CN107626201B - Chemical warfare agent simulant catalytically degraded by amphiphilic multi-niobium oxygen cluster emulsion - Google Patents
Chemical warfare agent simulant catalytically degraded by amphiphilic multi-niobium oxygen cluster emulsion Download PDFInfo
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Abstract
The invention discloses a method for catalyzing degradation of a chemical warfare agent simulant at normal temperature and normal pressure, and belongs to the field of catalytic chemistry. The method comprises the steps that (1) the amphipathic hexaniobate catalyst is obtained by hydrated hexaniobate and organic ammonium through an anion exchange method; (2) obtaining an amphiphilic niobium vanadium oxygen cluster catalyst by using a hydrated vanadium cap type multi-niobium vanadium oxygen cluster and organic amine through an anion exchange method; (3) amphiphilic hexaniobians and amphiphilic vanadyl niobians can form emulsions in water and toluene solvents, and the emulsion system can catalyze and degrade mustard gas simulant 2-chloroethyl ethyl sulfide (abbreviated as CEES) and nerve agent simulant (abbreviated as DECP). The catalyst prepared and used in the method can be recycled and reused by centrifugal demulsification. Under the condition of the catalyst, the CEES and DECP can be degraded mildly and efficiently.
Description
And (3) abstract:
the patent belongs to the field of catalytic chemistry, and relates to a preparation technology of an amphiphilic niobium-oxygen cluster catalyst and a method for degrading mustard gas simulants (CEES for short) and nerve agent simulants (DECP for short) in an emulsion system at normal temperature and normal pressure. The amphiphilic catalyst has good catalytic activity in an emulsion system.
Technical Field
The invention relates to a method for catalytically degrading a mustard gas simulant and a nerve agent simulant in an emulsion system under mild conditions, belonging to the field of catalytic chemistry.
Background
Chemical Warfare Agents (CWAs) continue to pose a danger to humans since the first world war. Nerve agents and foaming agents are two typical types of chemical warfare agents. A nerve agent is an organophosphate compound containing a P-X bond (X ═ F, CN or SR) that disrupts the transmission of signals from the nervous system to the muscles. Hydrolysis of neurotoxic agents or mimetics of neurotoxic agents has now mainly focused on the use of Zr-containing Metal Organic Frameworks (MOFs). Sulfur mustard (mustard or HD), used as a foaming agent for a long time in war, can cause blistering of the skin and irritation of the respiratory tract and eyes, even in large doses can lead to death. Mustard gas or its simulants can be catalytically degraded by metal oxides, polyoxometallates, MOFs. From the application point of view, it is desirable that a broad-spectrum catalyst can degrade nerve agents and foaming agents simultaneously.
Some POMs (e.g., { PV) because POMs have rapid and reversible multi-electron redox behavior2Mo10O40And iron-substituted phosphotungstates have been used for oxidative decontamination of sulfur mustard or its mimetics. Previous studies have shown that [ Nb ]6O19]8-As homogeneous catalysts K12[Ti2O2][GeNb12O40]As a heterogeneous catalyst for the catalytic degradation of CWA or its mimetics. Recently, we reported a novel dianionic complex H13[(CH3)4N]12[PNb12O40(VVO)2·(VIV 4O12)2]The catalytic CWA mimic can be efficiently hydrolyzed and oxidized. However, the above catalyst systems have a problem that the catalyst cannot be recycled. These existing problems make the current catalytic systems difficult to be put to practical use. Based on the development status of the field and according to the potential application requirements of the society at present, a new method for degrading the chemical warfare agent simulant at normal temperature and normal pressure and recycling the catalyst is necessary.
