CN115650278A - Nano copper hydroxide and preparation method thereof - Google Patents
Nano copper hydroxide and preparation method thereof Download PDFInfo
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- CN115650278A CN115650278A CN202211316742.6A CN202211316742A CN115650278A CN 115650278 A CN115650278 A CN 115650278A CN 202211316742 A CN202211316742 A CN 202211316742A CN 115650278 A CN115650278 A CN 115650278A
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- 239000005750 Copper hydroxide Substances 0.000 title claims abstract description 95
- 229910001956 copper hydroxide Inorganic materials 0.000 title claims abstract description 95
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 82
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 82
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 29
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 11
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 56
- 239000002245 particle Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001514 detection method Methods 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000004563 wettable powder Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- -1 mordants Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000005739 Bordeaux mixture Substances 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002794 Si K Inorganic materials 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 150000002191 fatty alcohols Chemical class 0.000 description 1
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- 230000005923 long-lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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Abstract
The application relates to the technical field of nano basic sodium hydroxide, in particular to nano copper hydroxide and a preparation method thereof, wherein the preparation method of the nano copper hydroxide comprises the following preparation steps: s1, preparing a polyvinylpyrrolidone aqueous solution with the concentration of more than or equal to 1 mol/L; s2, at the temperature of 25-35 ℃, simultaneously dripping the polyvinylpyrrolidone aqueous solution and ammonia water into the suspension of basic copper carbonate and water, stirring while dripping, wherein the reaction end point is pH =7.5-9.5; wherein, in the suspension of basic copper carbonate and water, the weight ratio of the basic copper carbonate to the water is 1: (3-10); s3, filtering the turbid liquid obtained in the S2 to obtain a solid; s4, drying the solid obtained in the S3 to obtain nano copper hydroxide; the method has the advantage of simplifying the preparation method of the nano copper hydroxide.
Description
Technical Field
The application relates to the technical field of nano basic sodium hydroxide, in particular to nano copper hydroxide and a preparation method thereof.
Background
Copper hydroxide is generally used as an analytical reagent, and is also used for medicines, pollution-free pesticides, catalysts, mordants, pigments, feed additives, paper stains, and the like. In addition, copper hydroxide is a main raw material for preparing a novel pollution-free green low-toxicity bactericide. The copper hydroxide can enter virus cells to kill viruses but cannot enter plant cells, is safe to crops, does not generate drug resistance, can be used in crop picking periods such as tea leaf picking periods and fruit picking periods, and is harmless to human and livestock. Therefore, copper hydroxide is an environmentally friendly protective bactericide advocated by various countries.
With the development of nanotechnology, nanometer basic sodium hydroxide is gradually developed and enters the market for application. The development of the nano technology provides a wider market prospect for the application of the copper hydroxide. Nano basic sodium hydroxideThe surface atoms are equivalent to the bulk atoms, the surface atom activity is greatly improved, the activity of the free active copper ions is multiplied, the released copper ions act with fungi and genes in cells, namely act with-SH-containing enzyme on the cell membrane of the thallus to inactivate the enzyme, and the enzyme reacts with cations on the cell surface, such as H + 、Ca 2+ 、Mg 2+ 、K + The isoexchange, which makes the protein of the cell membrane of the thallus coagulate, seeps into the thallus to combine with certain enzymes, influences the activity thereof and causes the death of the germs; the nanometer alkali type sodium hydroxide wettable powder has the advantages of uniform spraying, strong adhesion, rain erosion resistance, long lasting period of 20-25 days, and no need of re-spraying after rain. And the spraying amount of the traditional Bordeaux mixture is large, and the medicinal liquid is dripped into the ground to cause the land to be alkalized. The nanometer alkali type sodium hydroxide wettable powder has improved sterilizing effect, greatly reduces the dosage compared with the traditional copper hydroxide wettable powder, reduces the residue, is uniformly sprayed, does not drop the liquid medicine into the ground, and prevents the soil from being alkalized; the nanometer alkali sodium hydroxide can be directly diluted and sprayed, and the spraying labor capacity is reduced.
