Patent Application
20200254430
This invention belongs to the technical field of catalytic chemistry, particularly relates to one kind of hybrid compounds composed of carboxylic acid ligands functionalized polyoxometalates and metal cations and their preparation method and applications for catalyzing the oxidation degradation of sulfur mustard simulant 2-chloroethyl ethyl sulfide and the hydrolysis degradation of nerve agent simulant diethyl cyanophosphonate.
Chemical warfare agents (CWAs) have caused mass casualties from World War I to the attacks of chemical weapons in Syria in recent years. Vesicant agents and nerve agents are two types of widely used and toxic chemical warfare agents. Vesicant agents can cause severe blisters on the skin, eyes and respiratory tract, damage to the structures of DNA and in large doses even lead to death. As the most typical vesicant agent, sulfur mustard (bis (2-chloroethyl) sulfide) is mainly degraded through hydrolysis and oxidation. The hydrolysis usually is not complete owing to the immiscibility of sulfur mustard in water. The selective oxidation degradation of sulfur mustard to sulfoxide, no toxic over oxidation product, 2-chloroethyl ethyl sulfone, is a more promising route. Nerve agents can cause a range of incapacitation by disturbing signal transmission in the nervous system, the representative agent of which is organophosphonate. Organophosphate can be decomposed by hydrolysis through destroying P-X bonds. Owing to the high danger involved in managing with real CWAs, simulant molecules, 2-chloroethyl ethyl sulfide (CEES) and diethyl cyanophosphonate (DECP), are always used to investigate the degradation reaction by experimenters. Some solid materials including metal-organic frameworks and modified activated carbons have been reported to show considerable ability of degrading CWAs in the literatures. However, most of the reported materials only can destruct one kind of CWAs as monofunctional catalyst either by oxidation or by hydrolysis. Given the possibility of using various CWAs and the difficulty to predict what kind of CWAs will be used, therefore, it is an urgent issue to design and synthesize multifunctional catalysts that could degrade both sulfur mustard by oxidation and nerve agents via hydrolysis.
Polyoxometalates (POMs) are a kind of important inorganic metal oxide clusters with abundant molecular structures, electronic structures and charming topology properties, and have extensive applications in catalysis and material science. Hill's group has reported that the Fe-containing polyoxotungstates and [PV2Mo10O40]5− can catalyze the oxidation of the sulfur mustard simulant CEES. Then, polyoxoniobates [Nb6O19]8− and K12[Ti2O2][GeNb12O40]·19H2O were used to catalytically detoxify nerve agent simulants by hydrolysis (Guo. W. W.; Lv. H. J.; Sullivan. K. P.; Gordon. W. O.; Balboa A.; Wagner. G. W.; Musaev. D. G.; Bacsa. J.; Hill. C. L. Angew. Chem. Int. Ed.2016, 55, 7403-7407). Recently, a homogeneous polyoxometalate catalyst H13[(CH3)4N]12[PNb12O40(VO)2(V4O12)2]·22H2O and a gel material composed of polyoxovanadate TBA-polyV6 have been reported to degrade sulfur mustard simulants by oxidation and nerve agent simulants via hydrolysis (Dong. J.; Hu. J. F.; Chi. Y N.; Lin. Z. G.; Zou. B.; Yang. S.; Hill. C. L.; Hu. C. W. Angew. Chem. Int. Ed. 2017, 56, 4473-4477; Sullivan. K. P.; Neiwert. W. A.; Zeng. H. D.; Mehta. A. K.; Yin. Q. S.; Hillesheim. D. A.; Vivek. S.; Yin. P. C.; Collins-Wildman. D. L. Chem. Commun. 2017, 53, 11480-11483). In this regard, the above reported polyoxometalate-based catalysts have some problems, such as low degradation efficiency, low selectivity, and poor recyclability. Therefore, the search for more efficient multifunctional catalysts based on polyoxometalates that can rapidly and high-selectively destroy two types of CWAs still is highly desired.