Disclosure of Invention
Aiming at the problems of catalyst recovery and selectivity in the degradation process of chemical warfare agents and simulants under normal temperature and normal pressure in the prior art, the invention aims to provide a method for catalyzing mustard gas simulants CEES and hydrolyzed nerve agent simulants DECP based on an emulsion system under normal temperature and normal pressure, and the catalyst can be recovered and reused through centrifugal demulsification. The emulsion system not only improves the compatibility of the hydrophilic POM and the hydrophobic substrate, but also leads the performance of the catalyst to be similar to that of a homogeneous reaction system due to the increase of the reaction interface area. In addition, the catalyst can be recovered by demulsification separation and recycled, and the reaction is mainly selective to generate a sulfoxide product (98%) with lower toxicity. Under the action of the catalyst, CEES degradation and DECP hydrolysis conditions are mild, and the reaction is rapid.
The purpose of the invention is realized by the following technical scheme:
the method for catalyzing degradation of the mustard gas simulant and the nerve agent simulant at normal temperature and normal pressure comprises the following steps:
(1) preparation of amphiphilic hexaniobate catalyst K is weighed7HNb6O19·8H2O dissolved in 4mL NaH2PO4-Na2HPO4And (1M) obtaining a solution A in the buffer solution, weighing organic ammonium, dissolving the organic ammonium in water to obtain a solution B, slowly dripping the solution A into the solution B, stirring for a moment, and separating out a white precipitate. After 20 minutes of reaction the solid was collected by centrifugation and washed three times with deionized water to remove the surface unreacted polyacid. Then drying the mixture for 24 hours in a vacuum drying oven at 60 ℃. Obtaining white solid, namely the amphiphilic hexaniobate catalyst.
(2) Preparation of amphiphilic niobium-vanadium-oxygen cluster catalyst TMA is weighed respectively9PNb12V2O42·19H2O in 4mLNaH2PO4-Na2HPO4And (1M) obtaining a solution A in the buffer solution, weighing organic ammonium, dissolving the organic ammonium in water to obtain a solution B, slowly dripping the solution A into the solution B, and stirring for a moment to separate out a light yellow precipitate. After 20 minutes of reaction the solid was collected by centrifugation and washed three times with deionized water to remove unreacted polyacid. Then drying the mixture for 24 hours in a vacuum drying oven at 60 ℃. Obtaining light yellow solid, namely the amphiphilic niobium-vanadium-oxygen cluster catalyst.
(3) Adding 2-chloroethyl ethyl sulfide (CEES), amphiphilic hexaniobate catalyst or amphiphilic niobium-rich vanadium oxide cluster catalyst, equal volume of solvent toluene and water into a reaction vessel for catalytic degradation, and then dropwise adding H2O2An aqueous solution. Stirring and reacting for 30 minutes at normal temperature and normal pressure to obtain a CEES degradation product.
After the reaction is finished, the catalyst is recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃. Can be repeatedly used.
(4) Catalytic degradation diethyl cyanophosphonate (DECP), an amphiphilic hexaniobate catalyst or an amphiphilic niobium-rich vanadium oxide cluster catalyst, a solvent toluene and water in equal volume are added into a reaction vessel. Stirring and reacting for 2 hours at normal temperature and normal pressure to obtain a DECP hydrolyzed product.
After the reaction is finished, the catalyst is recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃. Can be repeatedly used.
Wherein the cation in the step (1) is [ C ]12H25N(CH3)3]Br，[C14H29N(CH3)3]Br，[C16H33N(CH3)3]Br，[C18H37N(CH3)3]One kind of Br.
The molar ratio of the hydrated hexaniobate to the organic ammonium is 1: 7.
The cation in the step (2) is [ C ]12H25N(CH3)3]Br, ammonium bromide [ C ]14H29N(CH3)3]Br，[C16H33N(CH3)3]Br，[C18H37N(CH3)3]One kind of Br.
The molar ratio of the hydrated vanadium cap type multi-niobium vanadium oxygen cluster to the organic ammonium is 1: 9.
The dosage of the catalyst in the step (3) is 1.14 × 10 of the dosage of the substrate2mmol％。
The solvent is water and toluene with equal volume, and an emulsion reaction system can be formed after the amphiphilic catalyst is added.
