CN108559100B - Metal ion guided carboxylic acid ligand functionalized polyacid compound, preparation method thereof and application of catalytic degradation chemical warfare agent simulant - Google Patents

Metal ion guided carboxylic acid ligand functionalized polyacid compound, preparation method thereof and application of catalytic degradation chemical warfare agent simulant Download PDF

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CN108559100B
CN108559100B CN201810495657.8A CN201810495657A CN108559100B CN 108559100 B CN108559100 B CN 108559100B CN 201810495657 A CN201810495657 A CN 201810495657A CN 108559100 B CN108559100 B CN 108559100B
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carboxylic acid
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安海艳
侯玉姣
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Dalian University of Technology
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Abstract

A metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound, a preparation method and application of catalytic degradation chemical warfare agent simulants are disclosed, wherein sodium molybdate, transition metal, alanine and p-hydroxybenzoic acid are used as raw materials, water is used as a solvent, stirring is carried out for 1h at the temperature of 80 ℃, and the solution is cooled and placed to obtain product crystalsA body; stirring the prepared polyacid hybrid compound catalyst, 2-chloroethyl ethyl sulfide and absolute ethyl alcohol in a reaction vessel for a while at room temperature, and adding H2O2Reacting the solution for 5min under stirring to complete the catalytic oxidative degradation of the 2-chloroethyl ethyl sulfide; the catalyst, diethyl cyanophosphate, N-dimethylformamide and water are fully stirred in a reaction vessel and react for 10min to complete the catalytic hydrolysis degradation of the diethyl cyanophosphate. The prepared polyacid hybrid compound catalyst has the advantages of high conversion rate, high selectivity and reusability for the catalytic degradation of the two chemical warfare agent mimics.

Description

Metal ion guided carboxylic acid ligand functionalized polyacid compound, preparation method thereof and application of catalytic degradation chemical warfare agent simulant
Technical Field
The invention belongs to the technical field of catalytic chemistry, and particularly relates to a hybrid compound formed by carboxylic acid ligand functionalized polyacid and metal ions, a preparation method of the hybrid compound, and application of the hybrid compound in catalytic oxidation degradation of mustard gas simulant 2-chloroethyl ethyl sulfide and catalytic hydrolysis degradation of nerve agent simulant diethyl cyanophosphate.
Background
Chemical warfare agents have contributed to a significant number of casualties from the first world war to the recent years of the syrian chemical weapon attack event. Vesicant agents and nerve agents are two more and more toxic chemical warfare agents. Foaming toxicants can cause local damage to skin, eyes, respiratory tract and the like, can destroy DNA structures of human bodies, can cause death in case of large dose, and are most representative of mustard gas (bis (2-chloroethyl) sulfide), and the degradation mode of the mustard gas mainly comprises hydrolysis, oxidation and the like. Because mustard gas is poorly soluble in water, it tends to be incompletely degraded by hydrolysis, and conversion to the non-toxic bis (2-chloroethyl) sulfoxide by selective oxidation without the production of the highly toxic peroxidation product bis (2-chloroethyl) sulfone is an ideal degradation pathway for mustard gas. Nerve agents, which are capable of disrupting the normal conduction function of the nervous system, are typically phosphate-based compounds that degrade by hydrolysis to break the P-X bond. Due to the high toxicity of real mustard and nerve gases, 2-chloroethyl ethyl sulfide (CEES) and diethyl cyanophosphate (DECP) are commonly used as their mimics to study their degradation process. Although some solid materials such as metal organic frameworks and activated carbon have been reported in the literature to have some ability to degrade chemical warfare agent mimics, most materials only act as monofunctional catalysts to degrade a single class of chemical warfare agent by oxidation or hydrolysis. However, in practice, considering the possibility of simultaneous use and unpredictability of multiple chemical warfare agents, designing and synthesizing a multifunctional catalyst having both oxidative and hydrolytic properties is a subject of urgent research.
