A layered hydroxide composite material for chemical poison decontamination and preparation method thereof

Abstract

The invention discloses a layered hydroxide composite material for chemical poison decontamination and a preparation method thereof, which specifically comprises the following steps: (1) dissolving a soluble metal salt in water and stirring to obtain a soluble metal salt solution; (2) dissolving an alkaline substance in water and stirring to obtain an alkaline solution; (3) mixing the soluble metal salt solution and the alkaline solution, adjusting the pH value, aging, centrifuging, washing, drying, grinding, sieving, calcining, cooling, and obtaining a semi-finished product; (4) dispersing the semi-finished product into an aqueous solution of a soluble salt, and continuously introducing N 2 , stirring, centrifuging, washing, and vacuum drying to obtain. The present invention is based on multiple reaction pathways and multiple cleaning mechanisms in synergy / or co-action to prepare a layered hydroxide composite material with rapid, efficient, and broad-spectrum cleaning performance for chemical poisons under environmental conditions.

Description

Technical Field

[0001] The invention relates to the technical field of chemical poison decontamination materials, and more particularly to a layered hydroxide composite material for chemical poison decontamination and a preparation method thereof. Background Art

[0002] Chemical poisons, especially neurotoxic and erosive chemical synthetic poisons, although banned by international conventions, still pose a serious long-term threat to humans and the environment. Neurotoxic poisons are highly toxic organophosphorus volatile chemicals, such as tabun, soman, sarin, vex, diethoxycyanophosphate, etc. They can irreversibly bind to acetylcholinesterase, prevent the decomposition of acetylcholine, cause continuous muscle contraction, and eventually lead to hypoxia and death. Erosive poisons represented by mustard gas can cause severe erosion of epithelial tissues, damage to the respiratory / digestive tract and visual system after contact.

[0003] Phosphotripterases in Pseudomonas microti in nature can use their Lewis acidic Zn-OH-Zn active sites to rapidly hydrolyze organophosphorus poisons, but the protein properties of the enzyme make it easily inactivated and difficult to preserve, lacking the stability required for practical applications.

[0004] Early heterogeneous chemical poison decomposition materials mainly include bleaching powder, modified clay, activated carbon, bleaching powder, liquid alcohol salt, halide, etc. Among them, modified clay, activated carbon, etc. mainly remove chemical poisons by physical adsorption, but physical adsorption cannot effectively detoxify; bleaching powder, halide and other materials can decompose chemical poisons under environmental conditions, but the decomposition kinetics are slow, and the bleaching powder is too corrosive during use. The shortcomings of these materials limit their practical application.

[0005] Nanocrystalline metal oxides, such as Al 2 O 3 、MnO 2 、CeO 2 、TiO 2 And their nanocomposites, which can achieve rapid adsorption of chemical poisons under environmental conditions, and catalytically degrade them through hydrolysis, elimination or oxidation reactions with chemical functional groups (such as hydroxyl groups, defects, acid-base sites). However, the degrading kinetics are slow, and nanomaterials are prone to aggregation. The active sites inside the granular materials cannot be fully utilized. Therefore, the decontamination task is often completed by increasing the amount of disinfectant used.

[0006] Zr-based metal-organic framework compounds (Zr-MOFs) have been widely used as high-performance decontamination materials for organophosphorus nerve poisons. However, Zr-MOFs catalysts require an alkaline reaction medium such as N-ethylmorpholine (NEM) buffer solution to achieve rapid hydrolysis. The high volatility and harmfulness of NEM to the environment and human health limit the practical application of Zr-MOFs under ambient conditions.

[0007] In addition, most of the materials reported so far only have good catalytic detoxification effects on one type or one type of chemical poison, resulting in single-function disinfection materials being unable to meet actual needs.

[0008] Therefore, how to develop a material that has rapid, efficient, and broad-spectrum decontamination performance against chemical poisons under environmental conditions is an urgent problem that technicians in this field need to solve. Summary of the invention

[0009] In view of this, the purpose of the present invention is to provide a layered hydroxide composite material for chemical poison decontamination and a preparation method thereof to solve the deficiencies in the prior art. The present invention is based on multiple reaction pathways and multiple decontamination mechanisms to synergize and / or work together to prepare a layered hydroxide composite material that has rapid, efficient, and broad-spectrum decontamination performance for chemical poisons under environmental conditions.