H2O2The molar ratio of the aqueous solution to the substrate was 1:1
The conditions of the catalytic degradation reaction are normal temperature and normal pressure.
The dosage of the catalyst in the step 4 is 0.02 mmol% of the dosage of the substrate.
The solvent is water and toluene, and an emulsion reaction system can be formed after the amphiphilic catalyst is added.
The conditions of the catalytic degradation reaction are normal temperature and normal pressure.
Has the advantages that:
(1) the invention synthesizes a series of amphiphilic niobium oxygen clusters from raw materials such as hydrated hexaniobate and organic ammonium by an anion exchange method, and the amphiphilic niobium oxygen clusters are used for the catalytic degradation of mustard gas simulant CEES and nerve agent simulant DECP. The catalytic activity is high (the conversion rate of CEES reaches 100%, the selectivity reaches 98%, and the conversion rate of DECP reaches 100%). In addition, the catalyst is inexpensive to prepare.
(2) The invention synthesizes a series of amphiphilic capped niobium-rich vanadium oxide clusters by using hydrated capped niobium-rich vanadium oxide clusters and organic ammonium and other raw materials through an anion exchange method, and the amphiphilic capped niobium-rich vanadium oxide clusters are used for catalytic degradation of mustard gas simulants CEES and nerve agent simulants DECP. The catalytic activity is high (the conversion rate of CEES reaches 100%, the selectivity reaches 98%, and the conversion rate of DECP reaches 100%). In addition, the catalyst is inexpensive to prepare.
(3) The catalyst can be recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃.
(4) The method for degrading CEES and DECP has mild reaction conditions, and the reaction can be carried out at normal temperature and normal pressure. Heating and pressurizing are not needed.
Description of the drawings:
FIG. 1 is a schematic diagram of the synthesis of the amphiphilic catalyst prepared in example 1.
The specific implementation mode is as follows:
the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments, but is not limited thereto.
Example 1
(1) Catalyst [ C12H25N(CH3)3]7HNb6O19The synthesis steps are as follows: respectively weighing 0.06g K7HNb6O19·8H2O dissolved in 4mL NaH2PO4-Na2HPO4(1M) to obtain solution A, and weighing 0.12g of [ C ]12H25N(CH3)3]Br is dissolved in water to obtain solution B, and the solution A is slowly dripped into the solution BIn the solution B, the mixture was stirred for a while, and a white precipitate was precipitated. After 20 minutes of reaction, the solid was collected by centrifugation and the unreacted polyacid was removed by three washes with deionized water. Then drying the mixture for 24 hours in a vacuum drying oven at 60 ℃. Obtaining white solid, namely the amphiphilic hexaniobate catalyst.
(2) The catalytic degradation of CEES is carried out by adding 0.5mmol of 2-chloroethylethyl sulfide to a 10mL glass reaction flask and reacting the catalyst synthesized in step (1) with 5.7 × 10-3mmol was added to 1.5mL each of water and toluene. Stirring for a while to form a uniform emulsion. Then adding H2O20.5mmol of the aqueous solution was stirred at room temperature. After 30min of reaction, 0.5mL of reaction solution is taken out, diluted by absolute ethyl alcohol and quantitatively analyzed by gas chromatography GC-FID, the conversion rate of the obtained 2-chloroethyl ethyl sulfide is 100 percent, and the selectivity of the 2-chloroethyl ethyl sulfoxide is more than 98 percent.
The catalyst can be recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃. Can be repeatedly used.
(3) Catalytic degradation DECP was carried out by charging DECP0.135mmol in a 10mL glass reaction flask and reacting the catalyst 2.7 × 10 synthesized in step (1)-3mmol was added to solvent water and toluene. Stirring for a while to form a uniform emulsion. After reacting for 2 hours, taking out 0.5mL of reaction solution, diluting with absolute ethyl alcohol, carrying out quantitative analysis through gas chromatography GC-FID, obtaining the DECP with the conversion rate of 100%, recovering the catalyst through centrifugal demulsification, washing with ethyl acetate and deionized water for three times respectively, and then drying for 24 hours at 60 ℃ in a vacuum drying oven. Can be repeatedly used.