Polyoxometallate is called Polyacid (POMs) for short, is an important inorganic polynuclear metal oxygen cluster, has abundant molecules, electronic structures and attractive topological properties, and has wide application in the fields of catalysis, material science and the like. Hill topic group studies in the United states show iron-containing polytungstates and [ PV2Mo10O40]5-Can catalyze, oxidize and degrade mustard gas simulant, poly niobate [ Nb ]6O19]8-And K12[Ti2O2][GeNb12O40]·19H2O is capable of catalyzing the hydrolytic degradation of nerve agent mimics (w.w.guo, h.j.lv, k.p.sullivan, w.o.gordon, a.balboa, g.w.wagner, d.g.musaev, j.bacsa, c.l.hill, angelw.chem.int.ed., 2016,55, 7403-jar 7407). More recently, a homogeneous polyacid catalyst H13[(CH3)4N]12[PNb12O40(VO)2(V4O12)2]·22H2O and a TBA-polyV6Gel materials are reported to be capable of simultaneously oxidatively degrading mustard gas mimetics and hydrolytically degrading mimetics of nerve gas phosphate (j.dong, j.f.hu, y.n.chi.z.g.lin, b.zuu.s.yang.c.l.hill, c.w.hu, angelw.chem.int.ed., 2017,56, 4473. f.i.d., 4477, k.p.sullivan, w.a.new wert, h.d.zeng, a.k.mehta, q.s.yin.d.a.hillsheim.s.vivek, p.c.yin, d.l.collins-Wildman, chem.commun.,2017,53, 11480. f. 11483). The above reported polyacid catalyst systems have the problems of low catalytic efficiency, low selectivity and difficult reuse of the catalyst. Based on this, it is necessary to develop multifunctional polyacid catalysts which are used for catalytic degradation of various chemical warfare agent mimics, have high efficiency and high selectivity, and can be continuously used.
Disclosure of Invention
The invention aims to synthesize a catalyst based on carboxylic acid ligand functionalized polyacid clusters and metal cations, the catalyst can efficiently and selectively oxidize and degrade 2-chloroethyl ethyl sulfide and hydrolyze and degrade diethyl cyanophosphate at normal temperature and normal pressure, and the catalyst can be repeatedly used.
The technical scheme of the invention is as follows:
a metal ion-guided carboxylic acid ligand functionalized polyacid compound, polymolybdate cluster [ AsMo ] functionalized by carboxylic acid ligand6O21(Ala)(PHBA)2]5-A 1D chain structure formed by covalent connection of cobalt ions, nickel ions, zinc ions or manganese ions, and the chemical formula is K2H[(H2O)4M][AsMo6O21(Ala)(PHBA)2]·nH2O; wherein M ═ Co2+,Ni2+,Zn2+,Mn2+(ii) a Ala ═ alanine; PHBA ═ p-hydroxybenzoic acid; n is 6.5,9,7.5,7.5, the value of n is corresponding to M is Co2+,Ni2+,Zn2 +,Mn2+。
The crystal of the metal ion guided carboxylic acid ligand functionalized polyacid hybrid compound belongs to a triclinic crystal system, and the space group is P-1;
when M is Co2+When the unit cell parameters of Compound 1 are
Figure BDA0001669092720000031
Figure BDA0001669092720000032
α＝76.700(4)°，β＝74.058(4)°，γ＝76.399(4)°；
When M is Ni2+When the unit cell parameters of compound 2 are
Figure BDA0001669092720000033
Figure BDA0001669092720000034
α＝76.4990(10)°，β＝74.053(2)°，γ＝76.535(2)°；
When M ═ Zn2+When the unit cell parameter of compound 3 is
Figure BDA0001669092720000035
Figure BDA0001669092720000036
α＝76.4430(10)°，β＝74.0620(10)°，γ＝76.2250(10)°；
When M is Mn2+When the unit cell parameter of compound 4 is
Figure BDA0001669092720000037
Figure BDA0001669092720000038
α＝76.319(3)°，β＝73.933(3)°，γ＝76.064(3)°；
The four compounds are isostructural, with a crystallographically independent [ AsMo ] in the asymmetric unit6O21]3-Polyacid anion, one cobalt ion, nickel ion, zinc ion or manganese ion, two potassium ions, two p-hydroxybenzoic acids and one protonated alanine; first of all [ AsMo6O21(Ala)(PHBA)2]5-The units form a 1D chain structure through Co/Ni/Zn/Mn-O-Mo, 2D supermolecule structures are formed among the 1D chains through hydrogen bonds, and the 2D net structures are connected into a 3D supermolecule structure through the hydrogen bond action.