[0010] In order to achieve the above object, the present invention adopts the following technical solution:

[0011] A method for preparing a layered hydroxide composite material for chemical poison decontamination, specifically comprising the following steps:

[0012] (1) dissolving a soluble metal salt in water and stirring to obtain a soluble metal salt solution;

[0013] (2) dissolving an alkaline substance in water and stirring to obtain an alkaline solution;

[0014] (3) mixing the soluble metal salt solution and the alkaline solution, adjusting the pH value, aging, centrifuging, washing, drying, grinding, sieving, calcining, and cooling to obtain a semi-finished product;

[0015] (4) Disperse the semi-finished product into an aqueous solution of a soluble salt and continuously introduce N 2 , stirring, centrifuging, washing and vacuum drying to obtain a layered hydroxide composite material for chemical poison decontamination.

[0016] Furthermore, in the above step (1), the soluble metal salt includes a soluble divalent metal salt, a soluble trivalent metal salt and a soluble tetravalent metal salt.

[0017] Furthermore, the soluble divalent metal salt is at least one of nitrates, sulfates, perchlorates and hydrochlorides of zinc, magnesium, calcium, copper and iron, preferably zinc nitrate hexahydrate (Zn(NO 3 ) 2 ﹒ 6H 2 O) or magnesium nitrate hexahydrate (Mg(NO 3 ) 2 ﹒ 6H 2 O), more preferably zinc nitrate hexahydrate (Zn(NO 3 ) 2 ﹒ 6H 2 The soluble trivalent metal salt is at least one of nitrates, sulfates, perchlorates and hydrochlorides of aluminum, cerium, iron and ruthenium, preferably aluminum nitrate nonahydrate (Al(NO 3 ) 3 ﹒ 9H 2 The soluble tetravalent metal salt is at least one of the nitrates, sulfates, perchlorates and hydrochlorides of zirconium, cerium, tin and hafnium, preferably zirconium oxynitrate (ZrO(NO 3 ) 2 ﹒ x H 2 O).

[0018] Furthermore, in the above-mentioned soluble metal salt solution, the ratio of the molar concentration of divalent metal ions to the sum of the molar concentrations of trivalent metal ions and tetravalent metal ions is (2-4):1, and the molar concentration ratio of tetravalent metal ions to trivalent metal ions is (0.1-2):1.

[0019] Furthermore, in the above soluble metal salt solution, the concentration of divalent metal ions is 0.05-5 mol / L, the concentration of trivalent metal ions is 0.025-2.5 mol / L, and the concentration of tetravalent metal ions is 0.0025-5 mol / L.

[0020] Furthermore, in the above step (2), the alkaline substance is at least one of potassium hydroxide, sodium hydroxide, sodium carbonate and sodium bicarbonate, preferably sodium hydroxide (NaOH) and sodium carbonate (Na 2 CO 3 ); the concentration of the alkaline solution is 0.2-2 mol / L.

[0021] Furthermore, in the above step (3), the mass ratio of the soluble metal salt solution to the alkaline solution is (1:10)-(50:1), preferably 1:1 or 2:1, more preferably 2:1; the pH value is adjusted to 3-11, preferably 8-8.5; the aging temperature is 50-200°C, preferably 80°C, and the time is 0.5-24h, preferably 1h; washing to neutral; the drying temperature is 30-150°C, preferably 80°C, and the time is 3-18h, preferably 12h; the sieve mesh number is 500 mesh; the calcination temperature is 300-700°C, preferably 450°C, the time is 2-16h, preferably 4h, and the heating rate is 2°C / min; and cooling to room temperature.

[0022] Furthermore, in the above step (4), the soluble salt is sodium hydroxide, sodium bicarbonate, potassium cobalt (III) tungstate, sodium salt of tetrakis(4-carboxyphenyl)porphine, sodium salt of tetrakis(4-carboxyphenyl)zincporphyrin, sodium salt of tetrakis(4-carboxyphenyl)copperporphyrin, sodium salt of tetrakis(4-carboxyphenyl)ironporphyrin, sodium salt of tetrakis(4-carboxyphenyl)manganeseporphyrin, potassium hydrogen persulfate, K 7 HkDJ 6 O 19 and H x Na 5- x PMo 10 V 2 O 40 At least one of the following, wherein x=0-5, preferably sodium hydroxide (NaOH); the concentration of the aqueous solution of the soluble salt is 0.01-5.0 mol / L, preferably 1 mol / L; the mass ratio of the semi-finished product and the aqueous solution of the soluble salt is 1:(130-1000), preferably 1:200.

[0023] Furthermore, in the above step (4), the stirring temperature is 15-80°C, the time is 0.5-6h, preferably 1.5h; washing is performed until neutral; the vacuum drying temperature is 30-80°C, preferably 80°C, the time is 6-12h, preferably 8h.

[0024] The present invention also claims protection for a layered hydroxide composite material for chemical poison decontamination prepared by the above preparation method.

