CN114314686A - One-pot preparation method of LDH micro-nano colloidal coating liquid - Google Patents
One-pot preparation method of LDH micro-nano colloidal coating liquid Download PDFInfo
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Abstract
The invention relates to a one-pot preparation method of LDH micro-nano colloid coating liquid, belonging to the technical field of nano material preparation. Preparation M2+‑M3+The method comprises the following steps of taking a salt solution as a solution A, taking an ammonia-ammonium chloride buffer solution as a solution B, taking concentrated ammonia water as a solution C, placing the solution B in a sealed penicillin bottle, placing the solution B in a constant-temperature metal bath vibration pot, injecting the solution A and the solution B into a special penicillin bottle for reaction at a certain temperature and a certain rotating speed by using an injection pump, standing, aging, centrifugally washing, drying, dispersing into a salt and acid mixed solution, and blowing and vibrating by nitrogen to obtain the free-carbon oxygen-free LDH micro-nano colloidal plating solution. The preparation method of the invention actively isolates carbon and oxygen, and the prepared LDH colloidal plating solution has high purity, regular appearance structure and extreme high purityWide application prospect.
Description
The technical field is as follows:
the invention relates to a one-pot preparation method of LDH micro-nano colloidal coating liquid in a carbon-free and oxygen-free atmosphere, belonging to the technical field of nano material preparation.
Background art:
the micro-nano colloid plating layer has high strength and excellent corrosion resistance, and is widely applied to the fields of catalyst materials, ceramic materials, medical materials, protective materials and the like. The colloid surface layer of the low-dimensional, small-size and functionalized micro-nano structure can obviously change the tissue structure of the material and endow the material with new performance. In the application of reaction catalysis, Layered Double Hydroxide (LDH) is used as a good inorganic functional material, and has abundant physicochemical properties due to the special structure and function. Nowadays, LDH plating solution relates to a plurality of fields such as medicine, catalysis, flame retardance and the like. Particularly, the surface effect and the volume effect of the micro-nano colloidal material of the catalyst coating determine the good catalytic activity and the selectivity of the catalytic reaction of the catalyst. But the good performance cannot be obtained due to the influence of preparation conditions, particularly the oxidation of carbon dioxide and oxygen, most of LDH preparation needs to passively remove the influence of carbon dioxide and oxygen, and the treatment process is quite complicated or neglected.
For example, chinese patent document CN101759213B discloses a method for preparing layered double hydroxides from metal powder, which utilizes divalent metal powder or its hydroxide, trivalent metal powder or its hydroxide, soluble salt and deionized water to prepare a water-heating solution according to a certain proportion. Then the solution is placed in a hydrothermal kettle, hydrothermal reaction is carried out in a standing state, and the layered double hydroxide is obtained after separation, washing and drying of the product. For another example, chinese patent document CN106334524B discloses a preparation method and application of a core-shell structure layered double hydroxide composite particle, the method comprising the following steps: (1) carrying out hydrothermal reaction on the glucose solution, washing, drying and grinding the obtained solid to obtain carbon microspheres; (2) mixing magnesium chloride and aluminum chloride, adding deionized water for dissolving, dropwise adding dilute ammonia water into the mixed solution, standing for crystallization, performing suction filtration and washing on a crystallized product, and performing peptization on a filter cake to convert the filter cake into sol; (3) dispersing carbon microspheres in methanol to obtain a solution A; dispersing the product obtained in the step (2) in methanol to obtain a colloidal solution B; and mixing the solution A and the solution B, centrifugally separating the obtained product, drying and grinding to obtain the core-shell structured layered double-metal hydroxide composite particles, which are applied to removing the 2, 4-dichlorophenoxyacetic acid in water. For example, chinese patent document CN107583471B discloses a layered double hydroxide composite nanofiltration membrane and a preparation method thereof, in which a polydopamine functional layer is first generated by modifying a base membrane, and then a double hydroxide functional skin layer is constructed in situ on the polydopamine modified membrane surface to obtain the composite nanofiltration membrane.
However, none of the above methods performs the preparation of the layered double hydroxide in a closed environment, and finally CO in air is not considered2The influence of (c). Obtained of
The purity of intercalated LDH is poor, interlayer anions are impure, and the prepared material is irregular in shape and structure. Therefore, the LDH with better purity, higher crystallinity and more regular appearance structure is provided, and the preparation process is simple and efficient, thereby having important significance. The invention is therefore proposed.
