阅读说明：本技术 一种化学战剂消解材料及其修饰的纤维材料的制备方法 (Chemical warfare agent digestion material and preparation method of fiber material modified by chemical warfare agent digestion material ) 是由 周云山 翟玉鹏 张立娟 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种化学战剂消解材料的制备方法：(1)将锆盐和六水氯化铁溶于水中,搅拌；(2)逐滴加入浓氨水至pH为4-12；(3)冲洗,晾干,研磨,即得。本发明还公开了一种纤维材料的制备方法：(1)将三羟甲基氨基甲烷溶于水中,调pH至4-12；(2)加入盐酸多巴胺和纳米纤维布,搅拌,捞出,冲洗,晾干；(3)将锆盐和六水氯化铁溶于水中,搅拌；(4)先将纳米纤维布浸泡在混合溶液中,逐滴加入浓氨水至pH为4-12,继续浸泡；(5)捞出,冲洗,晾干,即得。本发明利用价格便宜的Zr盐和Fe盐为原料,通过简单的共沉淀法合成含有Zr-OH-Fe结构的锆铁氢氧化物,在室温条件下直接与化学战剂混合即可高效消解。(The invention discloses a preparation method of a chemical warfare agent digestion material, which comprises the following steps: (1) dissolving zirconium salt and ferric chloride hexahydrate in water, and stirring; (2) dropwise adding concentrated ammonia water until the pH value is 4-12; (3) washing, air drying, and grinding. The invention also discloses a preparation method of the fiber material, which comprises the following steps: (1) dissolving tris (hydroxymethyl) aminomethane in water, and adjusting the pH value to 4-12; (2) adding dopamine hydrochloride and nanofiber cloth, stirring, taking out, washing and drying; (3) dissolving zirconium salt and ferric chloride hexahydrate in water, and stirring; (4) firstly, soaking the nanofiber cloth in a mixed solution, dropwise adding concentrated ammonia water until the pH value is 4-12, and continuing soaking; (5) taking out, washing and drying to obtain the product. The invention uses cheap Zr salt and Fe salt as raw materials, synthesizes Zr-OH-Fe structure-containing ferrozirconium hydroxide by a simple coprecipitation method, and can be efficiently digested by directly mixing with chemical warfare agents at room temperature.)

1. A preparation method of a chemical warfare agent digestion material is characterized by comprising the following steps:

(1) dissolving zirconium salt and ferric chloride hexahydrate in water, and stirring to obtain the Zr-containing solution⁴⁺And Fe³⁺The mixed solution of (1);

(2) adding strong ammonia water dropwise into the solution containing Zr⁴⁺And Fe³⁺To pH 4-12 to obtain ZrFe (OH)_xPrecipitating;

(3) ZrFe (OH)_xAnd washing, airing and grinding the precipitate to obtain the chemical warfare agent digestion material.

2. A method of producing a chemical warfare agent digestion material according to claim 1 wherein in step (1) the zirconium salt is zirconium oxychloride octahydrate or zirconium chloride;

the molar ratio of the zirconium salt to the ferric chloride hexahydrate is (1:10) - (10: 1);

the mass ratio of the water to the zirconium salt is (100-3000): 1.

3. A method of producing a chemical warfare agent digestion material according to claim 1, wherein in step (1), the stirring speed is 50-1000r/min and the time is 20-120 min.

4. The method for preparing a chemical warfare agent digestion material according to the claim 1, wherein in the step (2), the mass concentration of the strong ammonia water is 15-30%.

5. The method for preparing the digestion material for chemical warfare agents according to claim 1, wherein in the step (3), the digestion material is ground to ZrFe (OH)_xThe particle size of the precipitate is less than 30 μm.