Example 2
(1) Catalyst [ C14H29N(CH3)3]7HNb6O19The synthesis steps are as follows: respectively weighing 0.06g K7HNb6O19·8H2O dissolved in 4mL NaH2PO4-Na2HPO4(1M) to give solution A, 0.14g of [ C ] was weighed14H29N(CH3)3]Br is dissolved in water to obtainAnd (3) slowly dripping the solution A into the solution B, and stirring for a while to precipitate a white precipitate. After 20 minutes of reaction the solid was collected by centrifugation and washed three times with deionized water to remove unreacted polyacid. Then drying the mixture for 24 hours in a vacuum drying oven at 60 ℃. Obtaining white solid, namely the amphiphilic hexaniobate catalyst.
(2) The catalytic degradation of CEES is carried out by adding 0.5mmol of 2-chloroethylethyl sulfide to a 10mL glass reaction flask and reacting the catalyst synthesized in step (1) with 5.7 × 10-3mmol was added to 1.5mL each of water and toluene. Stirring for a while to form a uniform emulsion. Then adding H2O20.5mmol of the aqueous solution was stirred at room temperature. After 30min of reaction, 0.5mL of reaction solution is taken out, diluted by absolute ethyl alcohol and quantitatively analyzed by gas chromatography GC-FID, the conversion rate of the obtained 2-chloroethyl ethyl sulfide is 100 percent, and the selectivity of the 2-chloroethyl ethyl sulfoxide is more than 98 percent. The catalyst can be recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃. Can be repeatedly used.
(3) Catalytic degradation DECP was carried out by charging DECP0.135mmol in a 10mL glass reaction flask and reacting the catalyst 2.7 × 10 synthesized in step (1)-3mmol was added to solvent water and toluene. Stirring for a while to form a uniform emulsion. After reacting for 2 hours, taking out 0.5mL of reaction solution, diluting with absolute ethyl alcohol, carrying out quantitative analysis through gas chromatography GC-FID, obtaining the DECP with the conversion rate of 100%, recovering the catalyst through centrifugal demulsification, washing with ethyl acetate and deionized water for three times respectively, and then drying for 24 hours at 60 ℃ in a vacuum drying oven. Can be repeatedly used.
Example 3
(1) Catalyst [ C16H33N(CH3)3]7HNb6O19The synthesis steps are as follows: respectively weighing 0.06g K7HNb6O19·8H2O dissolved in 4mL NaH2PO4-Na2HPO4(1M) to give solution A, 0.16g of [ C ] was weighed16H33N(CH3)3]Br is dissolved in water to obtainAnd (3) slowly dripping the solution A into the solution B, and stirring for a while to precipitate a white precipitate. After 20 minutes of reaction the solid was collected by centrifugation and washed three times with deionized water to remove unreacted polyacid. Then drying the mixture for 24 hours in a vacuum drying oven at 60 ℃. Obtaining white solid, namely the amphiphilic hexaniobate catalyst.
(2) The catalytic degradation of CEES is carried out by adding 0.5mmol of 2-chloroethylethyl sulfide to a 10mL glass reaction flask and reacting the catalyst synthesized in step (1) with 5.7 × 10-3mmol was added to 1.5mL each of water and toluene. Stirring for a while to form a uniform emulsion. Then adding H2O20.5mmol of the aqueous solution was stirred at room temperature. After 30min of reaction, 0.5mL of reaction solution is taken out, diluted by absolute ethyl alcohol and quantitatively analyzed by gas chromatography GC-FID, the conversion rate of the obtained 2-chloroethyl ethyl sulfide is 100 percent, and the selectivity of the 2-chloroethyl ethyl sulfoxide is more than 98 percent. The catalyst can be recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃. Can be repeatedly used.