The invention content is as follows:
aiming at the defects of the prior art, the invention provides a preparation method of one-pot carbon-separation oxygen-free LDH micro-nano colloidal plating solution which is simple in preparation process, low in cost, environment-friendly and high in purity. The preparation process is simple and efficient, carbon and oxygen are actively isolated, and the prepared LDH colloidal plating solution has high purity, regular morphology and structure, low cost and environmental friendliness and has very wide application prospect.
The technical scheme of the invention is as follows:
a one-pot preparation method of LDH micro-nano colloid coating liquid comprises the following steps:
(1) preparing M under the protection of oxygen-free carbon dioxide-free nitrogen2+-M3+The salt solution is solution A, ammonia-ammonium chloride buffer solutionTaking solution B and strong ammonia water as solution C;
(2) under the protection of oxygen-free carbon dioxide and nitrogen, simultaneously adding the solution A and the solution C into the solution B, standing and aging after reaction; centrifuging, washing and drying the product to obtain a carbonate-free LDH solid; dispersing the LDH solid into a mixed solution of acid and salt, and oscillating to obtain the carbon-free and oxygen-free LDH micro-nano colloidal plating solution.
According to the present invention, preferably, in step (1), the pH of solution a is 1 to 2, M2+：M3+The molar ratio is (2-5): 1, preferably 3: 1; preferably, divalent M is2+Salts and trivalent M3+Dissolving salt in acidified, boiled and decarbonized deionized water to prepare solution A;
preferably, divalent M2+Is Mg2+、Co2+、Ni2+、Mn2+Or Cu2+Trivalent M3+Is Al3+Or Fe3+；
Preferably, divalent M2+Salts and trivalent M3+The anion of the salt is
Cl-Or
Can not be
According to the invention, preferably, the pH value of the solution B in the step (1) is 11-13, and a further preferred preparation process is as follows:
dissolving the ammonium chloride solid in boiled deionized water to obtain a saturated ammonium chloride solution, adding the saturated ammonium chloride solution into 25-28% concentrated ammonia water, and adjusting the pH value to 11-13 to obtain an ammonia-ammonium chloride buffer solution.
According to the invention, preferably, the step (2) is carried out under constant temperature and stirring conditions during the process of simultaneously adding the solution A and the solution C into the solution B, wherein the constant temperature is preferably 25-80 ℃, most preferably 70 ℃, and the stirring speed is 500-850r/min, most preferably 800 r/min.
According to the present invention, it is preferable that the volume ratio of the solution a, the solution B and the solution C in the step (2) is 1: (1-3): (1-2), most preferably 1:1: 1.4;
preferably, the reaction time is 0.5 to 2 hours.
According to the present invention, it is preferred that the temperature of aging in step (2) is 60 to 80 ℃, most preferably 70 ℃; preferably, the aging time is 20-30 h.
According to the invention, preferably, the product obtained in the step (2) is washed 3-4 times by using absolute ethyl alcohol after centrifugation, and dried for 8-12h at 80-100 ℃.
According to the present invention, it is preferred that the anion of the acid and salt in step (2) is
Cl-Or
The cation of the salt is Na+；
Preferably, the LDH solid is dispersed in the mixed solution of the acid and the salt and then is purged by nitrogen for a plurality of times;
preferably, the shaking time is 10-15 h.
The chemical formula of the Layered Double Hydroxide (LDH) prepared by the invention is as follows:
wherein M is2+Represents a divalent metal cation, M3+Represents a trivalent metal cation, An-Are interlayer anions, n ═ 1, 2 or 3, such as organic and inorganic ions and complex ions, and the interlayer anions are different, and the interlayer spacing of the LDHs is different. At x values between 0.17 and 0.33, structurally complete LDHs are obtained.