The application based on nano sodium hydroxide is gradually widened, and the demand amount of the nano sodium hydroxide is also gradually increased. However, the related preparation method still has great difficulty and high cost, and is not beneficial to mass production.
Disclosure of Invention
In order to simplify the preparation method of the nano copper hydroxide, the application provides the nano copper hydroxide and the preparation method thereof.
In a first aspect, the present application provides a method for preparing nano copper hydroxide, which adopts the following technical scheme:
a preparation method of nano copper hydroxide comprises the following preparation steps:
s1, preparing a polyvinylpyrrolidone aqueous solution with the concentration of more than or equal to 1 mol/L;
s2, dripping the polyvinylpyrrolidone aqueous solution and ammonia water into the suspension of basic copper carbonate and water at the temperature of 25-35 ℃, stirring while dripping, wherein the reaction end point is pH =7.5-9.5; wherein, in the suspension of basic copper carbonate and water, the weight ratio of basic copper carbonate to water is 1: (3-10);
s3, filtering the turbid liquid obtained in the S2 to obtain a solid;
and S4, drying the solid obtained in the S3 to obtain the nano copper hydroxide.
By adopting the technical scheme, the polyvinylpyrrolidone is added, so that the polyvinylpyrrolidone can be adsorbed on the particle surface of the nano copper hydroxide when the nano copper hydroxide is formed, steric hindrance is formed, the particles are limited from being continuously increased, the average particle size of the prepared nano copper hydroxide is smaller, and the specific surface area of the prepared nano copper hydroxide is larger; in addition, the preparation raw materials are simple, no additional raw materials are needed except polyvinylpyrrolidone, ammonia water and basic copper carbonate, and the reaction temperature is at room temperature.
Preferably, the method comprises the following steps: the mass fraction of the ammonia water is 10-25%.
By adopting the technical scheme, the average particle size of the nano copper hydroxide can be smaller when the mass fraction of the ammonia water is in the range, but when the mass fraction is too small, the consumption of the polyvinylpyrrolidone is larger, and the cost is increased; when the mass fraction is too large, the average particle size of the nano sodium hydroxide is increased to a certain extent.
Preferably, the method comprises the following steps: the dropping speed of the polyvinylpyrrolidone water solution and the ammonia water is 8-12mL/min.
By adopting the technical scheme, the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is an important factor for controlling the average particle size of the nano-copper hydroxide, and when the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is too high, the average particle size of the nano-sodium hydroxide is obviously increased; when the mass fraction of the ammonia water is 25 percent, the dropping speed of the ammonia water reaches 15mL/min, the average particle size of the nano sodium hydroxide is increased to 98nm, and therefore, the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is not suitable to be too large.
Preferably, the method comprises the following steps: the concentration of the polyvinylpyrrolidone aqueous solution is 1-3mol/L.
By adopting the technical scheme, the particle size of the nano copper hydroxide is gradually reduced along with the increase of the concentration of the polyvinylpyrrolidone, and the concentration of the polyvinylpyrrolidone is an important factor for controlling the average particle size of the nano copper hydroxide; the concentration is too small, and the average particle size of the nano sodium hydroxide can be increased to more than 120 nm; the concentration is too high to facilitate cost control.
Preferably, the method comprises the following steps: the weight ratio of the basic copper carbonate to the polyvinylpyrrolidone is 1: (0.5-2.5).
By adopting the technical scheme, the consumption of the polyvinylpyrrolidone is too high, the preparation cost is increased, and the consumption of the polyvinylpyrrolidone is reduced under the condition that the average particle size of the nano sodium hydroxide meets the requirement, so that the cost is reduced.
Preferably, the method comprises the following steps: the average molecular weight of the polyvinylpyrrolidone is 45000-58000.
By adopting the technical scheme, when the molecular weight of the polyvinylpyrrolidone is within the range of 45000-58000, the average particle size of the nano copper hydroxide is not changed greatly and is below 50nm, the average molecular weight of the polyvinylpyrrolidone is not suitable to be reduced to below 45000, and when the average molecular weight of the polyvinylpyrrolidone is reduced to 40000, the average particle size of the copper hydroxide is greatly increased and can reach 356nm.