[0025] It can be seen from the above technical solution that compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] 1. The raw materials are cheap and the preparation method is simple, which overcomes the practical problems of complex catalyst preparation process and high cost.

[0027] 2. The tetravalent metal ions in the layered hydroxide composite material layer plates of the present invention have strong Lewis acidity and can quickly degrade neurotoxic substances.

[0028] 3. The layered hydroxide composite material of the present invention introduces functional anions (soluble salts) between the layers, and based on the synergistic and / or joint action of multiple reaction pathways and multiple catalytic decontamination mechanisms, it can have a broad-spectrum rapid decontamination performance against neurological poisons and erosive poisons.

[0029] 4. The layered hydroxide composite material of the present invention has solid alkali properties, which can ensure the rapid hydrolysis reaction of neurotoxicants, avoid the disadvantage of Zr-MOFs materials that require the addition of liquid alkali to enhance the chemical poison decontamination performance, and overcome the disadvantages of other types of decontamination materials.

[0030] 5. The layered hydroxide composite material of the present invention can be directly mixed with chemical poisons under ambient conditions, is easy to use, and can achieve rapid detoxification of chemical poisons. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Example 1

[0033] The preparation method of the layered hydroxide composite material for chemical poison decontamination specifically comprises the following steps:

[0034] (1) 1.9833 g Zn(NO 3 ) 2 ﹒ 6H 2 O, 1.1194 g Al(NO 3 ) 3 ﹒ 9H 2 O and 0.0831gZrO(NO 3 ) 2 ﹒ x H 2 O was dissolved in 200 mL of water and ultrasonically stirred for 15 min to obtain a Zn 2+ 、Al 3+ and Zr 4+ A soluble metal salt solution;

[0035] (2) Mix 8 g NaOH and 3.18 g Na 2 CO 3 Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0036] (3) NaOH / Na 2 CO 3 The mixed alkali solution was added dropwise to the 2+ 、Al 3+ and Zr 4+ The soluble metal salt solution was adjusted to pH 8-8.5, stirred and aged at 80°C for 1 hour, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80°C for 12 hours, ground, and passed through a 500-mesh sieve to obtain ZnAlZr 0.1 -LDH;

[0037] (4) 1g ZnAlZr 0.1 -LDH was placed in a quartz boat and calcined in a tube furnace at 450℃ for 4h with a heating rate of 2℃ / min. After being taken out, it was cooled to room temperature to obtain ZnAlZr 0.1 -LDH-MMO;

[0038] (5) 0.25g ZnAlZr 0.1 -LDH-MMO was dispersed in 50 mL of 0.1 mol / L NaOH solution and N 2 , stirred for 1.5 hours, centrifuged, washed with deionized water until the supernatant was neutral, and vacuum dried at 80°C for 8 hours to obtain a layered hydroxide composite material ZnAlZr for chemical poison decontamination. 0.1 -LDH-OH.

[0039] Example 2

[0040] The preparation method of the layered hydroxide composite material for chemical poison decontamination specifically comprises the following steps:

[0041] (1) 1.9833 g Zn(NO 3 ) 2 ﹒ 6H 2 O, 0.9951 g Al(NO 3 ) 3 ﹒ 9H 2 O and 0.1662gZrO(NO 3 ) 2 ﹒ x H 2 O was dissolved in 200 mL of water and ultrasonically stirred for 15 min to obtain a Zn 2+ 、Al 3+ and Zr 4+ A soluble metal salt solution;

[0042] (2) Mix 8 g NaOH and 3.18 g Na 2 CO 3Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0043] (3) NaOH / Na 2 CO 3 The mixed alkali solution was added dropwise to the 2+ 、Al 3+ and Zr 4+ The soluble metal salt solution was adjusted to pH 8-8.5, stirred and aged at 80°C for 1 hour, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80°C for 12 hours, ground, and passed through a 500-mesh sieve to obtain ZnAlZr 0.2 -LDH;

[0044] (4) 1g ZnAlZr 0.2 -LDH was placed in a quartz boat and calcined in a tube furnace at 450℃ for 4h with a heating rate of 2℃ / min. After being taken out, it was cooled to room temperature to obtain ZnAlZr 0.2 -LDH-MMO;

[0045] (5) 0.25g ZnAlZr 0.2 -LDH-MMO was dispersed in 50 mL of 0.1 mol / L NaOH solution and N 2 , stirred for 1.5 hours, centrifuged, washed with deionized water until the supernatant was neutral, and vacuum dried at 80°C for 8 hours to obtain a layered hydroxide composite material ZnAlZr for chemical poison decontamination. 0.2 -LDH-OH.