6. A method of preparing a fibrous material modified with a chemical warfare agent counteracting material according to claim 1, comprising the steps of:

(1) dissolving tris (hydroxymethyl) aminomethane in water, and adjusting the pH to 4-12 with a dilute hydrochloric acid solution to obtain a pretreatment solution;

(2) adding dopamine hydrochloride and nanofiber cloth into the pretreatment solution, stirring, taking out the nanofiber cloth, washing, and drying to obtain pretreated nanofiber cloth for later use;

(3) dissolving zirconium salt and ferric chloride hexahydrate in water, and stirring to obtain the Zr-containing solution⁴⁺And Fe³⁺The mixed solution of (1);

(4) soaking the pretreated nano-fiber cloth in Zr⁴⁺And Fe³⁺Then adding strong ammonia water dropwise into the mixed solution containing Zr⁴⁺And Fe³⁺The mixed solution is soaked continuously until the pH value is 4-12, and the soaked nano-fiber cloth is obtained;

(5) and fishing out the soaked nanofiber cloth, washing and drying to obtain the fiber material modified by the chemical warfare agent digestion material.

7. The method for preparing the fiber material modified by the chemical warfare agent digestion material as claimed in claim 6, wherein in the step (1), the mass ratio of the tris (hydroxymethyl) aminomethane to the water is 1: (50-400);

the molar concentration of the dilute hydrochloric acid solution is 0.1-2.0 mol/L.

8. The method for preparing the fiber material modified by the chemical warfare agent digestion material as claimed in the claim 6, wherein in the step (2), the mass ratio of the dopamine hydrochloride to the water is 1 (15-100);

the nano-fiber cloth is synthetic fiber, natural fiber, plant fiber or animal fiber;

the stirring speed is 50-1000r/min, the temperature is 10-40 ℃, and the time is 20-120 min.

9. The method for preparing a fibrous material modified by a chemical warfare agent digestion material as claimed in claim 6, wherein in step (3), the zirconium salt is zirconium oxychloride octahydrate or zirconium chloride;

the molar ratio of the zirconium salt to the ferric chloride hexahydrate is (1:10) - (10: 1);

the mass ratio of the water to the zirconium salt is (100) -3000) 1;

the stirring speed is 50-1000r/min, and the time is 20-120 min.

10. The method for preparing the fiber material modified by the chemical warfare agent digestion material as claimed in claim 6, wherein in the step (4), the mass concentration of the strong ammonia water is 15% -30%;

the soaking time and the continuous soaking time are both 6-72 h.

Technical Field

The invention relates to the technical field of chemical warfare agent digestion protection materials, in particular to a chemical warfare agent digestion material and a preparation method of a fiber material modified by the chemical warfare agent digestion material.

Background

Chemical Warfare Agents (CWAs) are essential elements of chemical weapons and generally have the following characteristics: strong toxicity, quick action, durable toxic effect, multiple killing ways, wide killing range, difficult discovery, protection and treatment difficulty, easy production, stable property and convenient storage, is a basic raw material for manufacturing chemical weapons called poor atomic bombs and belongs to large-scale killing weapons. The low-cost nervous chemical warfare agent (a typical chemical warfare agent) is the biggest threat, and poses great threat to the life safety and national safety of human beings.

At present, the digestion materials of chemical warfare agents mainly comprise bleaching powder, liquid alkoxides, halides, zeolites, MOFs, biological enzymes, H₂O₂Active systems, and the like. Wherein, bleaching powder, halide, zeolite and other materials can realize the purpose of dissolving the neurochemical warfare agent under the solid condition, but the process takes longer time, and meanwhile, bleaching powder substances are corrosive to a reaction container, thereby further limiting the use of the materials; liquid alkoxides and H₂O₂The active system has good digestion capacity on the neurochemical warfare agent, but the specific use of the active system needs a solution-based system, and the actual use is greatly limited; the MOF digestion neurochemical warfare agent material mainly takes Zr-MOF as a main material, the MOF has porosity and large specific surface area, and exposed active sites can achieve good digestion effects on the neurochemical warfare agent, but the preparation process of the MOF generally needs longer time, and the low yield is also an important reason for limiting the MOF material; a small amount of biological enzyme can be utilized to show good digestion effect for digesting the nervous chemical warfare agent at normal temperature, but the material is not easy to store, easy to inactivate and extremely expensive, so that the biological enzyme material can not be utilized on a large scale.

Therefore, how to develop a chemical warfare agent digestion material is a problem which needs to be solved urgently by the technical personnel in the field.