A method for preparing a metal ion-guided carboxylic acid ligand functionalized polyacid compound comprises the following steps:
mixing and dissolving sodium molybdate, p-hydroxybenzoic acid, alanine, potassium chloride and arsenic trioxide in deionized water, adjusting the pH value to 3.5-4.5 by hydrochloric acid, and adding excessive metal cobalt chloride, wherein the molar ratio of the sodium molybdate, the p-hydroxybenzoic acid, the alanine, the potassium chloride, the arsenic trioxide to the cobalt chloride is 6:2:1:2-3:1: 1-3; and then stirring in a water bath at the temperature of 75-100 ℃ for 1-5h, cooling the solution, filtering, standing until crystals are generated, and washing and drying the crystals to obtain the metal ion guided carboxylic acid ligand functionalized polyacid hybrid compound.
The cobalt chloride is replaced by nickel chloride or zinc chloride or manganese chloride.
The cobalt chloride is replaced by cobalt nitrate or cobalt sulfate.
The application of a metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound in catalytic degradation of 2-chloroethyl ethyl sulfide and hydrolytic degradation of diethyl cyanophosphate is as follows:
degradation of 2-chloroethylethyl sulfide (CEES) experimental conditions: CEES, metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound and absolute ethyl alcohol are mixed, stirred and added with oxidant H2O2Reacting for 5min under the stirring condition to complete the catalytic oxidative degradation of CEES, wherein the molar ratio of CEES, the metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound and the oxidant is 200:3: 200-; the catalytic degradation route is as follows:
Figure BDA0001669092720000041
experiment for the degradation of diethyl cyanophosphate (DECP): mixing DECP, N-Dimethylformamide (DMF) and water, fully mixing and stirring, adding a metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound into the solution, and reacting for 10min under the stirring condition to complete the catalytic hydrolytic degradation of DECP, wherein the molar ratio of DECP to a catalyst is 1000: 1; the catalytic degradation route is as follows:
Figure BDA0001669092720000042
the yield and selectivity of the catalyst for catalyzing the 2-chloroethyl ethyl sulfide oxidation and the hydrolysis reaction of the cyano diethyl phosphate are measured by a gas chromatograph at room temperature.
The invention has the beneficial effects that:
(1) the catalyst can be used as a multifunctional catalyst to catalyze the degradation of 2-chloroethyl ethyl sulfide and cyano diethyl phosphate with high efficiency and high selectivity; in an experiment of catalytic oxidative degradation of 2-chloroethyl ethyl sulfide, the reaction is carried out for 5min, the degradation rate reaches 99%, the selectivity reaches 99.9%, and the catalyst is almost completely oxidized into nontoxic 2-chloroethyl ethyl sulfoxide (CEESO); in an experiment of catalyzing, hydrolyzing and degrading diethyl cyanophosphate, the reaction is carried out for 10min, and the degradation rate reaches 99%.
(2) The catalyst has the advantage of repeated use for many times; in the catalytic degradation of 2-chloroethyl ethyl sulfide, the catalyst is used as a heterogeneous catalyst, after the catalytic reaction is finished, solid powder obtained by filtering is used as the catalyst, and repeated catalytic experiments are carried out for multiple times, so that the reaction conversion rate and the selectivity are not obviously reduced; in the catalytic degradation of the diethyl cyanophosphate, after the reaction is completed, the diethyl cyanophosphate can be continuously added without any treatment, so that the continuous catalytic hydrolysis degradation is carried out, and the catalytic effect is unchanged.
(3) The method for preparing the metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound catalyst is a conventional aqueous solution method, is safe and simple to operate, and has the advantages of low raw material cost and product yield of 62%.
(4) The metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound catalyst prepared by the method disclosed by the invention is novel in structure and is an expanded structure formed by two different organic carboxylic acid ligand functionalized polyacid and metal ions in the first example.
Drawings
FIG. 1 is a diagram of asymmetric units of Compound 1 of the present invention.
Fig. 2 is a 1D chain structure diagram of compound 1 of the present invention.
FIG. 3 is a 2D supramolecular structure of Compound 1 of the present invention.
FIG. 4 shows the results of catalytic oxidation of CEES by the polyacid hybrid compound of example 1 of the present invention, FIG. a is the change in conversion rate of catalytic oxidation of CEES by the compounds 1-4 with time; panel b is the gas chromatographic signal for the catalytic oxidation reaction assay of compound 1.
FIG. 5 shows the CEES reaction procedure of catalytic oxidation of Compound 1 according to example 1 of the present invention1H nuclear magnetic test.