[0046] Example 3

[0047] The preparation method of the layered hydroxide composite material for chemical poison decontamination specifically comprises the following steps:

[0048] (1) 1.9833 g Zn(NO 3 ) 2 ﹒ 6H 2 O, 0.8730 g Al(NO 3 ) 3 ﹒ 9H 2 O and 0.2493gZrO(NO 3 ) 2 ﹒ x H 2 O was dissolved in 200 mL of water and ultrasonically stirred for 15 min to obtain a Zn 2+ 、Al 3+ and Zr 4+ A soluble metal salt solution;

[0049] (2) Mix 8 g NaOH and 3.18 g Na 2 CO 3 Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0050] (3) NaOH / Na 2 CO 3 The mixed alkali solution was added dropwise to the 2+ 、Al 3+ and Zr 4+ The soluble metal salt solution was adjusted to pH 8-8.5, stirred and aged at 80°C for 1 hour, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80°C for 12 hours, ground, and passed through a 500-mesh sieve to obtain ZnAlZr 0.3 -LDH;

[0051] (4) 1g ZnAlZr 0.3 -LDH was placed in a quartz boat and calcined in a tube furnace at 450℃ for 4h with a heating rate of 2℃ / min. After being taken out, it was cooled to room temperature to obtain ZnAlZr 0.3 -LDH-MMO;

[0052] (5) 0.25g ZnAlZr 0.3 -LDH-MMO was dispersed in 50 mL of 0.1 mol / L NaOH solution and N 2 , stirred for 1.5 hours, centrifuged, washed with deionized water until the supernatant was neutral, and vacuum dried at 80°C for 8 hours to obtain a layered hydroxide composite material ZnAlZr for chemical poison decontamination. 0.3 -LDH-OH.

[0053] Example 4

[0054] The preparation method of the layered hydroxide composite material for chemical poison decontamination specifically comprises the following steps:

[0055] (1) 1.9833 g Zn(NO 3 ) 2 ﹒ 6H 2 O, 0.7503 g Al(NO 3 ) 3 ﹒ 9H 2 O and 0.3323gZrO(NO 3 ) 2 ﹒ x H 2 O was dissolved in 200 mL of water and ultrasonically stirred for 15 min to obtain a Zn 2+、Al 3+ and Zr 4+ A soluble metal salt solution;

[0056] (2) Mix 8 g NaOH and 3.18 g Na 2 CO 3 Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0057] (3) NaOH / Na 2 CO 3 The mixed alkali solution was added dropwise to the 2+ 、Al 3+ and Zr 4+ The soluble metal salt solution was adjusted to pH 8-8.5, stirred and aged at 80°C for 1 hour, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80°C for 12 hours, ground, and passed through a 500-mesh sieve to obtain ZnAlZr 0.4 -LDH;

[0058] (4) 1g ZnAlZr 0.4 -LDH was placed in a quartz boat and calcined in a tube furnace at 450℃ for 4h with a heating rate of 2℃ / min. After being taken out, it was cooled to room temperature to obtain ZnAlZr 0.4 -LDH-MMO;

[0059] (5) 0.25g ZnAlZr 0.4 -LDH-MMO was dispersed in 50 mL of 0.1 mol / L NaOH solution and N 2 , stirred for 1.5 hours, centrifuged, washed with deionized water until the supernatant was neutral, and vacuum dried at 80°C for 8 hours to obtain a layered hydroxide composite material ZnAlZr for chemical poison decontamination. 0.4 -LDH-OH.

[0060] Example 5

[0061] The preparation method of the layered hydroxide composite material for chemical poison decontamination specifically comprises the following steps:

[0062] (1) 1.9833 g Zn(NO 3 ) 2 ﹒ 6H 2 O, 0.6252 g Al(NO 3 ) 3 ﹒ 9H 2 O and 0.4154gZrO(NO 3 ) 2 ﹒x H 2 O was dissolved in 200 mL of water and ultrasonically stirred for 15 min to obtain a Zn 2+ 、Al 3+ and Zr 4+ A soluble metal salt solution;

[0063] (2) Mix 8 g NaOH and 3.18 g Na 2 CO 3 Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0064] (3) NaOH / Na 2 CO 3 The mixed alkali solution was added dropwise to the 2+ 、Al 3+ and Zr 4+ The soluble metal salt solution was adjusted to pH 8-8.5, stirred and aged at 80°C for 1 hour, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80°C for 12 hours, ground, and passed through a 500-mesh sieve to obtain ZnAlZr 0.5 -LDH;

[0065] (4) 1g ZnAlZr 0.5 -LDH was placed in a quartz boat and calcined in a tube furnace at 450℃ for 4h with a heating rate of 2℃ / min. After being taken out, it was cooled to room temperature to obtain ZnAlZr 0.5 -LDH-MMO;

[0066] (5) 0.25g ZnAlZr 0.5 -LDH-MMO was dispersed in 50 mL of 0.1 mol / L NaOH solution and N 2 , stirred for 1.5 hours, centrifuged, washed with deionized water until the supernatant was neutral, and vacuum dried at 80°C for 8 hours to obtain a layered hydroxide composite material ZnAlZr for chemical poison decontamination. 0.5 -LDH-OH.