Disclosure of Invention

In view of the above, the present invention aims to provide a chemical warfare agent digestion material and a preparation method of a fiber material modified by the chemical warfare agent digestion material, so as to solve the defects in the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a chemical warfare agent digestion material and a fiber material modified by the chemical warfare agent digestion material specifically comprises the following steps:

(1) dissolving zirconium salt and ferric chloride hexahydrate in water, and stirring to obtain the Zr-containing solution⁴⁺And Fe³⁺The mixed solution of (1);

(2) adding strong ammonia water dropwise into the solution containing Zr⁴⁺And Fe³⁺To pH 4-12 to obtain ZrFe (OH)_xPrecipitating;

(3) ZrFe (OH)_xAnd washing, airing and grinding the precipitate to obtain the chemical warfare agent digestion material.

The invention has the beneficial effects that: cheap Zr salt and Fe salt are used as raw materials, zirconium iron hydroxide containing Zr-OH-Fe structure is synthesized by a simple coprecipitation method, and the zirconium iron hydroxide can be efficiently digested by directly mixing with chemical warfare agents at room temperature.

Further, in the step (1), the zirconium salt is zirconium oxychloride octahydrate or zirconium chloride; the molar ratio of the zirconium salt to the ferric chloride hexahydrate is (1:10) - (10: 1); the mass ratio of water to zirconium salt is (100) -3000) 1; the stirring speed is 50-1000r/min, and the time is 20-120 min.

The technical scheme has the beneficial effects that the raw materials of the invention adopt the zirconium oxychloride octahydrate or the zirconium chloride and the ferric chloride, chloride ions do not enter product lattices in the hydrolysis reaction process, and pure ZrFe (OH) can be obtained_xAnd (5) producing the product. Acid radicals with strong coordination capacity, such as phosphate, hydrogen phosphate, dihydrogen phosphate, sulfate or oxalate, of other zirconium and iron salts can enter product crystal lattices in the hydrolysis process of metal ions to obtain the product containing the acid radicalsThe co-existing product with hydroxyl leads to a reduction in the number of "metal-OH-metal" active sites similar to the Zn-OH-Zn active sites in phosphotriesterase, thereby reducing its catalytic digestion capacity.

Further, in the step (2), the mass concentration of the strong ammonia water is 15-30%.

The beneficial effect of adopting the further technical proposal is that the raw material can fully generate hydrolysis reaction to obtain ZrFe (OH) in the pH range of 4-12_xAnd (5) producing the product.

Further, in the step (3), the polishing is performed until ZrFe (OH)_xThe particle size of the precipitate is less than 30 μm.

The beneficial effect of adopting the further technical proposal is that ZrFe (OH)_xThe smaller the particle size of the precipitate, the larger the specific surface area of the particles, the more chance of contact with the toxicant and the higher the catalytic digestion efficiency.

A preparation method of the fiber material modified by the chemical warfare agent digestion material comprises the following steps:

(1) dissolving tris (hydroxymethyl) aminomethane in water, and adjusting the pH to 4-12 with a dilute hydrochloric acid solution to obtain a pretreatment solution;

(2) adding dopamine hydrochloride and nanofiber cloth into the pretreatment solution, stirring, taking out the nanofiber cloth, washing, and drying to obtain pretreated nanofiber cloth for later use;

(3) dissolving zirconium salt and ferric chloride hexahydrate in water, and stirring to obtain the Zr-containing solution⁴⁺And Fe³⁺The mixed solution of (1);

(4) soaking the pretreated nano-fiber cloth in Zr⁴⁺And Fe³⁺Then adding strong ammonia water dropwise into the mixed solution containing Zr⁴⁺And Fe³⁺The mixed solution is soaked continuously until the pH value is 4-12, and the soaked nano-fiber cloth is obtained;

(5) and fishing out the soaked nanofiber cloth, washing and airing to obtain the fiber material modified by the chemical warfare agent digestion material.

Further, in the step (1), the mass ratio of the tris to the water is 1: (50-400); the molar concentration of the dilute hydrochloric acid solution is 0.1-2.0 mol/L.