The present invention is aimed to obtain one kind of catalysts based on carboxylic acid ligands functionalized polyoxometalates and metal cations. These catalysts can rapidly and high-selectively detoxify sulfur mustard simulant CEES by oxidation and the nerve agent simulant DECP via hydrolysis. And these catalysts can be reused.
One kind of metal ion-directed carboxylic acid functionalized polyoxometalates, show 1D chain-like structures through carboxylic acid functionalized polyoxometalate [AsMo6O21(Ala)(PHBA)2]5− covalently joint by metal cations (Co2+, Ni2+, Zn2+, or Mn2+)The chemical formulas are K2H[(H2O)4M][AsMo6O21(Ala)(PHBA)2]·nH2O, wherein M=Co2+1, Ni2+2, Zn2+3, Mn2+4; Ala=alanine, PHBA=p-hydroxybenzonic acid, n=6.5, 9, 7.5, 7.5, the value of n corresponds to M=Co2+, Ni2+, Zn2+, Mn2+.
The described metal ion-directed carboxylic acid functionalized poloxometalates belong to the triclinic crystal system, and P-1 space group;
When M=Co2+, the cell parameters of compound 1 are a=12.0872(8) Å, b=12.5682(8) Å, c=17.2255(13) Å, α=76.700(4)°, β=74.058(4)°, γ=76.399(4)°;
When M=Ni2+, the cell parameters of compound 2 are a=11.9612(4) Å, b=12.5318(3) Å, c=17.1943(4) Å, α=76.4990(10)°, β=74.053(2)°, γ=76.535(2)°;
When M=Zn2+, the cell parameters of compound 3 are a=12.1425(2) Å, b=12.5739(2) Å, c=17.2226(3) Å, α=76.4430(10)°, β=74.0620(10)°, γ=76.2250(10)°;
When M=Mn2+, the cell parameters of compound 4 are a=12.2865(7) Å, b=12.6065(7) Å, c=17.2145(11) Å, α=76.319(3)°, β=73.933(3)°, γ=76.064(3)°;
Compounds 1-4 are isostructural, and the asymmetric unit of compounds 1-4 contains one crystallographically independent [AsMo6O21]3− anion, one Co2+, Ni2+, Zn2+ or Mn2+ cation, two K+ cations, two p-hydroxybenzoic acids and one protonated alanine molecule. Firstly, the [AsMo6O21(Ala)(PHBA)2]5− units are joined together by metal cations via Co/Ni/Zn/Mn—O—Mo bonds to produce a 1D linear chain. Then, a 2D supramolecular layer is formed by strong hydrogen bonds between 1D chains. Finally, these 2D layers are linked together to produce the 3D supramolecular framework via the hydrogen bonds.
The preparation method of the metal ion-directed carboxylic acid functionalized polyoxometalates is as follows:
Na2MoO4, PHBA, Ala, KCl and As2O3 were dissolved in water, and the pH value of the mixture was adjusted to 3.5-4.5 with 4 M HCl. Then, excessive CoCl2 was added to the reaction system. The ratio of these materials Na2MoO4, PHBA, Ala, KClAs2O3 and CoCl2 are 6:2:1:2-3:1:1-3. Finally, the solution was heated and stirred for 1-5 h in water bath at 75-100° C. The filtrate was kept undisturbed after it cooled under ambient conditions until the crystals produced. The crystals are the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds, which were then washed and dried.
The described CoCl2 can be replaced by NiCl2, ZnCl2, or MnCl2.
The described CoCl2 can be replaced by Co(NO3)2 or CoSO4.
One kind of metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds catalyze the degradation of CEES and DECP. The operations are as follows:
The experimental condition for the degradation of CEES: CEES and the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds were mixed together in anhydrous ethanol, and oxidant H2O2 was subsequently added to this reaction system under stirring. The catalytic reaction was finished after 5 minutes. The ratio of CEES, the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds and oxidant is 200:3:200-300. The catalytic degradation route is as follow:
The experimental condition for the degradation of DECP: DECP, DMF and H2O were mixed together under stirring, and then the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds were subsequently added to the catalytic system. The catalytic reaction was completed after 10 minutes. The ratio of DECP and catalyst is 1000:1. The catalytic degradation route is as follow:
The conversion and selectivity for the oxidation of CEES and the hydrolysis of DECP catalyzed by the described catalysts, were analyzed and confirmed by gas chromatography (GC) at room temperature.