[0067] Example 6

[0068] The preparation method of the layered hydroxide composite material for chemical poison decontamination specifically comprises the following steps:

[0069] (1) 1.9833 g Zn(NO 3 ) 2 ﹒ 6H 2 O, 0.5002g Al(NO 3 ) 3 ﹒ 9H2 O and 0.4985gZrO(NO 3 ) 2 ﹒ x H 2 O was dissolved in 200 mL of water and ultrasonically stirred for 15 min to obtain a Zn 2+ 、Al 3+ and Zr 4+ A soluble metal salt solution;

[0070] (2) Mix 8 g NaOH and 3.18 g Na 2 CO 3 Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0071] (3) NaOH / Na 2 CO 3 The mixed alkali solution was added dropwise to the 2+ 、Al 3+ and Zr 4+ The soluble metal salt solution was adjusted to pH 8-8.5, stirred and aged at 80°C for 1 hour, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80°C for 12 hours, ground, and passed through a 500-mesh sieve to obtain ZnAlZr 0.6 -LDH;

[0072] (4) 1g ZnAlZr 0.6 -LDH was placed in a quartz boat and calcined in a tube furnace at 450℃ for 4h with a heating rate of 2℃ / min. After being taken out, it was cooled to room temperature to obtain ZnAlZr 0.6 -LDH-MMO;

[0073] (5) 0.25g ZnAlZr 0.6 -LDH-MMO was dispersed in 50 mL of 0.1 mol / L NaOH solution and N 2 , stirred for 1.5 hours, centrifuged, washed with deionized water until the supernatant was neutral, and vacuum dried at 80°C for 8 hours to obtain a layered hydroxide composite material ZnAlZr for chemical poison decontamination. 0.6 -LDH-OH.

[0074] Example 7

[0075] The preparation method of the layered hydroxide composite material for chemical poison decontamination specifically comprises the following steps:

[0076] (1) 7.68 g Mg(NO 3 ) 2 ﹒ 6H2 O, 2.625 g Al(NO 3 ) 3 ﹒ 9H 2 O and 0.693gZrO(NO 3 ) 2 ﹒ x H 2 O was dissolved in 100 mL of water and ultrasonically stirred for 15 min to obtain a solution containing Mg 2+ 、Al 3+ and Zr 4+ A soluble metal salt solution;

[0077] (2) Mix 8 g NaOH and 5.3 g Na 2 CO 3 Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0078] (3) The Mg 2+ 、Al 3+ and Zr 4+ Soluble metal salt solution and NaOH / Na 2 CO 3 The mixed alkali solution was simultaneously added dropwise to 20 mL of deionized water, the pH value was adjusted to 10, the mixture was stirred and aged at 80 ° C for 12 h, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80 ° C for 12 h, ground, and passed through a 500-mesh sieve to obtain MgAlZr 0.3 -LDH;

[0079] (4) 1g MgAlZr 0.3 -LDH was placed in a quartz boat and calcined in a tube furnace at 450°C for 4 h at a heating rate of 2°C / min. After being taken out, it was cooled to room temperature to obtain MgAlZr 0.3 -LDH-MMO;

[0080] (5) 0.25 g MgAlZr 0.3 -LDH-MMO was dispersed in 50 mL of 1 mol / L NaOH solution and N was continuously introduced. 2 , stirred for 1.5 hours, centrifuged, washed with deionized water until the supernatant was neutral, and vacuum dried at 80°C for 8 hours to obtain the layered hydroxide composite material MgAlZr for chemical poison decontamination. 0.3 -LDH-OH.

