1 or 2, wherein the polyethylene glycol is one or more of PEG-1500, PEG-2000, PEG-4000, PEG-6000 and PEG-8000.
5. The preparation method of the metal-organic framework gel for hazardous chemical decontamination according to claim 1, comprising the following steps:
s1, dissolving polydichlorophosphazene in anhydrous tetrahydrofuran to obtain a polymer solution with the mass concentration of 8.0-12.0 g/L; dissolving polyethylene glycol and sodium hydride in anhydrous tetrahydrofuran, and stirring at room temperature for 10-12 h to obtain a brown solution, wherein the mass concentration of the polyethylene glycol in the brown solution is 8.0-11.0 g/L, and the mass concentration of the sodium hydride in the brown solution is 2.0-3.0 g/L; dropwise adding the brown solution into the polymer solution, and reacting at room temperature for 20-24 h to obtain a partially substituted polymer;
s2, dissolving glycine ethyl ester hydrochloride and triethylamine in anhydrous tetrahydrofuran, and stirring at room temperature for 6-8 hours to obtain a mixed solution, wherein the mass concentration of the glycine ethyl ester hydrochloride in the mixed solution is 8-10 g/L, and the mass concentration of the triethylamine is 0.1-0.2 g/L; adding the mixed solution into the partially substituted polymer prepared in the step S1, and stirring and reacting for 12-15 hours at room temperature to obtain a hydrogel precursor mixture;
s3, dissolving the hydrogel precursor mixture prepared in the step S2 in deionized water, wherein the mass ratio of the hydrogel precursor mixture to the deionized water is 1: (10-12), mixing the mixture with an alpha-cyclodextrin water solution with the mass concentration of 10% at room temperature, adding nano-cellulose serving as a cross-linking agent and bentonite serving as a fire extinguishing agent, and uniformly stirring to form a stable hydrogel suspension;
s4, uniformly mixing a zeolite imidazole ester framework material ZIF-8, a zirconium-based metal organic framework material UiO-66 and an iron-based metal organic framework material MIL-100(Fe) according to a ratio to obtain a mixed metal organic framework material, adding the mixed metal organic framework material into the hydrogel suspension obtained in the step S3 to obtain a suspension, mixing the obtained suspension with a 1% carboxymethyl cellulose aqueous solution by mass concentration, reacting for 5-10 min to form a cross-linked cluster, and standing for 10-20 min to obtain the final mixed metal organic framework gel.
6. The method for preparing the metal-organic framework gel for hazardous chemical decontamination according to claim 5, wherein in the step S4, the suspension is subjected to ultrasonic treatment for 15-20 min by using a probe, and then the obtained suspension is mixed with a carboxymethyl cellulose aqueous solution with a mass concentration of 1% by using a vortex mixer to react for 5-10 min to form a cross-linked cluster.
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| US20200197901A1 (en) * | 2018-10-25 | 2020-06-25 | Uti Limited Partnership | Metal organic framework (mof) composite materials, methods, and uses thereof |
| US11007391B1 (en) * | 2018-03-09 | 2021-05-18 | The United States Of America As Represented By The Secretary Of The Army | Metal organic framework polymer composites |
| CN112831058A (en) * | 2021-01-07 | 2021-05-25 | 中国农业大学 | Integrated CG-ZIF-8 metal organic framework foam material and preparation method and application thereof |
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| US11007391B1 (en) * | 2018-03-09 | 2021-05-18 | The United States Of America As Represented By The Secretary Of The Army | Metal organic framework polymer composites |
| US20200197901A1 (en) * | 2018-10-25 | 2020-06-25 | Uti Limited Partnership | Metal organic framework (mof) composite materials, methods, and uses thereof |
| CN112831058A (en) * | 2021-01-07 | 2021-05-25 | 中国农业大学 | Integrated CG-ZIF-8 metal organic framework foam material and preparation method and application thereof |
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