Preferably, the method comprises the following steps: and in the step S4, vacuum drying is adopted, and the vacuum drying temperature is 30-60 ℃.
By adopting the technical scheme, when the vacuum drying temperature is too high, the structure of the nano sodium hydroxide is easy to dehydrate and collapse.
Preferably, the method comprises the following steps: the preparation method of the polyvinylpyrrolidone aqueous solution comprises the following steps:
respectively calculating the use amounts of polyvinylpyrrolidone and water according to the concentration of a polyvinylpyrrolidone aqueous solution, then weighing the polyvinylpyrrolidone and the water according to the use amounts, then adding the polyvinylpyrrolidone into one fifth to one third of the volume of the water, performing ultrasonic dispersion for 25-35min at 25-30 ℃, then adding the rest water, uniformly mixing, and standing for 25-35min for later use.
By adopting the technical scheme, the dissolving speed of the polyvinylpyrrolidone can be improved by dispersing through ultrasound.
In a second aspect, the present application provides a nano copper hydroxide, which adopts the following technical scheme:
a nano copper hydroxide, which is prepared by the preparation method of the nano copper hydroxide according to any one of claims 1 to 8.
Preferably, the method comprises the following steps: the average grain diameter of the nano copper hydroxide is 5-50nm.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the method, the polyvinylpyrrolidone is added, so that the polyvinylpyrrolidone can be adsorbed on the particle surface of the copper hydroxide when the nano copper hydroxide is formed, steric hindrance is formed, the particles are limited to be increased continuously, the average particle size of the prepared nano copper hydroxide is small, and the specific surface area of the prepared nano copper hydroxide is large.
2. With the increase of the concentration of the polyvinylpyrrolidone, the particle size of the nano copper hydroxide is gradually reduced; the average particle size of the nano sodium hydroxide is reduced to a certain extent along with the gradual reduction of the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water; when the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is too high, the average grain diameter of the nano sodium hydroxide is obviously increased; when the average molecular weight of the polyvinylpyrrolidone is in the range of 45000-58000, the average particle size of the nanometer copper hydroxide is small, and when the average molecular weight is reduced to 40000, the average particle size of the copper hydroxide is greatly increased; the concentration of polyvinylpyrrolidone, the dropping speed of polyvinylpyrrolidone water solution and ammonia water and the average molecular weight of polyvinylpyrrolidone are all important factors for controlling the average grain diameter of nano copper hydroxide.
3. The average particle size of the nano copper hydroxide prepared by the method is below 50nm, and the minimum particle size can reach 5nm; the conversion rate of the basic copper carbonate is 90.1 percent and above; after the reaction is finished, the weight ratio of the basic copper carbonate to the polyvinylpyrrolidone is 1: (0.5-2.5); it is demonstrated that nano copper hydroxide with a small average particle size can be prepared by controlling each reaction condition in the presence of polyvinylpyrrolidone.
Drawings
Fig. 1 and 2 are SEM images of copper hydroxide prepared in example 14.
FIG. 3 is an EDS map of copper hydroxide prepared in example 14.
Figure 4 is an XRD pattern of copper hydroxide prepared in example 14.
Detailed Description
The present application is described in further detail below with reference to specific contents.
Starting materials
The raw materials used in the examples of the application are all common commercial products.
Examples
Example 1
A preparation method of nano copper hydroxide comprises the following preparation steps:
s1, preparing 1mol/L polyvinylpyrrolidone aqueous solution:
respectively calculating the use amounts of polyvinylpyrrolidone and water according to the concentration of a polyvinylpyrrolidone aqueous solution, then weighing polyvinylpyrrolidone and water according to the use amounts, then adding polyvinylpyrrolidone into a quarter volume of water, performing ultrasonic dispersion at 30 ℃ for 30min, then adding the rest water, uniformly mixing, and standing for 30min for later use; wherein the molecular weight of the polyvinylpyrrolidone is 45000;
s2, simultaneously dripping the polyvinylpyrrolidone aqueous solution and ammonia water into the suspension of basic copper carbonate and water at the temperature of 30 ℃, wherein the dripping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is 12mL/min, stirring is carried out while dripping is carried out, and the reaction end point is pH =7.5; wherein, in the suspension of basic copper carbonate and water, the weight ratio of the basic copper carbonate to the water is 1:10; wherein the mass fraction of the ammonia water is 10 percent;
s3, filtering the turbid liquid obtained in the S2 to obtain a solid;
and S4, carrying out vacuum drying on the solid obtained in the step S3 at the vacuum drying temperature of 30 ℃ to obtain the nano copper hydroxide.