FIG. 6 shows the conversion and selectivity of the cyclic catalytic oxidation of CEES of Compound 1 as described in example 1 of the present invention.
FIG. 7 is a comparison of infrared spectra before and after catalysis of Compound 1 of example 1 of the present invention.
Fig. 8 shows X-ray powder diffraction patterns of polyacid compound 1 of example 1 of the present invention before and after catalysis.
FIG. 9 is a diagram of a possible mechanism for the catalytic oxidation of CEES by Compound 1 as described in example 1 of the present invention.
FIG. 10 shows the DECP results of the catalytic hydrolysis of the polyacid hybrid compound described in example 1 of the present invention.
FIG. 11 shows the conversion of DECP by cyclic catalytic hydrolysis of Compound 1 as described in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are provided herein for purposes of illustration and are not intended to be limiting.
Example 1 preparation of a metal ion-directed carboxylic acid ligand functionalized polyacid hybrid catalyst, the specific steps are as follows:
dissolving 0.145g of sodium molybdate, 0.0197g of arsenic dioxide, 0.0224g of potassium chloride, 0.0089g of alanine and 0.0274g of p-hydroxybenzoic acid in 20mL of water, stirring, adjusting the pH value to 3.5 by using HCl, stirring for 1 hour at room temperature, adding 0.0714g of cobalt chloride, finally refluxing for one hour at 80 ℃, and cooling to obtain the required compound.
The 0.0714g of cobalt chloride was replaced by 0.0678g of nickel chloride or 0.0861g of zinc chloride or 0.0486g of manganese chloride.
Example 2 preparation of a metal ion-guided carboxylic acid ligand functionalized polyacid hybrid catalyst, the specific steps are as follows:
dissolving 0.145g of sodium molybdate, 0.0197g of arsenic dioxide, 0.0224g of potassium chloride, 0.0089g of alanine and 0.0274g of p-hydroxybenzoic acid in 20mL of water, stirring, adjusting the pH value to 3.5 by using HCl, stirring for 1 hour at room temperature, adding 0.0873g of nickel nitrate, finally refluxing for one hour at 80 ℃, and cooling to obtain the required compound.
Example 3 preparation of a metal ion-directed carboxylic acid ligand functionalized polyacid hybrid catalyst, the specific steps are as follows:
the preparation of the catalyst of the metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound of example 4, which is prepared by dissolving 0.145g of sodium molybdate, 0.0197g of arsenic dioxide, 0.0224g of potassium chloride, 0.0089g of alanine and 0.0274g of p-hydroxybenzoic acid in 20mL of water and stirring them with HCl to adjust the pH to 3.5, then stirring them at room temperature for 1 hour, adding 0.0893g of zinc nitrate, finally refluxing at 80 ℃ for one hour, and cooling, is carried out, and the specific steps are as follows:
dissolving 0.145g of sodium molybdate, 0.0197g of arsenic dioxide, 0.0149g of potassium chloride, 0.0089g of alanine and 0.0274g of p-hydroxybenzoic acid in 20mL of water, stirring, adjusting the pH value to 3.5 by using HCl, stirring for 1 hour at room temperature, adding 0.0843g of cobalt sulfate, finally refluxing for one hour at 80 ℃, and cooling to obtain the required compound.
Example 5 preparation of a metal ion-directed carboxylic acid ligand functionalized polyacid hybrid catalyst, the specific steps are as follows:
dissolving 0.145g of sodium molybdate, 0.0197g of arsenic dioxide, 0.0149g of potassium chloride, 0.0089g of alanine and 0.0274g of p-hydroxybenzoic acid in 20mL of water, stirring, adjusting the pH value to 3.5 by using HCl, stirring for 1 hour at room temperature, adding 0.0788g of nickel sulfate, finally refluxing for one hour at 80 ℃, and cooling to obtain the required compound.
Example 6 preparation of a metal ion-directed carboxylic acid ligand functionalized polyacid hybrid catalyst, the specific steps are as follows:
dissolving 0.145g of sodium molybdate, 0.0197g of arsenic dioxide, 0.0149g of potassium chloride, 0.0089g of alanine and 0.0274g of p-hydroxybenzoic acid in 20mL of water, stirring, adjusting the pH value to 3.5 by using HCl, stirring for 1 hour at room temperature, adding 0.0863g of zinc sulfate, finally refluxing for one hour at 80 ℃, and cooling to obtain the required compound.