(1) The catalysts of this invention as multifunctional catalysts can rapidly and high-selectively catalyze the degradation of CEES and DECP. Within 5 min, CEES was high-selectively oxidized to the corresponding nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) (conv. %=99%, sele. %>99.9%). Within 10 min, DECP can be almost entirely decomposed (conv. %=99.0%).
(2) The catalysts of this invention have the advantage of recyclability. In the catalytic degradation of CEES, these compounds as heterogeneous catalysts, were collected by simple filtration after the catalytic reaction. The conversion and selectivity of CEES remain stable after the following cycles using the collected catalysts. In the catalytic degradation of DECP, when the catalytic reaction was finished, the reusability was tested by adding the same amount of DECP under similar condition. The catalytic effect remained stable for the following cycles.
(3) The metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds of this invention were synthesized by the conventional aqueous solution reaction strategy, which is safe and simple. The raw materials of this reaction system are very cheap, and the yield can be reached to 62%.
(4) The structures of these metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds of this invention are novel, and represent the first extended architectures constructed from two different organic ligands modified polyoxometalates and metal cations.
This invention is further illustrated by the following detailed description of some embodiments, which only explain the invention, but not limit this invention.
The preparation method of the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds is as follows:
0.145 g Na2MoO4, 0.0197 g As2O3, 0.0224 g KCl, 0.0089 g Ala, and 0.0274 g PHBA, were dissolved in 20 mL water. The pH value of the mixture was adjusted to 3.5 by HCl and the solution was stirred for 1 h at room temperature. Then, 0.0714 g CoCl2 was added to the reaction system. Finally, the solution was heated and stirred for 1 h at 80° C. The filtrate was kept undisturbed after it cooled under ambient conditions until the crystals produced.
The described 0.0714 g CoCl2 can be replaced by 0.0678 g NiCl2 or 0.0861 g ZnCl2 or 0.0486 g MnCl2.
The preparation method of the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds is as follows:
0.145 g Na2MoO4, 0.0197 g As2O3, 0.0224 g KCl, 0.0089 g Ala, and 0.0274 g PHBA, were dissolved in 20 mL water. The pH value of the mixture was adjusted to 3.5 by HCl and the solution was stirred for 1 h at room temperature. Then, 0.0873 g Ni(NO3)2 was added to the reaction system. Finally, the solution was heated and stirred for 1 h at 80° C. The filtrate was kept undisturbed after it cooled under ambient conditions until the crystals produced.
The preparation method of the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds is as follows:
0.145 g Na2MoO4, 0.0197 g As2O3, 0.0224 g KCl, 0.0089 g Ala, and 0.0274 g PHBA, were dissolved in 20 mL water. The pH value of the mixture was adjusted to 3.5 by HCl and the solution was stirred for 1 h at room temperature. Then, 0.0893 g Zn(NO3)2 was added to the reaction system. Finally, the solution was heated and stirred for 1 h at 80° C. The filtrate was kept undisturbed after it cooled under ambient conditions until the crystals produced.
The preparation method of the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds is as follows:
0.145 g Na2MoO4, 0.0197 g As2O3, 0.0149 g KCl, 0.0089 g Ala, and 0.0274 g PHBA, were dissolved in 20 mL water. The pH value of the mixture was adjusted to 3.5 by HCl and the solution was stirred for 1 h at room temperature. Then, 0.0843 g CoSO4 was added to the reaction system. Finally, the solution was heated and stirred for 1 h at 80° C. The filtrate was kept undisturbed after it cooled under ambient conditions until the crystals produced.