The further technical scheme has the beneficial effects that the trihydroxymethyl aminomethane and the hydrochloric acid are dissolved in water, and stable buffer solutions with different pH values are obtained according to different proportions of the trihydroxymethyl aminomethane and the hydrochloric acid.

Further, in the step (2), the mass ratio of the dopamine hydrochloride to the water is 1 (15-100); the nano-fiber cloth is synthetic fiber, natural fiber, plant fiber or animal fiber; stirring at 50-1000r/min and 10-40 deg.C for 20-120 min.

The technical scheme has the beneficial effects that the dopamine hydrochloride can be O-doped in the air₂The poly-dopamine is uniformly coated on the surface of the nano-fiber through various acting forces including hydrogen bonds, and hydroxyl on the poly-dopamine has excellent chelation and can form coordinate bonds with metal ions Zr/Fe at the site, so that ZrFe (OH) can be firmly grown on the surface of the nano-fiber_x。

Further, in the step (3), the zirconium salt is zirconium oxychloride octahydrate or zirconium chloride; the molar ratio of the zirconium salt to the ferric chloride hexahydrate is (1:10) - (10: 1); the mass ratio of water to zirconium salt is (100) -3000) 1; the stirring speed is 50-1000r/min, and the time is 20-120 min.

The technical scheme has the beneficial effects that the raw materials of the invention adopt the zirconium oxychloride octahydrate or the zirconium chloride and the ferric chloride, chloride ions do not enter product lattices in the hydrolysis reaction process, and pure ZrFe (OH) can be obtained_xAnd (5) producing the product. And acid radicals with strong coordination capacity, such as phosphate, hydrogen phosphate, dihydrogen phosphate, sulfate or oxalate, of other zirconium and iron salts enter product lattices in the hydrolysis process of metal ions to obtain products containing the acid radicals and hydroxide radicals, so that the number of metal-OH-metal active sites similar to the Zn-OH-Zn active sites in phosphotriesterase is reduced, and the catalytic digestion capacity of the phosphotriesterase is reduced.

Further, in the step (4), the mass concentration of the strong ammonia water is 15-30%; the soaking time and the continuous soaking time are both 6-72 h.

The beneficial effect of adopting the further technical proposal is that the raw material can fully generate hydrolysis reaction to obtain ZrFe (OH) in the pH range of 4-12_xProducing a product; the soaking time selected by the method can ensure that the loading capacity of the catalyst on the surface of the nanofiber is maximized.

According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:

1. metal hydroxide ZrFe (OH) in the present invention_xThe active site containing the high-efficiency digestion neurochemical warfare agent can quickly make the neurochemical warfare agent lose toxicity, and has the advantages of easy synthesis, convenient use, mild reaction conditions, low price and the like; the metal hydroxide is connected to clothing materials through polydopamine, and the prepared functional fiber cloth can efficiently and quickly digest the nervous chemical warfare agent and can be used for manufacturing functional fields such as protective clothing.

2. ZrFe (OH) prepared by the invention_xThe active site of 'metal-OH-metal' similar to the active site of Zn-OH-Zn in phosphotriesterase has stronger nucleophilicity due to the bridge hydroxyl oxygen, and can attack electropositive P in the neurochemical warfare agent to digest the neurochemical warfare agent, and has very quick digestion capability on typical neurochemical warfare agents such as VX (Vickers) nerve agent, GD (soman) nerve agent and GB (sarin) nerve agent; ZrFe (OH) prepared by the invention_xThe protective material combined on the nanofiber cloth can fully exert ZrFe (OH)_xThereby playing a role in protecting life.

Drawings

FIGS. 1 to 9 are views showing Zr (OH) obtained in comparative example 1 in the order named₄Chemical warfare agent digestion Material ZrFe (OH) prepared in examples 1-7_xAnd Fe (OH) obtained in comparative example 2₃The extractive solution after 1min, 3min, 5min and 10min for eliminating VX nerve agent³¹A P-NMR spectrum;

FIG. 10 shows Zr (OH) obtained in comparative example 1₄Chemical warfare agent digestion Material ZrFe (OH) prepared in examples 1-7_xAnd Fe (OH) obtained in comparative example 2₃A histogram of the rate of resolution of VX nerve agent as a function of time;