Example 2
The preparation method of the nano copper hydroxide is different from the embodiment 1 in that the mass fraction of ammonia water is 15%, and the rest steps are the same as the embodiment 1.
Example 3
The preparation method of the nano copper hydroxide is different from the embodiment 1 in that the mass fraction of ammonia water is 20%, and the rest steps are the same as the embodiment 1.
Example 4
The preparation method of the nano copper hydroxide is different from the embodiment 1 in that the mass fraction of ammonia water is 25%, and the rest steps are the same as the embodiment 1.
Example 5
The preparation method of the nano copper hydroxide is different from the embodiment 2 in that the concentration of the polyvinylpyrrolidone aqueous solution is 2mol/L, and the other steps are the same as the embodiment 2.
Example 6
The preparation method of the nano copper hydroxide is different from the embodiment 2 in that the concentration of the polyvinylpyrrolidone aqueous solution is 3mol/L, and the rest steps are the same as the embodiment 2.
Example 7
A preparation method of nano copper hydroxide is different from that of the embodiment 5 in that the dropping speed of a polyvinylpyrrolidone aqueous solution and ammonia water is 10mL/min, and the other steps are the same as the embodiment 5.
Example 8
A preparation method of nano copper hydroxide is different from that of the embodiment 5 in that the dropping speed of a polyvinylpyrrolidone aqueous solution and ammonia water is 8mL/min, and the other steps are the same as the embodiment 5.
Example 9
The difference between the preparation method of the nano copper hydroxide and the preparation method of the nano copper hydroxide in the embodiment 8 is that the average molecular weight of polyvinylpyrrolidone is 50000, and the rest steps are the same as the steps in the embodiment 8.
Example 10
The preparation method of nano copper hydroxide is different from the embodiment 8 in that the average molecular weight of polyvinylpyrrolidone is 58000, and the rest steps are the same as the embodiment 8.
Example 11
The preparation method of the nano copper hydroxide is different from the embodiment 8 in that the reaction end point in S2 is pH =8, and the rest steps are the same as the embodiment 8.
Example 12
The preparation method of the nano copper hydroxide is different from the embodiment 8 in that the reaction end point in S2 is pH =9.5, and the rest steps are the same as the embodiment 8.
Example 13
A method for preparing nano copper hydroxide, which is different from that in example 11 in that the weight part ratio of basic copper carbonate to water in a suspension of the basic copper carbonate and water is 1:7, the rest of the procedure was the same as in example 11.
Example 14
A method for preparing nano copper hydroxide, which is different from that in example 11, in the suspension of basic copper carbonate and water, the weight ratio of the basic copper carbonate to the water is 1:3, the rest of the procedure was the same as in example 11.
Example 15
The preparation method of the nano copper hydroxide is different from the embodiment 1 in that the vacuum drying temperature in S4 is 60 ℃, and the other steps are the same as the embodiment 1.
Comparative example
Comparative example 1
The preparation method of the nano copper hydroxide is different from that of the embodiment 1 in that polyvinylpyrrolidone is replaced by fatty alcohol polyoxypropylene ether SPO-30 with equal weight parts, and the rest steps are the same as those of the embodiment 1.
Comparative example 2
A preparation method of nano copper hydroxide is different from that of the embodiment 4 in that the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is 15mL/min, and the other steps are the same as the embodiment 4.
Comparative example 3
The preparation method of the nano copper hydroxide is different from the embodiment 1 in that the concentration of the polyvinylpyrrolidone aqueous solution is 0.5mol/L, and the rest steps are the same as the embodiment 1.