According to the invention, a preferable embodiment of the one-pot preparation method of the LDH micro-nano colloid plating solution comprises the following steps:
solution A, preparing M with pH of 1-22+-M3+Salt solution of divalent M2+Salts and trivalent M3+Dissolving salt in acidified and boiled decarbonated deionized water, and maintaining M2+：M3+The molar ratio is (2-5): 1;
preparing ammonia-ammonium chloride buffer solution, dissolving 33g of ammonium chloride solid in 100ml of boiled deionized water to obtain saturated ammonium chloride solution with the pH value of 4.46, adding the saturated ammonium chloride solution into 25-28% concentrated ammonia water, and adjusting the pH value to 11-13 to obtain ammonia-ammonium chloride buffer solution;
and C, liquid C: 25 to 28 percent of strong ammonia water;
(1) pumping a sealed penicillin bottle to a negative pressure of 0.07MPa by using a vacuum pump, then purging by using nitrogen, repeating the steps for three times and pumping the vacuum again to the negative pressure of 0.07MPa to ensure that no carbon dioxide exists in the absence of oxygen, placing the solution B in the sealed penicillin bottle under the protection of the nitrogen, placing the sealed penicillin bottle in a constant-temperature metal bath shaking pot, slowly injecting the solution A and the solution C into the sealed penicillin bottle by using an injection pump at the rotating speed of 800r/min at 70 ℃, and preparing a mixed solution, wherein the volume ratio of the solution A to the solution B to the solution C is 1:1: 1.4;
(2) after the injection of the solution A and the solution C is finished, keeping the rotating speed to react for 1h, then adjusting the rotating speed to 0r/min, and aging for 24h at a constant temperature of 70 ℃ in a standing state;
(3) centrifuging the product, washing with anhydrous ethanol for 3-4 times, and drying at 80-100 deg.C for 8-12h to obtain carbonate-free LDH solid;
(4) dispersing the prepared LDH into 1mol/L sodium salt and 3.3mmol/L acid solution, purging with nitrogen for several times, and oscillating at room temperature for 12h to obtain the carbon-free and oxygen-free LDH micro-nano colloidal plating solution.
The invention has the following beneficial effects:
1. the present inventors have found that the reason why the product obtained by the conventional method is impure is that the conventional method ignores the influence of oxygen and carbon dioxide in the air. Therefore, the whole preparation process removes O in the air under the protection of nitrogen2Oxidation, CO2Dissolved in water to produce water-soluble organic compounds
Influence the experiment. Compared with the traditional method, the method has the advantages of simple process, purer LDH interlayer anions prepared by isolating air, higher LDH crystallinity and more regular appearance.
2. The whole synthesis process of the carbon-free and oxygen-free LDH micro-nano colloidal plating solution is carried out in a closed environment (such as a penicillin bottle), and the one-pot synthesis is more efficient, cheap and environment-friendly.
3. The method can also control the shape and size of the LDH material by controlling the conditions of metal ion concentration, reaction temperature, reaction time and the like. The whole process has no corrosion to equipment, does not pollute the environment and is suitable for industrial production.
Description of the drawings:
FIG. 1 is a schematic flow diagram of the preferred preparation process of the present invention.
FIG. 2 shows examples 1 to 1 wherein the interlayer anion is NO3 -The appearance photo of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid plating solution.
FIG. 3 shows that the interlayer anion obtained in example 1 is NO when irradiated with a light beam3 -The Tndall phenomenon picture of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid coating liquid.
FIG. 4 shows that the interlayer anion obtained in example 1 is NO3 -SEM photograph of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid plating solution.
FIG. 5 shows examples 2 to 2 wherein the interlayer anion is Cl-The appearance photo of the carbon-free and oxygen-free Fe/Fe-LDH micro-nano colloid coating solution.
FIG. 6 shows that the interlayer anion obtained in example 2 was Cl when irradiated with a light beam-The Tndall phenomenon picture of the carbon-free and oxygen-free Fe/Fe-LDH micro-nano colloid coating liquid.
FIG. 7 shows that the interlayer anion obtained in example 2 is Cl-SEM photograph of the carbon-free and oxygen-free Fe/Fe-LDH micro-nano colloid coating solution.
FIG. 8 shows interlayer anions of examples 3 to 3
The appearance photo of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid plating solution.
FIG. 9 shows interlayer anions obtained in example 3 by irradiating with a light beam
The Tndall phenomenon picture of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid coating liquid.
FIG. 10 shows interlayer anions obtained in example 3
SEM photograph of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid plating solution.