FIGS. 11 to 14 are sequential views of Zr (OH) obtained in comparative example 1₄Chemical warfare agent digestion Material ZrFe (OH) prepared in examples 1-7_xAnd Fe (OH) obtained in comparative example 2₃UV-vis-graph plots of digestion rates of GB nerve agents at 1min, 3min, 5min and 10min respectively;

FIG. 15 shows Zr (OH) obtained in comparative example 1₄Chemical warfare agent digestion Material ZrFe (OH) prepared in examples 1-7_xAnd Fe (OH) obtained in comparative example 2₃Histogram of the rate of digestion of GB nerve agents as a function of time;

FIGS. 16-19 are views of the chemical warfare agent digestion material ZrFe (OH) prepared in the sequence of examples 2, 4 and 6_xZr (OH) obtained in comparative example 1₄And Fe (OH) obtained in comparative example 2₃A UV-vis-graph of 1min, 3min, 5min and 10min respectively for the digestion rate of the GD nerve agent;

FIG. 20 shows the digestion material ZrFe (OH) for chemical warfare agent prepared in examples 2, 4 and 6_xZr (OH) obtained in comparative example 1₄And Fe (OH) obtained in comparative example 2₃A histogram of the rate of digestion of GD nerve agents as a function of time;

FIG. 21 shows in sequence PA-6 fiber cloth, [email protected] PDA fiber cloth, and [email protected] PDA @ ZrFe (OH) prepared in example 8_xReal shooting of the fiber cloth;

FIGS. 22-24 show in sequence PA-6 fiber cloth, [email protected] PDA fiber cloth, and [email protected] PDA @ ZrFe prepared in example 8_xA trend graph of the degradation rate of the fiber cloth to GB nerve agents along with time;

FIG. 25 shows PA-6 fiber cloth, [email protected] PDA fiber cloth, and [email protected] PDA @ ZrFe (OH) prepared in example 8_xAnd (3) a degradation rate trend chart of the GB nerve agent digested by the fiber cloth.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The preparation method of the chemical warfare agent digestion material specifically comprises the following steps:

(1) zirconium oxychloride octahydrate (ZrOCl)₂·8H₂O, 4.3943g, 13.6mmol) and ferric chloride hexahydrate (FeCl)₃·6H₂O, 0.3686g, 1.36mmol) was dissolved in 150mL of water and stirred at 100r/min for 20min to obtain a solution containing Zr⁴⁺And Fe³⁺The mixed solution of (1);

(2) dropwise adding strong ammonia water with the mass concentration of 25% into the solution containing Zr⁴⁺And Fe³⁺To pH 9.0 to obtain ZrFe (OH)_xPrecipitating;

(3) ZrFe (OH)_xWashing the precipitate with deionized water for 5 times, centrifuging, air drying at room temperature, grinding into powder with particle size less than 30 μm to obtain digestion material for chemical warfare agent, as Zr, Fe is 10:1ZrFe (OH)_x。

Example 2

The preparation method of the chemical warfare agent digestion material specifically comprises the following steps:

(1) zirconium oxychloride octahydrate (ZrOCl)₂·8H₂O, 3.4527g, 10.72mmol) and ferric chloride hexahydrate (FeCl)₃·6H₂O, 1.1584g, 4.29mmol) was dissolved in 150mL of water and stirred at 100r/min for 20min to obtain a solution containing Zr⁴⁺And Fe³⁺The mixed solution of (1);

(2) dropwise adding strong ammonia water with the mass concentration of 25% into the solution containing Zr⁴⁺And Fe³⁺To pH 9.0 to obtain ZrFe (OH)_xPrecipitating;

(3) ZrFe (OH)_xWashing the precipitate with deionized water for 5 times, centrifuging, air drying at room temperature, grinding into powder with particle size less than 30 μm to obtain digestion material Zr (Fe: 10:4ZrFe (OH))_x。

Example 3

The preparation method of the chemical warfare agent digestion material specifically comprises the following steps:

(1) zirconium oxychloride octahydrate (ZrOCl)₂·8H₂O, 2.84g, 8.82mmol) and ferric chloride hexahydrate (FeCl)₃·6H₂O, 1.667g, 6.17mmol) was dissolved in 150mL of water and stirred at 100r/min for 20min to obtain Zr-containing solution⁴⁺And Fe³⁺The mixed solution of (1);