(3) Catalytic degradation DECP was carried out by charging DECP0.135mmol in a 10mL glass reaction flask and reacting the catalyst 2.7 × 10 synthesized in step (1)-3mmol was added to solvent water and toluene. Stirring for a while to form a uniform emulsion. After reacting for 2 hours, taking out 0.5mL of reaction solution, diluting with absolute ethyl alcohol, carrying out quantitative analysis through gas chromatography GC-FID, obtaining the DECP with the conversion rate of 100%, recovering the catalyst through centrifugal demulsification, washing with ethyl acetate and deionized water for three times respectively, and then drying for 24 hours at 60 ℃ in a vacuum drying oven. Can be repeatedly used.
Example 4
(1) Catalyst [ C18H37N(CH3)3]7HNb6O19The synthesis steps are as follows: respectively weighing 0.06g K7HNb6O19·8H2O dissolved in 4mL NaH2PO4-Na2HPO4(1M) to obtain solution A, 0.18g of [ C ] was weighed18H37N(CH3)3]Dissolving Br in water to obtain B solutionAnd (3) slowly dripping the solution A into the solution B, and stirring for a moment to precipitate a white precipitate. After 20 minutes of reaction the solid was collected by centrifugation and washed three times with deionized water to remove unreacted polyacid. Then drying the mixture for 24 hours in a vacuum drying oven at 60 ℃. Obtaining white solid, namely the amphiphilic hexaniobate catalyst.
(2) The catalytic degradation of CEES is carried out by adding 0.5mmol of 2-chloroethylethyl sulfide to a 10mL glass reaction flask and reacting the catalyst synthesized in step (1) with 5.7 × 10-3mmol was added to 1.5mL each of water and toluene. Stirring for a while to form a uniform emulsion. Then adding H2O20.5mmol of the aqueous solution was stirred at room temperature. After 30min of reaction, 0.5mL of reaction solution is taken out, diluted by absolute ethyl alcohol and quantitatively analyzed by gas chromatography GC-FID, the conversion rate of the obtained 2-chloroethyl ethyl sulfide is 100 percent, and the selectivity of the 2-chloroethyl ethyl sulfoxide is more than 98 percent. The catalyst can be recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃. Can be repeatedly used.
(3) Catalytic degradation DECP was carried out by charging DECP0.135mmol in a 10mL glass reaction flask and reacting the catalyst 2.7 × 10 synthesized in step (1)-3mmol was added to solvent water and toluene. Stirring for a while to form a uniform emulsion. After reacting for 2 hours, taking out 0.5mL of reaction solution, diluting with absolute ethyl alcohol, carrying out quantitative analysis through gas chromatography GC-FID, obtaining the DECP with the conversion rate of 100%, recovering the catalyst through centrifugal demulsification, washing with ethyl acetate and deionized water for three times respectively, and then drying for 24 hours at 60 ℃ in a vacuum drying oven. Can be repeatedly used.
Example 5
(1) Catalyst [ C12H25N(CH3)3]9PNb12V2O42The synthesis steps are as follows: 0.15g of TMA was weighed out separately9PNb12V2O42·19H2O dissolved in 4mL NaH2PO4-Na2HPO4(1M) to obtain solution A, and weighing 0.12g of [ C ]12H25N(CH3)3]Br is dissolved in water to obtain a solution B, the solution A is slowly dripped into the solution B, and the mixture is stirred for a moment to precipitate a light yellow precipitate. After 20 minutes of reaction the solid was collected by centrifugation and washed three times with deionized water to remove unreacted polyacid. Then drying the mixture for 24 hours in a vacuum drying oven at 60 ℃. Obtaining light yellow solid, namely the amphiphilic niobium-vanadium-oxygen cluster catalyst.