Comparative example 4
The preparation method of the nano copper hydroxide is different from the preparation method of the embodiment 1 in that the average molecular weight of the polyvinylpyrrolidone is 40000, and the other steps are the same as the preparation method of the embodiment 1.
Comparative example 5
The preparation method of the nano copper hydroxide is different from the embodiment 1 in that the vacuum drying temperature in S4 is 70 ℃, and the rest steps are the same as the embodiment 1.
Performance test
Detection method/test method
Preparing nano copper hydroxide according to the preparation methods of examples 1 to 13 and comparative examples 1 to 5, respectively, detecting the average particle size of the nano copper hydroxide through a scanning electron microscope, and calculating the weight ratio of the basic copper carbonate to the polyvinylpyrrolidone consumed when the reaction is finished; the results are shown in Table 1.
Conversion rate of basic copper carbonate: basic copper carbonate conversion = (actual product moles/theoretically produced product moles) 100%.
Wherein, after the product obtained in the comparative example 5 is dried in vacuum, the structure of the product has certain collapse, and all data are not detected.
In FIGS. 1 and 2, it can be seen that the average particle size of the nano-copper hydroxide prepared in example 14 is about 5 nm.
EDS spectrum processing in fig. 3: no peaks that were ignored; all analyzed elements (normalized) were repeated 5 times; wherein the standard samples are as follows:
the detection data are as follows:
| element(s) | Weight (D) | Atom(s) |
| Percentage of | Percentage of | |
| C K | 25.52 | 45.36 |
| O K | 29.33 | 39.14 |
| Si K | 0.43 | 0.33 |
| Cl K | 0.51 | 0.31 |
| Cu L | 44.25 | 14.87 |
| Ta M | -0.03 | 0.00 |
| Total amount of | 100.00 |
The XRD pattern in fig. 4 is the same as the characteristic peak of the nano copper hydroxide, and it can be determined that the prepared product is the nano copper hydroxide.
TABLE 1 test results of examples 1 to 15 and comparative examples 1 to 4
As can be seen from the detection data of examples 1-15 and comparative examples 1-5, and table 1, the average particle size of the nano copper hydroxide prepared by the method is below 50nm, and the minimum particle size can reach 5nm; the conversion rate of the basic copper carbonate is 90.1 percent or more; after the reaction is finished, the weight ratio of the basic copper carbonate to the polyvinylpyrrolidone is 1: (0.5-2.5); it is demonstrated that the nano copper hydroxide with small average grain diameter can be prepared by controlling each reaction condition in the presence of polyvinylpyrrolidone.
As can be seen from the detection data of the embodiments 1 to 4, when the mass fraction of the ammonia water is increased, the increase range of the average particle size of the nano copper hydroxide is small; but the consumption of polyvinylpyrrolidone is less when the reaction is finished, which is beneficial to reducing the cost.
As can be seen from the detection data of the example 2 and the examples 5-6, the particle size of the nano copper hydroxide is gradually reduced along with the increase of the concentration of the polyvinylpyrrolidone; in combination with comparative example 3, the concentration of polyvinylpyrrolidone should not be too small; from the detection data of the embodiment 5 and the embodiments 7 to 8, it can be seen that the average particle size of the nano sodium hydroxide is reduced to a certain extent along with the gradual reduction of the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water; in combination with comparative example 2, when the dropping speed of the polyvinylpyrrolidone aqueous solution and the ammonia water is too high, the average grain diameter of the nano sodium hydroxide is obviously increased; the concentration of the polyvinylpyrrolidone, the dropping speed of the polyvinylpyrrolidone water solution and the ammonia water are all important factors for controlling the average grain diameter of the nano copper hydroxide.
From the test data of example 8 and examples 9 to 10, it can be seen that the average particle size of the nano copper hydroxide is not greatly changed when the molecular weight of polyvinylpyrrolidone is in the range of 45000-58000. However, in combination with the data of comparative example 4, the average molecular weight of polyvinylpyrrolidone is not preferably reduced to 45000 or less, and when the average molecular weight is reduced to 40000, the average particle size of copper hydroxide is greatly increased.