Example 7 preparation of a metal ion-directed carboxylic acid ligand functionalized polyacid hybrid catalyst, the specific steps are as follows:
dissolving 0.145g of sodium molybdate, 0.0197g of arsenic dioxide, 0.0149g of potassium chloride, 0.0089g of alanine and 0.0274g of p-hydroxybenzoic acid in 20mL of water, stirring, adjusting the pH value to 3.5 by using HCl, stirring for 1 hour at room temperature, adding 0.0669g of manganese sulfate, finally refluxing for one hour at 80 ℃, and cooling to obtain the required compound.
Example 8 preparation of a metal ion-directed carboxylic acid ligand functionalized polyacid hybrid catalyst, the specific steps are as follows:
dissolving 0.145g of sodium molybdate, 0.0197g of arsenic dioxide, 0.0224g of potassium chloride, 0.0089g of alanine and 0.0274g of p-hydroxybenzoic acid in 20mL of water, stirring, adjusting the pH value to 4.2 by using HCl, stirring for 1 hour at room temperature, adding 0.0714g of cobalt chloride, finally refluxing for one hour at 80 ℃, and cooling to obtain the required compound.
The 0.0714g of cobalt chloride was replaced by 0.0678g of nickel chloride or 0.0861g of zinc chloride or 0.0486g of manganese chloride.
Example 9 preparation of a metal ion-directed carboxylic acid ligand functionalized polyacid hybrid catalyst, the specific steps are as follows:
dissolving 0.145g of sodium molybdate, 0.0197g of arsenic dioxide, 0.0224g of potassium chloride, 0.0089g of alanine and 0.0274g of p-hydroxybenzoic acid in 20mL of water, stirring, adjusting the pH value to 3.5 by using HCl, stirring for 1 hour at room temperature, adding 0.0476g of cobalt chloride, finally refluxing for one hour at 80 ℃, and cooling to obtain the required compound.
The 0.0476g of cobalt chloride was replaced by 0.0452g of nickel chloride or 0.0574g of zinc chloride or 0.0324g of manganese chloride.
The product of the above example was tested to give a compound of formula K2H[(H2O)4M][AsMo6O21(Ala)(PHBA)2]·nH2O1-4 (M ═ Co, Ni, Zn, Mn; Ala ═ alanine; PHBA ═ p-hydroxybenzoic acid; n ═ 6.5,9,7.5,7.5), the crystal structures of the polyacid hybrid compounds of the invention are shown in FIGS. 1,2 and 3.
The catalytic results of the compound prepared in example 1 were examined by gas chromatography, and FIG. 4a, the change in the measured CEES conversion over time, shows that almost all of the CEES was converted to CEESO within 5min, and FIG. 4b is a comparison of the peaks of the gas chromatography of the different substances measured at different times, further demonstrating that compound 1 was able to convert CEES almost completely to CEESO within 5 min.
By using1H Nuclear magnetism the catalytic results of the compound prepared in example 1 were examined, FIG. 5 at various times1H NMR plot shows that the catalyst prepared in example 1 almost completely converts CEES within 5 min.
The stability before and after the catalytic reaction of the compound prepared in example 1 was tested by infrared spectroscopy, and fig. 7 is an infrared contrast chart before and after the catalytic reaction of the polyacid hybrid compound of the present invention, and no significant change in the characteristic peak position indicates that the compound has not changed before and after the catalysis of the heterogeneous catalyst.
XRD was used to test the stability of the compound prepared in example 1 before and after catalytic reaction, and FIG. 8 is the fitting and XRD contrast after catalytic reaction of the polyacid hybrid compound of the present invention, which shows that the compound has not changed before and after catalysis as a heterogeneous catalyst.
The catalytic results of the compound prepared in example 1 were examined by gas chromatography and figure 10, the change in measured DECP conversion over time, shows that DECP was almost completely converted within 10 min.