[0081] Example 8

[0082] The preparation method of the layered hydroxide composite material for chemical poison decontamination specifically comprises the following steps:

[0083] (1) 7.68 g Mg(NO 3 ) 2 ﹒ 6H 2 O, 2.25 g Al(NO 3 ) 3 ﹒ 9H 2 O and 0.924gZrO(NO 3 ) 2 ﹒ x H 2 O was dissolved in 200 mL of water and ultrasonically stirred for 15 min to obtain a solution containing Mg 2+ 、Al 3+ and Zr 4+ A soluble metal salt solution;

[0084] (2) Mix 8 g NaOH and 5.3 g Na 2 CO 3 Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0085] (3) The Mg 2+ 、Al 3+ and Zr 4+ Soluble metal salt solution and NaOH / Na 2 CO 3 The mixed alkali solution was simultaneously added dropwise to 20 mL of deionized water, the pH value was adjusted to 10, the mixture was stirred and aged at 80 ° C for 12 h, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80 ° C for 12 h, ground, and passed through a 500-mesh sieve to obtain MgAlZr 0.4 -LDH;

[0086] (4) 1g MgAlZr 0.4 -LDH was placed in a quartz boat and calcined in a tube furnace at 450°C for 4 h at a heating rate of 2°C / min. After being taken out, it was cooled to room temperature to obtain MgAlZr 0.4 -LDH-MMO;

[0087] (5) 0.25 g MgAlZr 0.4 -LDH-MMO was dispersed in 50 mL of 1 mol / L NaOH solution and N was continuously introduced. 2 , stirred for 1.5 hours, centrifuged, washed with deionized water until the supernatant was neutral, and vacuum dried at 80°C for 8 hours to obtain the layered hydroxide composite material MgAlZr for chemical poison decontamination. 0.4 -LDH-OH.

[0088] Example 9

[0089] The preparation method of the layered hydroxide composite material for chemical poison decontamination specifically comprises the following steps:

[0090] (1) 1.9833 g Zn(NO 3 ) 2 ﹒ 6H 2 O, 0.5002g Al(NO 3 ) 3 ﹒ 9H 2 O and 0.4985gZrO(NO 3 ) 2 ﹒ x H 2 O was dissolved in 200 mL of water and ultrasonically stirred for 15 min to obtain a Zn 2+ 、Al 3+ and Zr 4+ A soluble metal salt solution;

[0091] (2) Mix 8 g NaOH and 3.18 g Na 2 CO 3 Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0092] (3) NaOH / Na 2 CO 3 The mixed alkali solution was added dropwise to the 2+ 、Al 3+ and Zr 4+ The soluble metal salt solution was adjusted to pH 8-8.5, stirred and aged at 80 ° C for 1 h, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80 ° C for 12 h, and ground to obtain ZnAlZr 0.6 -LDH;

[0093] (4) 0.1g ZnAlZr 0.6 -LDH was dispersed in 90 mL of anhydrous methanol, stirred for 6 h, and then 664 μL of nitric acid was added, stirred for another 6 h, centrifuged, washed 5 times with anhydrous methanol, and vacuum dried at 80 °C for 12 h to obtain ZnAlZr 0.6 -LDH-NO 3 ;

[0094] (5) 0.1g ZnAlZr 0.6 -LDH-NO 3 Disperse into 20 mL of decarbonated water, add 0.4 g of potassium cobalt (III) tungstate and continue to flow N 2, react at 70℃ for 8h, centrifuge, wash with deionizer until the supernatant is neutral, and vacuum dry at 80℃ for 8h to obtain the layered hydroxide composite material ZnAlZr for chemical poison decontamination. 0.6 -LDH-CoW 12 .

[0095] Comparative Example 1

[0096] The preparation method of the layered hydroxide composite material for chemical poison decontamination (the only difference from Example 1 is that it does not contain zirconium oxynitrate) specifically comprises the following steps:

[0097] (1) 1.9833 g Zn(NO 3 ) 2 ﹒ 6H 2 O and 1.1194gAl(NO 3 ) 3 ﹒ 9H 2 O was dissolved in 100 mL of water and ultrasonically stirred for 15 min to obtain a Zn 2+ and Al 3+ A soluble metal salt solution;

[0098] (2) Mix 8 g NaOH and 3.18 g Na 2 CO 3 Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0099] (3) NaOH / Na 2 CO 3 The mixed alkali solution was added dropwise to the 2+ and Al 3+ A soluble metal salt solution was prepared, the pH value was adjusted to 8-8.5, stirred and aged at 80°C for 1 hour, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80°C for 12 hours, ground, and passed through a 500-mesh sieve to obtain ZnAl-LDH;

[0100] (4) 1 g of ZnAl-LDH was placed in a quartz boat and calcined in a tube furnace at 450 °C for 4 h at a heating rate of 2 °C / min. After being taken out, it was cooled to room temperature to obtain ZnAl-LDH-MMO;

[0101] (5) Disperse 0.25 g ZnAl-LDH-MMO into 50 mL of 1 mol / L NaOH solution and continuously introduce N 2 , stirred for 1.5 hours, centrifuged, washed with deionized water until the supernatant was neutral, and vacuum dried at 80°C for 8 hours to obtain a layered hydroxide composite material ZnAl-LDH-OH for chemical poison decontamination.