(2) adding 28 mass percent of strong ammonia water dropwise into Zr-containing solution⁴⁺And Fe³⁺To pH 9.0 to obtain ZrFe (OH)_xPrecipitating;

(3) ZrFe (OH)_xWashing the precipitate with deionized water for 5 times, centrifuging, air drying at room temperature, grinding into powder with particle size less than 30 μm to obtain digestion material for chemical warfare agent, wherein the formula is Zr, Fe is 10:7ZrFe (OH)_x。

Example 4

The preparation method of the chemical warfare agent digestion material specifically comprises the following steps:

(1) zirconium oxychloride octahydrate (ZrOCl)₂·8H₂O, 2.4168g, 7.5mmol) and ferric chloride hexahydrate (FeCl)₃·6H₂O, 2.0273g, 7.5mmol) was dissolved in 150mL of water and stirred at 100r/min for 20min to obtain a solution containing Zr⁴⁺And Fe³⁺The mixed solution of (1);

(2) dropwise adding strong ammonia water with the mass concentration of 25% into the solution containing Zr⁴⁺And Fe³⁺To pH 9.0 to obtain ZrFe (OH)_xPrecipitating;

(3) ZrFe (OH)_xWashing the precipitate with deionized water for 5 times, centrifuging, air drying at room temperature, grinding into powder with particle size less than 30 μm to obtain digestion material for chemical warfare agent, wherein the formula is Zr, Fe is 10:10ZrFe (OH)_x。

Example 5

The preparation method of the chemical warfare agent digestion material specifically comprises the following steps:

(1) zirconium oxychloride octahydrate (ZrOCl)₂·8H₂O, 1.988g, 6.17mmol) and ferric chloride hexahydrate (FeCl)₃·6H₂O, 2.3839g, 8.82mmol) was dissolved in 150mL of water and stirred at 100r/min for 20min to obtain a solution containing Zr⁴⁺And Fe³⁺The mixed solution of (1);

(2) dropwise adding strong ammonia water with the mass concentration of 25% into the solution containing Zr⁴⁺And Fe³⁺To pH 9.0 to obtain ZrFe (OH)_xPrecipitating;

(3) ZrFe (OH)_xWashing the precipitate with deionized water for 5 times, centrifuging, air drying at room temperature, grinding into powder with particle size less than 30 μm to obtain digestion material for chemical warfare agent, wherein the formula is Zr, Fe is 7:10ZrFe (OH)_x。

Example 6

The preparation method of the chemical warfare agent digestion material specifically comprises the following steps:

(1) zirconium oxychloride octahydrate (ZrOCl)₂·8H₂O, 1.3812g, 4.29mmol) and ferric chloride hexahydrate (FeCl)₃·6H₂O, 2.896g, 10.72mmol) was dissolved in 150mL of water and stirred at 100r/min for 20min to obtain a solution containing Zr⁴⁺And Fe³⁺The mixed solution of (1);

(2) dropwise adding strong ammonia water with the mass concentration of 25% into the solution containing Zr⁴⁺And Fe³⁺To pH 9.0 to obtain ZrFe (OH)_xPrecipitating;

(3) ZrFe (OH)_xWashing the precipitate with deionized water for 5 times, centrifuging, air drying at room temperature, grinding into powder with particle size less than 30 μm to obtain digestion material for chemical warfare agent, wherein the formula is Zr, Fe is 4:10ZrFe (OH)_x。

Example 7

The preparation method of the chemical warfare agent digestion material specifically comprises the following steps:

(1) zirconium oxychloride octahydrate (ZrOCl)₂·8H₂O, 0.4394g, 1.36mmol) and ferric chloride hexahydrate (FeCl)₃·6H₂O, 3.686g, 13.6mmol) was dissolved in 150mL of water and stirred at 100r/min for 20min to obtain a solution containing Zr⁴⁺And Fe³⁺The mixed solution of (1);