(2) The catalytic degradation of CEES is carried out by adding 0.5mmol of 2-chloroethylethyl sulfide to a 10mL glass reaction flask and reacting the catalyst synthesized in step (1) with 5.7 × 10-3mmol was added to 1.5mL each of water and toluene. Stirring for a while to form a uniform emulsion. Then adding H2O20.5mmol of the aqueous solution was stirred at room temperature. After 30min of reaction, 0.5ml of reaction solution is taken out, diluted by absolute ethyl alcohol and quantitatively analyzed by gas chromatography GC-FID, the conversion rate of the obtained 2-chloroethyl ethyl sulfide is more than 95 percent, and the selectivity of the 2-chloroethyl ethyl sulfoxide is more than 96 percent. The catalyst can be recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃. Can be repeatedly used.
(3) Catalytic degradation DECP was carried out by charging DECP0.135mmol in a 10mL glass reaction flask and reacting the catalyst 2.7 × 10 synthesized in step (1)-3mmol was added to solvent water and toluene. Stirring for a while to form a uniform emulsion. After reacting for 2 hours, taking out 0.5mL of reaction solution, diluting with absolute ethyl alcohol, carrying out quantitative analysis through gas chromatography GC-FID, obtaining the DECP with the conversion rate of 100%, recovering the catalyst through centrifugal demulsification, washing with ethyl acetate and deionized water for three times respectively, and then drying for 24 hours at 60 ℃ in a vacuum drying oven. Can be repeatedly used.
Example 6
(1) Catalyst [ C14H29N(CH3)3]9PNb12V2O42The synthesis steps are as follows: 0.15g of TMA was weighed out separately9PNb12V2O42·19H2O dissolved in 4mL NaH2PO4-Na2HPO4(1M) to give solution A, 0.14g of [ C ] was weighed4H29N(CH3)3]Br is dissolved in water to obtain a solution B, the solution A is slowly dripped into the solution B, and the mixture is stirred for a moment to precipitate a light yellow precipitate. After 20 minutes of reaction the solid was collected by centrifugation and washed three times with deionized water to remove unreacted polyacid. Then drying the mixture for 24 hours in a vacuum drying oven at 60 ℃. Obtaining light yellow solid, namely the amphiphilic niobium-vanadium-oxygen cluster catalyst.
(2) The catalytic degradation of CEES is carried out by adding 0.5mmol of 2-chloroethylethyl sulfide to a 10mL glass reaction flask and reacting the catalyst synthesized in step (1) with 5.7 × 10-3mmol was added to 1.5mL each of water and toluene. Stirring for a while to form a uniform emulsion. Then adding H2O20.5mmol of the aqueous solution was stirred at room temperature. After 30min of reaction, 0.5mL of reaction solution is taken out, diluted by absolute ethyl alcohol and quantitatively analyzed by gas chromatography GC-FID, the conversion rate of the obtained 2-chloroethyl ethyl sulfide is more than 95 percent, and the selectivity of the 2-chloroethyl ethyl sulfoxide is more than 96 percent. The catalyst can be recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃. Can be repeatedly used.
(3) Catalytic degradation DECP was carried out by charging DECP0.135mmol in a 10mL glass reaction flask and reacting the catalyst 2.7 × 10 synthesized in step (1)-3mmol was added to solvent water and toluene. Stirring for a while to form a uniform emulsion. After reacting for 2 hours, taking out 0.5mL of reaction solution, diluting with absolute ethyl alcohol, carrying out quantitative analysis through gas chromatography GC-FID, obtaining the DECP with the conversion rate of 100%, recovering the catalyst through centrifugal demulsification, washing with ethyl acetate and deionized water for three times respectively, and then drying for 24 hours at 60 ℃ in a vacuum drying oven. Can be repeatedly used.