FIG. 11 is a drawing showing examples 4 to
Interlayer anion is NO3-The appearance of the Mn/Al-LDH nano-suspension is shown.
FIG. 12 shows the result of irradiating example 4 with a light beam
Interlayer anion is NO3-The Tndall phenomenon of the Mn/Al-LDH nano-suspension.
FIG. 13 shows the compound obtained in example 4
Interlayer anion is NO3-SEM photograph of the Mn/Al-LDH nano-suspension.
FIG. 14 shows interlayer anions of comparative examples 1 to
The appearance photo of the Mn/Al-LDH micro-nano colloid plating solution.
FIG. 15 shows interlayer anions obtained by irradiating comparative example 1 with a light beam of
The Tndall phenomenon picture of the Mn/Al-LDH micro-nano colloid coating liquid.
FIG. 16 shows that the interlayer anion obtained in comparative example 1 is
Mn/Al of (2)SEM photograph of LDH micro-nano colloid plating solution.
Fig. 17 is an XRD diffraction pattern of each sample tested in the experimental example.
The specific implementation mode is as follows:
the present invention will be further described by way of examples, but not limited thereto, with reference to the accompanying drawings.
Example 1:
accurately weighing Co (NO) in stoichiometric ratio3)2·6H2O and Al (NO)3)3·9H2O, acidifying boiling cooled deionized water to pH 2 with nitric acid to obtain Co2+：Al3+The solution of Co-Al salt with a total metal ion concentration of 0.1mol/l was used as solution A at 3: 1. Dissolving 33g of ammonium chloride solid in 100ml of boiled deionized water, adding a saturated ammonium chloride solution into 25-28% concentrated ammonia water, and adjusting the pH value to 12 to obtain an ammonia-ammonium chloride buffer solution as a solution B. A certain amount of 25 to 28 percent of strong ammonia water is used as the solution C.
Sealing a clean 20ml penicillin bottle, blowing nitrogen gas into the bottle for several times, adding the solution B, and placing the bottle in a constant-temperature metal bath shaking pot at the set temperature of 70 ℃ and the rotating speed of 800 r/min. The injection pump is provided with the liquid A and the liquid C, is connected with a penicillin bottle and is slowly injected into the liquid B, and the volume ratio of the liquid A to the liquid B to the liquid C is 1:1: 1.4. after the injection is finished, the rotating speed is kept for reaction for 1h, then the rotating speed is adjusted to be 0r/min, the penicillin bottle is put into a centrifugal machine (6000r/min) for centrifugation after being aged for 24h under the constant temperature in a standing state under the constant temperature, and is washed for 3-4 times by absolute ethyl alcohol and dried for 12h at 80 ℃. Adding 20ml of 1mol sodium nitrate and 3.3mmol nitric acid solution into the solid in a penicillin bottle, purging with nitrogen for several times, and shaking at room temperature for 12h to obtain interlayer anion of
The carbon-free and oxygen-free Co/Al-LDH micro-nano colloid coating solution.
The interlayer anion obtained in this example was NO3 -The appearance photograph of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid plating solution is shown in figure 2.
Irradiating the specimen with a light beamThe interlayer anion obtained in the examples is NO3 -The phenomenon photo of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid plating solution is shown in figure 3. As can be seen from FIG. 3, the Co/Al-LDH plating solution has obvious Tyndall effect, which proves its colloidal characteristics.
The interlayer anion obtained in this example was NO3 -The SEM photograph of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid plating solution is shown in figure 4. From FIG. 4, it is understood that the particles are well dispersed, and mostly exhibit a layered structure of hydrotalcite-like compounds, and the particle size and shape exhibit a certain dispersibility.
Example 2:
accurately weighing FeCl according to stoichiometric ratio2·2H2O and FeCl3·6H2O, acidifying boiling cooled deionized water with nitric acid to pH 1 to obtain Fe2+：Fe3+As solution a, an Fe — Fe salt solution having a total metal ion concentration of 0.01mol/l was used as solution a. Dissolving 33g of ammonium chloride solid in 100ml of boiled deionized water, adding a saturated ammonium chloride solution into 25-28% concentrated ammonia water, and adjusting the pH value to 13 to obtain an ammonia-ammonium chloride buffer solution as a solution B. A certain amount of 25 to 28 percent of strong ammonia water is used as the solution C.