[0102] Comparative Example 2

[0103] The preparation method of the layered hydroxide composite material for chemical poison decontamination (which differs from Example 8 only in that it does not contain zirconium oxynitrate) specifically comprises the following steps:

[0104] (1) 7.68 g Mg(NO 3 ) 2 ﹒ 6H 2 O and 3.75 gAl(NO 3 ) 3 ﹒ 9H 2 O was dissolved in 100 mL of water and ultrasonically stirred for 15 min to obtain a solution containing Mg 2+ and Al 3+ A soluble metal salt solution;

[0105] (2) Mix 8 g NaOH and 5.3 g Na 2 CO 3 Dissolve in 100 mL of water and stir to obtain NaOH / Na 2 CO 3 Mixing alkaline solution;

[0106] (3) The Mg 2+ and Al 3+ Soluble metal salt solution and NaOH / Na 2 CO 3 The mixed alkali solution was simultaneously added dropwise to 20 mL of deionized water, the pH value was adjusted to 10, the mixture was stirred and aged at 80°C for 12 h, centrifuged, washed with deionized water until the supernatant was neutral, dried at 80°C for 12 h, ground, and passed through a 500-mesh sieve to obtain MgAl-LDH;

[0107] (4) 1 g of MgAl-LDH was placed in a quartz boat and calcined in a tube furnace at 450 °C for 4 h at a heating rate of 2 °C / min. After being taken out, it was cooled to room temperature to obtain MgAl-LDH-MMO;

[0108] (5) Disperse 0.25 g of MgAl-LDH-MMO into 50 mL of 1 mol / L NaOH solution and continuously introduce N 2 , stirred for 1.5 hours, centrifuged, washed with deionized water until the supernatant was neutral, and vacuum dried at 80°C for 8 hours to obtain the layered hydroxide composite material MgAl-LDH-OH for chemical poison decontamination.

[0109] Performance Testing

[0110] 1. Digestion of diethoxycyanophosphate

[0111] 1. Take 15 mg of the products (digestion materials) obtained in steps (3) and (5) of Example 6 and step (5) of Example 9 respectively and place them in a centrifuge tube, add 5 μL of diethoxy cyanophosphate, mix well and react for different time periods (15 s, 30 s and 60 s) to make diethoxy cyanophosphate fully contact with the digestion material, and extract the remaining diethoxy cyanophosphate with 1 mL of isopropanol. The content of the remaining diethoxy cyanophosphate in the system is quantitatively analyzed by gas chromatography internal standard method to obtain the digestion rate of diethoxy cyanophosphate.

[0112] The digestion rate of diethoxycyanophosphate = (5 μL - the content of remaining diethoxycyanophosphate) / 5 μL × 100%.

[0113] The results are shown in Table 1.

[0114] Table 1 Digestion rate of diethoxycyanophosphate by different digestion materials at different times

[0115]

[0116] As shown in Table 1, the digestion material of the present invention exhibits excellent catalytic performance in the digestion reaction of diethoxycyanophosphate. - The addition of ZnAlZr 0.6 -LDH digestion rate of diethoxycyanophosphate.

[0117] 2. Take 20 mg of the products (digestion materials) obtained in steps (3) and (5) of Examples 7-8 and Comparative Example 2, respectively, and place them in a centrifuge tube, add 30 μL of diethoxy cyanophosphate, mix well, and react for different time periods (15 s, 1 min, 2 min, and 3 min) to allow diethoxy cyanophosphate to fully contact the digestion materials, and extract the remaining diethoxy cyanophosphate with 1 mL of isopropanol. The content of the remaining diethoxy cyanophosphate in the system is quantitatively analyzed by gas chromatography internal standard method to obtain the digestion rate of diethoxy cyanophosphate.

[0118] The digestion rate of diethoxycyanophosphate = (30 μL - the content of remaining diethoxycyanophosphate) / 30 μL × 100%.

[0119] The results are shown in Table 2.

[0120] Table 2 Digestion rate of diethoxycyanophosphate by different digestion materials at different times

[0121]

[0122]

[0123] As shown in Table 2, the digestion material of the present invention exhibits excellent catalytic performance in the digestion reaction of diethoxycyanophosphate. 4+ The catalytic activity increased significantly with the increase of the doping amount of - The introduction of can greatly improve the material's digestion performance for diethoxycyanophosphate, all OH - The performance of the intercalated materials in catalyzing the digestion of diethoxycyanophosphate is better than that of the materials without OH - materials.