TABLE 1 comparison of catalytic oxidative degradation of CEES by different catalysts in recent years
Figure BDA0001669092720000091
Figure BDA0001669092720000101
TABLE 2 DECP comparison by catalytic hydrolysis of various catalysts in recent years
Figure BDA0001669092720000102

Claims (6)

1. A metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound is prepared from carboxylic acid ligand functionalized polymolybdic acid cluster [ AsMo6O21(Ala)(PHBA)2]5-By cobalt ion, nickel ion, zinc1D chain structure formed by covalent connection of ions or manganese ions and having chemical formula K2H[(H2O)4M][AsMo6O21(Ala)(PHBA)2]·nH2O; wherein M ═ Co2+,Ni2+,Zn2+,Mn2+(ii) a Ala ═ alanine; PHBA ═ p-hydroxybenzoic acid; n is 6.5,9,7.5,7.5, the value of n is corresponding to M is Co2+,Ni2+,Zn2 +,Mn2+；
The crystal of the metal ion guided carboxylic acid ligand functionalized polyacid hybrid compound belongs to a triclinic crystal system, and the space group is P-1;
when M is Co2+When the unit cell parameters of Compound 1 are
Figure FDA0002801169970000011
Figure FDA0002801169970000012
α＝76.700(4)°，β＝74.058(4)°，γ＝76.399(4)°；
When M is Ni2+When the unit cell parameters of compound 2 are
Figure FDA0002801169970000013
Figure FDA0002801169970000014
α＝76.4990(10)°，β＝74.053(2)°，γ＝76.535(2)°；
When M ═ Zn2+When the unit cell parameter of compound 3 is
Figure FDA0002801169970000015
Figure FDA0002801169970000016
α＝76.4430(10)°，β＝74.0620(10)°，γ＝76.2250(10)°；
When M is Mn2+When the unit cell parameter of compound 4 is
Figure FDA0002801169970000017
Figure FDA0002801169970000018
α＝76.319(3)°，β＝73.933(3)°，γ＝76.064(3)°；
The four compounds are isostructural, with a crystallographically independent [ AsMo ] in the asymmetric unit6O21]3-Polyacid anion, one cobalt ion, nickel ion, zinc ion or manganese ion, two potassium ions, two p-hydroxybenzoic acids and one protonated alanine; first of all [ AsMo6O21(Ala)(PHBA)2]5-The units form a 1D chain structure through Co/Ni/Zn/Mn-O-Mo, 2D supermolecule structures are formed among the 1D chains through hydrogen bonds, and the 2D net structures are connected into a 3D supermolecule structure through the hydrogen bond action.
2. A method for preparing a metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound according to claim 1, comprising the steps of:
mixing and dissolving sodium molybdate, p-hydroxybenzoic acid, alanine, potassium chloride and arsenic trioxide in deionized water, adjusting the pH value to 3.5-4.5 by hydrochloric acid, and adding excessive metal cobalt chloride, wherein the molar ratio of the sodium molybdate, the p-hydroxybenzoic acid, the alanine, the potassium chloride, the arsenic trioxide to the cobalt chloride is 6:2:1:2-3:1: 1-3; and then stirring in a water bath at the temperature of 75-100 ℃ for 1-5h, cooling the solution, filtering, standing until crystals are generated, and washing and drying the crystals to obtain the metal ion guided carboxylic acid ligand functionalized polyacid hybrid compound.
3. The method according to claim 2, wherein the cobalt chloride is replaced by nickel chloride or zinc chloride or manganese chloride.
4. The method according to claim 2, wherein the cobalt chloride is replaced with cobalt nitrate or cobalt sulfate.
5. The application of the metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound in the catalytic degradation of 2-chloroethyl ethyl sulfide as claimed in claim 1, characterized by the following operation:
experimental conditions for degrading 2-chloroethylethyl sulfide: CEES, metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound and absolute ethyl alcohol are mixed, stirred and added with oxidant H2O2Reacting for 5min under the stirring condition to complete the catalytic oxidative degradation of CEES, wherein the molar ratio of CEES, the metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound and the oxidant is 200:3: 200-; the catalytic degradation route is as follows:
Figure FDA0002801169970000021
6. the application of the metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound in the catalytic degradation of diethyl cyanophosphate according to claim 1, characterized by the following operations:
experiment for degrading diethyl cyanophosphate: mixing DECP, N-dimethylformamide and water, fully mixing and stirring, adding a metal ion-guided carboxylic acid ligand functionalized polyacid hybrid compound into the solution, and reacting for 10min under the stirring condition to complete the catalytic hydrolysis degradation of DECP, wherein the molar ratio of DECP to catalyst is 1000: 1; the catalytic degradation route is as follows:
Figure FDA0002801169970000031
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