The preparation method of the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds is as follows:
0.145 g Na2MoO4, 0.0197 g As2O3, 0.0149 g KCl, 0.0089 g Ala, and 0.0274 g PHBA, were dissolved in 20 mL water. The pH value of the mixture was adjusted to 3.5 by HCl and the solution was stirred for 1 h at room temperature. Then 0.0788 g NiSO4 was added to the reaction system. Finally, the solution was heated and stirred for 1 h at 80° C. The filtrate was kept undisturbed after it cooled under ambient conditions until the crystals produced.
The preparation method of the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds is as follows:
0.145 g Na2MoO4, 0.0197 g As2O3, 0.0149 g KCl, 0.0089 g Ala, and 0.0274 g PHBA, were dissolved in 20 mL water. The pH value of the mixture was adjusted to 3.5 by HCl and the solution was stirred for 1 h at room temperature. Then, 0.0863 g ZnSO4 was added to the reaction system. Finally, the solution was heated and stirred for 1 h at 80° C. The filtrate was kept undisturbed after it cooled under ambient conditions until the crystals produced.
The preparation method of the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds is as follows:
0.145 g Na2MoO4, 0.0197 g As2O3, 0.0149 g KCl, 0.0089 g Ala, and 0.0274 g PHBA, were dissolved in 20 mL water. The pH value of the mixture was adjusted to 3.5 by HCl and the solution was stirred for 1 h at room temperature. Then, 0.0669 g MnSO4 was added to the reaction system. Finally, the solution was heated and stirred for 1 h at 80° C. The filtrate was kept undisturbed after it cooled under ambient conditions until the crystals produced.
The preparation method of the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds is as follows:
0.145 g Na2MoO4, 0.0197 g As2O3, 0.0224 g KCl, 0.0089 g Ala, and 0.0274 g PHBA, were dissolved in 20 mL water. The pH value of the mixture was adjusted to 4.2 by HCl and the solution was stirred for 1 h at room temperature. Then, 0.0714 g CoCl2 was added to the reaction system. Finally, the solution was heated and stirred for 1 h at 80° C. The filtrate was kept undisturbed after it cooled under ambient conditions until the crystals produced.
The described 0.0714 g CoCl2 can be replaced by 0.0678 g NiCl2 or 0.0861 g ZnCl2 or 0.0486 g MnCl2.
The preparation method of the metal ion-directed carboxylic acid functionalized polyoxometalate hybrid compounds is as follows:
0.145 g Na2MoO4, 0.0197 g As2O3, 0.0224 g KCl, 0.0089 g Ala, and 0.0274 g PHBA, were dissolved in 20 mL water. The pH value of the mixture was adjusted to 3.5 by HCl and the solution was stirred for 1 h at room temperature. Then, 0.0476 g CoCl2 was added to the reaction system. Finally, the solution was heated and stirred for 1 h at 80° C. The filtrate was kept undisturbed after it cooled under ambient conditions until the crystals produced.
The described 0.0476 g CoCl2 can be replaced by 0.0452 g NiCl2 or 0.0574 g ZnCl2 or 0.0324 g MnCl2.
The products of the above embodiments were tested. The chemical formulas of these compounds are K2H[(H2O)4M][AsMo6O21(Ala)(PHBA)2]·nH2O 1-4 (M=Co2+1, Ni2+2, Zn2+3, Mn2+4; n=6.5, 9, 7.5, 7.5; Ala=alanine, PHBA=p-hydroxybenzonic acid). The crystal structues of these compounds are displayed in
The catalytic results of compounds described in example 1 were confirmed by GC.
1HNMR spectroscopy was also utilized to monitor the conversion and ascertain the product to demonstrate the accuracy of the reaction. The comparison of 1HNMR spectroscopy at different reaction time indicated nearly entire CEES was degraded by compound 1 described in example 1 within 5 min in
The stability of compounds described in example 1 before and after the catalytic reaction was proved by the IR spectra.
The stability of compounds described in example 1 was also proved by the XRD patterns of before and after the catalytic reaction.
The catalytic result for compounds described in example 1 was detected by GC.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2018/087127 | 5/16/2018 | WO | 00 |