[0124] 2. Digestion of 2-chloroethyl ethyl sulfide

[0125] 100 mg of the products (digestion materials) obtained in steps (3) and (5) of Example 6 and steps (3) and (5) of Example 8 were placed in a centrifuge tube, 5 μL of 2-chloroethyl ethyl sulfide was added, and the mixture was mixed and reacted for different time periods (10 min, 1 h, and 3 h) to allow 2-chloroethyl ethyl sulfide to fully contact with the digestion materials, and the remaining 2-chloroethyl ethyl sulfide was extracted with 1 mL of dichloromethane. The content of the remaining 2-chloroethyl ethyl sulfide in the system was quantitatively analyzed by ultraviolet-visible spectrometry to obtain the digestion rate of 2-chloroethyl ethyl sulfide.

[0126] The digestion rate of 2-chloroethyl ethyl sulfide=(5 μL-the content of the remaining 2-chloroethyl ethyl sulfide) / 5 μL×100%.

[0127] The results are shown in Table 3.

[0128] Table 3 Digestion rate of 2-chloroethyl ethyl sulfide by different digestion materials at different times

[0129]

[0130] It can be seen from Table 3 that under natural environmental conditions, the above materials have good degradation effects on the mustard gas simulant 2-chloroethyl ethyl sulfide.

[0131] The above experiments show that the digestion material of the present invention has excellent performance on two types of chemical poisons, diethoxycyanophosphate and 2-chloroethyl ethyl sulfide, under the same experimental conditions, which proves the broad-spectrum property of the digestion material of the present invention.

[0132] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a layered hydroxide composite material for decontaminating diethoxycyanophosphate under ambient conditions, characterized in that: The specific steps include: (1) dissolving a soluble metal salt in water and stirring to obtain a soluble metal salt solution; The soluble metal salt is a soluble divalent metal salt, a soluble trivalent metal salt and a soluble tetravalent metal salt; The soluble divalent metal salt is at least one of nitrates, sulfates, perchlorates and hydrochlorides of zinc, magnesium and calcium; The soluble trivalent metal salt is at least one of aluminum nitrate, sulfate, perchlorate and hydrochloride; The soluble tetravalent metal salt is at least one of zirconium nitrate, sulfate, perchlorate and hydrochloride; (2) dissolving an alkaline substance in water and stirring to obtain an alkaline solution; The alkaline substance is at least one of potassium hydroxide, sodium hydroxide, sodium carbonate and sodium bicarbonate; (3) mixing the soluble metal salt solution and the alkaline solution, adjusting the pH value, aging, centrifuging, washing, drying, grinding, sieving, calcining, and cooling to obtain a semi-finished product; The calcination temperature is 300-700°C and the time is 2-16h; (4) dispersing the semi-finished product into an aqueous solution of a soluble salt, and continuously introducing N2, stirring, centrifuging, washing, and vacuum drying to obtain the layered hydroxide composite material for chemical poison decontamination; The soluble salt is sodium hydroxide, sodium bicarbonate, and potassium cobalt (III) tungstate; the concentration of the aqueous solution of the soluble salt is 0.01-5.0 mol / L; the mass ratio of the semi-finished product to the aqueous solution of the soluble salt is 1:(130-1000).

2. The preparation method according to claim 1, characterized in that: In step (1), in the soluble metal salt solution, the ratio of the molar concentration of divalent metal ions to the sum of the molar concentrations of trivalent metal ions and tetravalent metal ions is (2-4):1, and the molar concentration ratio of tetravalent metal ions to trivalent metal ions is (0.1-2):

1.

3. The preparation method according to claim 2, characterized in that: In step (1), in the soluble metal salt solution, the concentration of divalent metal ions is 0.05-5 mol / L, the concentration of trivalent metal ions is 0.025-2.5 mol / L, and the concentration of tetravalent metal ions is 0.0025-5 mol / L.

4. The preparation method according to claim 1, characterized in that: In step (2), the concentration of the alkaline solution is 0.2-2 mol / L.

5. The preparation method according to claim 1, characterized in that: In step (3), the mass ratio of the soluble metal salt solution to the alkaline solution is (1:10)-(50:1); the pH value is adjusted to 3-11; the aging temperature is 50-200°C and the time is 0.5-24h; the washing is performed until neutral; the drying temperature is 30-150°C and the time is 3-18h; the sieving mesh size is 500 mesh; and the cooling is performed to room temperature.

6. The preparation method according to claim 1, characterized in that: In step (4), the stirring temperature is 15-80°C and the time is 0.5-6h; the washing is performed until neutral; and the vacuum drying temperature is 30-80°C and the time is 6-12h.

7. A layered hydroxide composite material for decontaminating diethoxycyanophosphate under ambient conditions, prepared by the preparation method according to any one of claims 1 to 6.

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