Sealing a clean 20ml penicillin bottle, blowing nitrogen gas into the bottle for several times, adding the solution B, and placing the bottle in a constant-temperature metal bath shaking pot at the set temperature of 70 ℃ and the rotating speed of 800 r/min. The injection pump is provided with the liquid A and the liquid C, is connected with a penicillin bottle and is slowly injected into the liquid B, and the volume ratio of the liquid A to the liquid B to the liquid C is 1:1: 1.4. after the injection is finished, the rotating speed is kept for reaction for 1h, then the rotating speed is adjusted to be 0r/min, the penicillin bottle is put into a centrifugal machine (6000r/min) for centrifugation after being aged for 24h under the constant temperature in a standing state under the constant temperature, and is washed for 3-4 times by absolute ethyl alcohol and dried for 12h at 80 ℃. Adding 20ml of 1mol sodium chloride and 3.3mmol hydrochloric acid solution into the solid in a penicillin bottle, purging with nitrogen for several times, and shaking at room temperature for 12h to obtain Cl as interlayer anion-The carbon-free and oxygen-free Fe/Fe-LDH micro-nano colloid coating solution.
The interlayer anion obtained in this example was Cl-The appearance photograph of the carbon-free and oxygen-free Fe/Fe-LDH micro-nano colloid coating solution is shown in FIG. 5。
The interlayer anion obtained in this example by irradiating with a light beam was Cl-The phenomenon photo of the carbon-free and oxygen-free Fe/Fe-LDH micro-nano colloid coating solution is shown in figure 6. As can be seen from FIG. 6, the Fe/Fe-LDH plating solution has obvious Tyndall effect, which proves its colloidal property.
The interlayer anion obtained in this example was Cl-The SEM photograph of the carbon-free and oxygen-free Fe/Fe-LDH micro-nano colloid plating solution is shown in figure 7. From FIG. 7, it is understood that the particles are well dispersed, and mostly exhibit a layered structure of hydrotalcite-like compounds, and the particle size and shape exhibit a certain dispersibility.
Example 3:
accurately weighing CoSO according to stoichiometric ratio4·7H2O and Al2(SO4)3·18H2O, acidifying boiling cooled deionized water to pH 2 with sulfuric acid to obtain Co2+：Al3+The solution of Co-Al salt with a total metal ion concentration of 0.05mol/l was used as solution A at 3: 1. Dissolving 33g of ammonium chloride solid in 100ml of boiled deionized water, adding a saturated ammonium chloride solution into 25-28% concentrated ammonia water, and adjusting the pH value to 12 to obtain an ammonia-ammonium chloride buffer solution as a solution B. A certain amount of 25 to 28 percent of strong ammonia water is used as the solution C.
Sealing a clean 20ml penicillin bottle, blowing nitrogen gas into the bottle for several times, adding the solution B, and placing the bottle in a constant-temperature metal bath shaking pot at the set temperature of 70 ℃ and the rotating speed of 800 r/min. The injection pump is provided with the liquid A and the liquid C, is connected with a penicillin bottle and is slowly injected into the liquid B, and the volume ratio of the liquid A to the liquid B to the liquid C is 1:1: 1.4. after the injection is finished, the rotating speed is kept for reaction for 1h, then the rotating speed is adjusted to be 0r/min, the penicillin bottle is put into a centrifugal machine (6000r/min) for centrifugation after being aged for 24h under the constant temperature in a standing state under the constant temperature, and is washed for 3-4 times by absolute ethyl alcohol and dried for 12h at 80 ℃. Adding 20ml of 1mol sodium sulfate and 3.3mmol sulfuric acid solution into the solid in a penicillin bottle, purging with nitrogen for several times, and shaking at room temperature for 12h to obtain interlayer anion of
Carbon-free and oxygen-free Co/Al-LDH micro-nano colloidAnd (4) coating liquid.
The interlayer anion obtained in this example was
The appearance photograph of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid plating solution is shown in figure 8.