Example 7
(1) Catalyst [ C16H33N(CH3)3]9PNb12V2O42The synthesis steps are as follows: 0.15g of TMA was weighed out separately9PNb12V2O42·19H2O dissolved in 4mL NaH2PO4-Na2HPO4(1M) in a buffer solutionTo obtain solution A, 0.16g of [ C ] was weighed16H33N(CH3)3]Br is dissolved in water to obtain a solution B, the solution A is slowly dripped into the solution B, and the mixture is stirred for a moment to precipitate a light yellow precipitate. After 20 minutes of reaction the solid was collected by centrifugation and washed three times with deionized water to remove unreacted polyacid. Then drying the mixture for 24 hours in a vacuum drying oven at 60 ℃. Obtaining light yellow solid, namely the amphiphilic niobium-vanadium-oxygen cluster catalyst.
(2) The catalytic degradation of CEES is carried out by adding 0.5mmol of 2-chloroethylethyl sulfide to a 10mL glass reaction flask and reacting the catalyst synthesized in step (1) with 5.7 × 10-3mmol was added to 1.5mL each of water and toluene. Stirring for a while to form a uniform emulsion. Then adding H2O20.5mmol of the aqueous solution was stirred at room temperature. After 30min of reaction, 0.5mL of reaction solution is taken out, diluted by absolute ethyl alcohol and quantitatively analyzed by gas chromatography GC-FID, the conversion rate of the obtained 2-chloroethyl ethyl sulfide is more than 95 percent, and the selectivity of the 2-chloroethyl ethyl sulfoxide is more than 96 percent. The catalyst can be recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃. Can be repeatedly used.
(3) Catalytic degradation DECP was carried out by charging DECP0.135mmol in a 10mL glass reaction flask and reacting the catalyst 2.7 × 10 synthesized in step (1)-3mmol was added to solvent water and toluene. Stirring for a while to form a uniform emulsion. After reacting for 2 hours, taking out 0.5ml of reaction solution, diluting the reaction solution with absolute ethyl alcohol, carrying out quantitative analysis through gas chromatography GC-FID, obtaining the DECP with the conversion rate of 100 percent, recovering the catalyst through centrifugal demulsification, washing the DECP with ethyl acetate and deionized water for three times respectively, and then drying the DECP in a vacuum drying oven at 60 ℃ for 24 hours. Can be repeatedly used.
Example 8
(1) Catalyst [ C18H37N(CH3)3]9PNb12V2O42The synthesis steps are as follows: 0.15g of TMA was weighed out separately9PNb12V2O42·19H2O dissolved in 4mL NaH2PO4-Na2HPO4(1M) to obtain solution A, 0.18g of [ C ] was weighed18H37N(CH3)3]Br is dissolved in water to obtain a solution B, the solution A is slowly dripped into the solution B, and the mixture is stirred for a moment to precipitate a light yellow precipitate. After 20 minutes of reaction the solid was collected by centrifugation and washed three times with deionized water to remove unreacted polyacid. Then drying the mixture for 24 hours in a vacuum drying oven at 60 ℃. Obtaining light yellow solid, namely the amphiphilic niobium-vanadium-oxygen cluster catalyst.
(2) The catalytic degradation of CEES is carried out by adding 0.5mmol of 2-chloroethylethyl sulfide to a 10mL glass reaction flask and reacting the catalyst synthesized in step (1) with 5.7 × 10-3mmol was added to 1.5mL each of water and toluene. Stirring for a while to form a uniform emulsion. Then adding H2O20.5mmol of the aqueous solution was stirred at room temperature. After 30min of reaction, 0.5ml of reaction solution is taken out, diluted by absolute ethyl alcohol and quantitatively analyzed by gas chromatography GC-FID, the conversion rate of the obtained 2-chloroethyl ethyl sulfide is more than 95 percent, and the selectivity of the 2-chloroethyl ethyl sulfoxide is more than 96 percent. The catalyst can be recovered by centrifugal demulsification, washed by ethyl acetate and deionized water for three times respectively, and then dried for 24 hours in a vacuum drying oven at 60 ℃. Can be repeatedly used.