(2) dropwise adding strong ammonia water with the mass concentration of 25% into the solution containing Zr⁴⁺And Fe³⁺To pH 9.0 to obtain ZrFe (OH)_xPrecipitating;

(3) ZrFe (b)OH)_xWashing the precipitate with deionized water for 5 times, centrifuging, air drying at room temperature, grinding into powder with particle size less than 30 μm to obtain digestion material for chemical warfare agent, wherein the formula is Zr, Fe is 1:10ZrFe (OH)_x。

Example 8

The preparation method of the fiber material modified by the chemical warfare agent digestion material specifically comprises the following steps:

(1) dissolving 0.366g of Tris (hydroxymethyl) aminomethane (Tris) in 300mL of water, and adjusting the pH to 8.5 by using a dilute hydrochloric acid solution with the molar concentration of 1.0mol/L to obtain a pretreatment solution;

(2) firstly, adding 1.8g of dopamine hydrochloride (abbreviated as PDA) and 1.1568g of polyamide-6 (abbreviated as PA-6) nanofiber cloth into a pretreatment solution, stirring for 24 hours at the speed of 100r/min at the temperature of 25 ℃, then fishing out the PA-6 nanofiber cloth, washing for 3 times by using deionized water, and naturally airing to obtain the pretreated PA-6 nanofiber cloth for later use;

(3) zirconium oxychloride octahydrate (ZrOCl)₂·8H₂O, 9.666g, 30.00mmol) and ferric chloride hexahydrate (FeCl)₃·6H₂O, 8.106g, 30.00mmol) in 200mL of deionized water, and stirring at 100r/min for 20min to obtain Zr-containing solution⁴⁺And Fe³⁺The mixed solution of (1);

(4) soaking the pretreated PA-6 nano-fiber cloth in Zr⁴⁺And Fe³⁺Then adding 25% strong ammonia water into the mixed solution dropwise, wherein the strong ammonia water is added into the mixed solution for 24 hours⁴⁺And Fe³⁺The mixed solution is soaked for 72 hours till the pH value is 9.0, and the soaked PA-6 nano-fiber cloth is obtained;

(5) and fishing out the soaked PA-6 nano-fiber cloth, washing with deionized water for 5 times, and naturally drying to obtain the fiber material modified by the chemical warfare agent digestion material.

Comparative example 1

The only difference from example 1 is that no ferric chloride hexahydrate is present and the final product is Zr (OH)₄。

Comparative example 2

Differs from example 1 only in that zirconium oxychloride octahydrate is absent and the final product is Fe (OH)₃。

Performance testing

1. The chemical warfare agent digestion materials ZrFe (OH) prepared in examples 1-7_xAnd Zr (OH) obtained in comparative example 1₄And Fe (OH) obtained in comparative example 2₃The method is used as a digestion material for digesting the neurochemical warfare agent VX, and comprises the following specific steps:

each 50mg of the chemical warfare agent digestion material ZrFe (OH) prepared in examples 1 to 7 was taken_xAnd Zr (OH) obtained in comparative example 1₄And Fe (OH) obtained in comparative example 2₃Adding 5 μ l VX nerve agent into a centrifuge tube, mixing, reacting for 1min, 3min, 5min and 10min respectively to make the nerve VX nerve agent fully contact with the digestion material, and extracting residual VX nerve agent and its hydrolysate with deuterated methanol acetonitrile solution.

(1) The integral area of P is tested by liquid nuclear magnetism, and the resolution ratio of P in the VX nerve agent standard liquid is known by comparing the area of P. The results are shown in FIGS. 1 to 9.

(2) And plotting the resolution rate of the VX nerve agent at different times and the type of the material to obtain a bar chart of the resolution rate of the VX nerve agent digested by different materials. The results are shown in FIG. 10.

As can be seen from FIGS. 1-9 and 10, the chemical warfare agent digestion material 10:10ZrFe (OH) produced in example 4_xCan completely digest VX nerve agent within 3min, and has the fastest digestion rate.