The interlayer anion obtained in this example by irradiating with a light beam is
The phenomenon photo of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid plating solution is shown in figure 9. As can be seen from FIG. 9, the Co/Al-LDH plating solution has obvious Tyndall effect, which proves its colloidal characteristics.
The interlayer anion obtained in this example was
The SEM photograph of the carbon-free and oxygen-free Co/Al-LDH micro-nano colloid plating solution is shown in figure 10. From FIG. 10, it is understood that the particles are well dispersed, and mostly exhibit a layered structure of hydrotalcite-like compounds, and the particle size and shape exhibit a certain dispersibility.
Example 4:
accurately weighing Mn (NO) in stoichiometric ratio3)2·4H2O and Al (NO)3)3·9H2O, acidifying boiling cooled deionized water with nitric acid to pH 2 to obtain Mn2+：Al3+As solution a, a Mn — Al salt solution having a total metal ion concentration of 0.01mol/l was used as solution a. Dissolving 33g of ammonium chloride solid in 100ml of boiled deionized water, adding a saturated ammonium chloride solution into 25-28% concentrated ammonia water, and adjusting the pH value to 13 to obtain an ammonia-ammonium chloride buffer solution as a solution B. A certain amount of 25 to 28 percent of strong ammonia water is used as the solution C.
Sealing a clean 20ml penicillin bottle, blowing nitrogen gas into the bottle for several times, adding the solution B, and placing the bottle in a constant-temperature metal bath shaking pot at the set temperature of 70 ℃ and the rotating speed of 800 r/min. The injection pump is provided with the liquid A and the liquid C, is connected with a penicillin bottle and is slowly injected into the liquid B, and the volume ratio of the liquid A to the liquid B to the liquid C is 1:1: 1.4. after the injection is finished, the rotation is keptReacting for 1h quickly, adjusting the rotation speed to 0r/min, aging for 24h at constant temperature under a standing state without changing the temperature, placing a penicillin bottle into a centrifuge (6000r/min), centrifuging, washing for 3-4 times by using absolute ethyl alcohol, and drying at 80 ℃ for 12 h. Adding 20ml of 1mol of sodium nitrate and 3.3mmol of nitric acid solution into the solid in a penicillin bottle, purging with nitrogen for several times, and shaking at room temperature for 12h to obtain a solution
Interlayer anion is NO3-The Mn/Al-LDH nano-suspension.
Obtained in this example
Interlayer anion is NO3-The appearance photograph of the Mn/Al-LDH nano-suspension of (1) is shown in FIG. 11.
The light beam was irradiated to the phosphor obtained in this example
Interlayer anion is NO3-The phenomenon picture of the Mn/Al-LDH nano-suspension is shown in FIG. 12. From fig. 12, it can be seen that the plating solution has a significant tyndall effect, demonstrating its colloidal properties.
Obtained in this example
Interlayer anion is NO3-The SEM photograph of the Mn/Al-LDH nano-suspension of (1) is shown in FIG. 13. From FIG. 13, it is understood that the particles are well dispersed, and mostly exhibit a layered structure of hydrotalcite-like compounds, and the particle size and shape exhibit a certain dispersibility. And the resulting layered structure is larger.
Comparative example 1
As described in example 1, except that:
the whole process is carried out in air without nitrogen protection. To give a interlayer anion of
The Co/Al-LDH micro-nano colloid plating solution.
The interlayer anion obtained in this comparative example was NO- 3The photo of the appearance of the Co/Al-LDH micro-nano colloid plating solution is shown in FIG. 14.
The interlayer anion obtained in this comparative example was NO when irradiated with a light beam3 -The phenomenon photo of the Co/Al-LDH micro-nano colloid plating solution is shown in figure 15. From FIG. 15, it can be seen that the method can also obtain a significant Tyndall effect, with colloidal characteristics.
The interlayer anion obtained in this comparative example was NO3 -The SEM photograph of the Co/Al-LDH micro-nano colloid plating solution is shown in figure 16. From FIG. 16, it is known that the prepared LDH has an unobvious layered structure, a rod-like structure and a small particle size.
It can be seen that the product obtained without the protection of nitrogen has no good lamellar structure and has more impurities.
Test examples
The products of example 1 and comparative example 1 were tested for purity and the XRD diffraction pattern is shown in figure 17.