As can be seen from the detection data of example 8 and examples 11-12, the conversion rate of the basic copper carbonate is improved to a certain extent along with the increase of the pH value at the end point of the reaction, the average particle size of the nano sodium hydroxide is not obviously influenced, and the consumption of the polyvinylpyrrolidone is increased to a certain extent.
It can be seen from the detection data of example 11 and examples 13-14 that when the concentration of the basic copper carbonate suspension is reduced, the particle size of the nano copper hydroxide is reduced to 5nm at the lowest, but the conversion rate of the basic copper carbonate is reduced, and the consumption of the polyvinylpyrrolidone is increased.
The detection data of the embodiment 1 and the embodiment 15 show that the vacuum drying temperature of the nano copper hydroxide can be below 60 ℃; in combination with comparative example 5, the vacuum drying temperature should not be too high.
The embodiments of the present invention are preferred embodiments of the present application, and the scope of the present application is not limited by the embodiments of the present application, so: equivalent changes in structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. A preparation method of nano copper hydroxide is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
s1, preparing a polyvinylpyrrolidone aqueous solution with the concentration of more than or equal to 1 mol/L;
s2, at the temperature of 25-35 ℃, simultaneously dripping the polyvinylpyrrolidone aqueous solution and ammonia water into the suspension of basic copper carbonate and water, stirring while dripping, wherein the reaction end point is pH =7.5-9.5; wherein, in the suspension of basic copper carbonate and water, the weight ratio of basic copper carbonate to water is 1: (3-10);
s3, filtering the turbid liquid obtained in the S2 to obtain a solid;
and S4, drying the solid obtained in the S3 to obtain the nano copper hydroxide.
2. The method for preparing nano copper hydroxide according to claim 1, wherein the method comprises the following steps: the mass fraction of the ammonia water is 10-25%.
3. The method for preparing nano copper hydroxide according to claim 2, wherein the method comprises the following steps: the dropping speed of the polyvinylpyrrolidone water solution and the ammonia water is 8-12mL/min.
4. The method for preparing nano copper hydroxide according to claim 3, wherein the method comprises the following steps: the concentration of the polyvinylpyrrolidone water solution is 1-3mol/L.
5. The method for preparing nano copper hydroxide according to claim 1, wherein the method comprises the following steps: the weight ratio of the basic copper carbonate to the polyvinylpyrrolidone is 1: (0.5-2.5).
6. The method for preparing nano copper hydroxide according to claim 1, characterized in that: the average molecular weight of the polyvinylpyrrolidone is 45000-58000.
7. The method for preparing nano copper hydroxide according to claim 1, wherein the method comprises the following steps: and in the step S4, vacuum drying is adopted, and the vacuum drying temperature is 30-60 ℃.
8. The method for preparing nano copper hydroxide according to claim 1, wherein the method comprises the following steps: the preparation method of the polyvinylpyrrolidone aqueous solution comprises the following steps:
respectively calculating the use amounts of polyvinylpyrrolidone and water according to the concentration of a polyvinylpyrrolidone aqueous solution, then weighing the polyvinylpyrrolidone and the water according to the use amounts, then adding the polyvinylpyrrolidone into one fifth to one third of the volume of the water, performing ultrasonic dispersion for 25-35min at 25-30 ℃, then adding the rest water, uniformly mixing, and standing for 25-35min for later use.
9. A nanometer copper hydroxide is characterized in that: the nano copper hydroxide is prepared by the preparation method of the nano copper hydroxide as claimed in any one of claims 1 to 8.
10. The nano-copper hydroxide according to claim 7, wherein: the average grain diameter of the nano copper hydroxide is 5-50nm.
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| CN105347382A (en) * | 2015-12-10 | 2016-02-24 | 济南大学 | Method for preparing garland-shaped nanometer copper oxide material |
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| CN105347382A (en) * | 2015-12-10 | 2016-02-24 | 济南大学 | Method for preparing garland-shaped nanometer copper oxide material |
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| Title |
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| 徐爽: ""杀菌剂用纳米氢氧化铜的制备及应用性能研究研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 12, pages 30 - 60 * |
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