2. The chemical warfare agent digestion materials ZrFe (OH) prepared in examples 1-7_xAnd Zr (OH) obtained in comparative example 1₄And Fe (OH) obtained in comparative example 2₃The method is used as a digestion material for digesting GB nerve agents, and comprises the following specific steps:

each 20mg of the chemical warfare agent digestion material ZrFe (OH) prepared in examples 1 to 7 was taken_xAnd Zr (OH) obtained in comparative example 1₄And Fe (OH) obtained in comparative example 2₃Adding 2 μ l GB nerve agent into a centrifuge tube, mixing, reacting for 1min, 3min, 5min and 10min respectively to make GB nerve agent fully contact with digestion material, and extracting residual GB nerve agent with isopropanol solution.

(1) And testing the absorbance of the GB nerve agent by using an ultraviolet spectrophotometer, and calculating the concentration of the residual GB nerve agent according to a standard curve equation so as to obtain the degradation rate of the GB nerve agent. The results are shown in FIGS. 11-14.

(2) And drawing by using different time digestion rates and material types of the GB nerve agents to obtain a digestion rate histogram of different materials for digesting the GB nerve agents. The results are shown in FIG. 15.

As can be seen from FIGS. 11-14 and 15, the chemical warfare agent digestion material 10:10ZrFe (OH) made in example 4_xCan completely eliminate GB nerve agents within 10min, and has the fastest elimination rate.

3. The chemical warfare agent digestion material ZrFe (OH) prepared in the examples 2, 4 and 6_xAnd Zr (OH) obtained in comparative example 1₄And Fe (OH) obtained in comparative example 2₃The digestion material is used for digesting GD nerve agents and comprises the following specific steps:

each 20mg of the chemical warfare agent digestion material ZrFe (OH) prepared in example 2, 4, 6, 8, 9_xAnd Zr (OH) obtained in comparative example 1₄And Fe (OH) obtained in comparative example 2₃Adding 2 μ l GD nerve agents into a centrifuge tube, uniformly mixing, reacting for 1min, 3min, 5min and 10min respectively to make the GD nerve agents fully contact with the digestion material, and extracting residual GD nerve agents by using an isopropanol solution.

(1) And testing the absorbance of the GD nerve agent by using an ultraviolet spectrophotometer, and calculating the concentration of the residual GD nerve agent according to a standard curve equation so as to obtain the degradation rate of the GD nerve agent. The results are shown in FIGS. 15-19.

(2) And drawing by using the digestion rates of the GD nerve agents in different time and the types of the materials to obtain a digestion rate histogram of the GD nerve agents digested by the different materials. The results are shown in FIG. 20.

As can be seen from FIGS. 15-19 and 20, the chemical warfare agent digestion material 10:10ZrFe (OH) made in example 4_x92.75% of GD nerve agents can be digested within 10min, and the digestion rate is fastest.

4. Fibrous Material modified with the chemical warfare agent digestion Material prepared in example 8 ([email protected] PDA @ ZrFe (OH))_xFiber cloth) and PA-6 fiber cloth and [email protected] PDA fiber cloth as digestion materials for digesting GB nerve agent (as shown in fig. 21), the specific steps are as follows:

60mg each of [email protected] PDA @ ZrFe (OH) from example 8 were taken_xPutting the fiber cloth, the PA-6 fiber cloth and the [email protected] PDA fiber cloth into a centrifugal tube, uniformly adding 10 mu L of GB isopropanol solution, reacting for 5min, 10min, 15min, 20min, 25min and 30min respectively, fully contacting the GB nerve agent with the digestion material, and extracting residual GB nerve agent by using the isopropanol solution.

(1) The absorbance was measured with an ultraviolet spectrophotometer. The results are shown in FIGS. 22-24.

(2) And (3) calculating the concentration of the residual GB nerve agent according to a standard curve equation so as to obtain the degradation rate of the GB nerve agent, and drawing a graph by using the digestion rates and times of the GB nerve agent at different times so as to obtain a graph of the degradation rates of different materials for digesting the GB nerve agent. The results are shown in FIG. 25.

As can be seen from FIGS. 22-24 and 25, [email protected] PDA @ ZrFe (OH) was compared with PA-6 fiber cloth and [email protected] PDA fiber cloth_xThe fiber cloth has the best digestion capability of the GB nerve agents, and can completely digest the GB nerve agents within 10 min.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.