(3) Catalytic degradation DECP was carried out by charging DECP0.135mmol in a 10mL glass reaction flask and reacting the catalyst 2.7 × 10 synthesized in step (1)-3mmol was added to solvent water and toluene. Stirring for a while to form a uniform emulsion. After reacting for 2 hours, taking out 0.5ml of reaction solution, diluting the reaction solution with absolute ethyl alcohol, carrying out quantitative analysis through gas chromatography GC-FID, obtaining the DECP with the conversion rate of 100 percent, recovering the catalyst through centrifugal demulsification, washing the DECP with ethyl acetate and deionized water for three times respectively, and then drying the DECP in a vacuum drying oven at 60 ℃ for 24 hours. Can be repeatedly used.
The present invention includes, but is not limited to, the above examples, and any equivalent substitutions or partial modifications made under the principle of the spirit of the present invention are considered to be within the scope of the present invention.
Claims (3)
1. A method for catalytic degradation of chemical warfare agent simulants at normal temperature and pressure is characterized in that:
(1) preparation of amphiphilic niobium-oxygen cluster catalyst: dissolving the niobium-oxygen-rich clusters in a buffer solution, and reacting with organic ammonium to prepare an amphiphilic niobium-oxygen-rich cluster catalyst;
(2) and (3) emulsion catalytic degradation: the amphiphilic niobium-oxygen cluster catalyst is dissolved in a mixed solvent of toluene and water to form emulsion, the emulsion system is used for catalyzing and degrading chemical warfare agent mimics, and the system can be repeatedly used;
in the step (1), the organic ammonium is [ C ]12H25N(CH3)3]Br，[C14H29N(CH3)3]Br，[C16H33N(CH3)3]Br，[C18H37N(CH3)3]One kind of Br; in the step (1), the niobium-oxygen cluster is K7HNb6O19，(TMA)9PNb12V2O42One of (1);
the chemical warfare agent mimic used in step (2) is the nerve agent mimic diethyl cyanophosphonate (DECP).
2. The method as claimed in claim 1, wherein the buffer solution used in step (1) is NaH2PO4-Na2HPO4。
3. The method of claim 1 where the [ HNb ] is a chemical agent simulant6O19]The molar ratio of the anion to the organic ammonium cation is 1: 7; [ PNb)12V2O42]The molar ratio of anion to organoammonium cation is 1: 9.
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| CN113292595A (en) * | 2021-04-30 | 2021-08-24 | 南京工业大学 | Hydrophobic vanadyl-organic molecular cage-based porous liquid for extracting L-tryptophan and preparation method and application thereof |
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| WO2019218275A1 (en) * | 2018-05-16 | 2019-11-21 | 大连理工大学 | Polyacid compound guided by metal ions and functionalized by carboxylate ligand, preparation method therefor and use thereof in catalytic degradation of chemical warfare agent simulants |
| CN108559100B (en) * | 2018-05-16 | 2021-02-19 | 大连理工大学 | Metal ion guided carboxylic acid ligand functionalized polyacid compound, preparation method thereof and application of catalytic degradation chemical warfare agent simulant |
| CN109261212B (en) * | 2018-08-22 | 2020-10-27 | 北京理工大学 | Multi-niobium-oxygen cluster-double-metal hydroxide compound, preparation method thereof and method for heterogeneous catalytic degradation of chemical warfare agent analogue |
| CN109126010B (en) * | 2018-09-10 | 2020-08-04 | 北京理工大学 | Decontaminating agent containing niobium-oxygen clusters, preparation method and method for degrading V-type chemical warfare agent simulant by using decontaminating agent |
| CN110960825B (en) * | 2019-12-12 | 2021-07-30 | 北京化工大学 | Double-functional chemical warfare agent degradation material and preparation method thereof |
| CN111439784A (en) * | 2020-03-26 | 2020-07-24 | 南通大学 | Heteropolysilver niobate for degrading printing and dyeing wastewater and preparation method and application thereof |
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