As can be seen from the XRD diffractogram result of fig. 17, the characteristic diffraction peaks of hydrotalcite (003), (006), (012), (015), (018), (110), and (118) appear in the sample, and the sample of the example has better crystallinity, strong diffraction intensity, and sharp peak pattern. While comparative example 1, which has a weak diffraction intensity of the peak type and a slow peak type, shows that the crystallinity of the comparative example is poor. Further shows that the product obtained by the invention has good crystallinity and higher purity.
Claims (10)
1. A one-pot preparation method of LDH micro-nano colloid coating liquid comprises the following steps:
(1) preparing M under the protection of oxygen-free carbon dioxide-free nitrogen2+-M3+The salt solution is solution A, the ammonia-ammonium chloride buffer solution is solution B, and the strong ammonia water is solution C;
(2) under the protection of oxygen-free carbon dioxide and nitrogen, simultaneously adding the solution A and the solution C into the solution B, standing and aging after reaction; centrifuging, washing and drying the product to obtain a carbonate-free LDH solid; dispersing the LDH solid into a mixed solution of acid and salt, and oscillating to obtain the carbon-free and oxygen-free LDH micro-nano colloidal plating solution.
2. The one-pot preparation method of the LDH micro-nano colloid coating solution according to claim 1, wherein in the step (1), the pH of the solution A is 1-2, and M is2+∶M3+The molar ratio is (2-5) to 1;
preferably, divalent M is2+Salts and trivalent M3+Dissolving salt in acidified deionized water, boiling and decarbonizing to obtain solution A.
3. The one-pot preparation method of the LDH micro-nano colloid coating solution as claimed in claim 1, wherein in the step (1), divalent M is used2+Is Mg2+、Co2+、Ni2+、Mn2+Or Cu2+Trivalent M3+Is Al3+Or Fe3+；
Preferably, divalent M2+Salts and trivalent M3+The anion of the salt is
Cl-Or
Can not be
4. The one-pot preparation method of the LDH micro-nano colloid plating solution as claimed in claim 1, wherein the pH value of the solution B in the step (1) is 11-13.
5. The one-pot preparation method of the LDH micro-nano colloid plating solution according to claim 1, wherein the preparation process of the solution B in the step (1) is as follows:
dissolving the ammonium chloride solid in boiled deionized water to obtain a saturated ammonium chloride solution, adding the saturated ammonium chloride solution into 25-28% concentrated ammonia water, and adjusting the pH value to 11-13 to obtain an ammonia-ammonium chloride buffer solution.
6. The one-pot preparation method of the LDH micro-nano colloid plating solution as claimed in claim 1, wherein the step (2) is performed under the conditions of constant temperature and stirring in the process of simultaneously adding the solution A and the solution C into the solution B, the constant temperature is 25-80 ℃, and the stirring speed is 500-850 r/min.
7. The one-pot preparation method of the LDH micro-nano colloid coating solution in claim 1, wherein the volume ratio of the solution A to the solution B to the solution C in the step (2) is 1: 1-3: 1-2;
preferably, the reaction time is 0.5 to 2 hours.
8. The one-pot preparation method of the LDH micro-nano colloid plating solution as claimed in claim 1, wherein the aging temperature in the step (2) is 60-80 ℃; preferably, the aging time is 20-30 h.
9. The one-pot preparation method of the LDH micro-nano colloid plating solution as claimed in claim 1, wherein the product obtained in step (2) is centrifuged, washed with absolute ethanol for 3-4 times, and dried at 80-100 ℃ for 8-12 h.
10. The one-pot preparation method of the LDH micro-nano colloid coating solution as claimed in claim 1, wherein the anion of the acid and salt in the step (2) is
Cl-Or
The cation of the salt is Na+；
Preferably, the LDH solid is dispersed in the mixed solution of the acid and the salt and then is purged by nitrogen for a plurality of times;
preferably, the shaking time is 10-15 h.
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| WO2023134244A1 (en) * | 2022-01-14 | 2023-07-20 | 青岛理工大学 | One-pot preparation method for ldh micro-nano colloidal coating liquid |
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| CN114314686A (en) * | 2022-01-14 | 2022-04-12 | 青岛理工大学 | One-pot preparation method of LDH micro-nano colloidal coating liquid |
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