CN114195182A - Preparation method of soil additive component containing copper metal compound - Google Patents

Preparation method of soil additive component containing copper metal compound Download PDF

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CN114195182A
CN114195182A CN202210079196.2A CN202210079196A CN114195182A CN 114195182 A CN114195182 A CN 114195182A CN 202210079196 A CN202210079196 A CN 202210079196A CN 114195182 A CN114195182 A CN 114195182A
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solution
water
mixed solution
particles
reaction kettle
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周铁莉
刘宏晔
东莎莎
王天宇
孙茂成
侯聚敏
杨柳
马井喜
吴淑清
阮伟东
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Changchun University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/12—Sulfides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Nanotechnology (AREA)
  • Plant Pathology (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agronomy & Crop Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to the field of soil treatment, in particular to a preparation method of a soil additive component containing a copper metal compound, which comprises a synthesis method of CuS nano particles; the synthesis method of the CuS nano-particles comprises the following steps: s1: adding copper sulfate pentahydrate and polyvinylpyrrolidone into water for dissolving to prepare a solution A; s2: dissolving sodium thiosulfate pentahydrate in water to prepare a solution B; s3: evenly mixing the A, B solution, and transferring the mixture into a 100mL polytetrafluoroethylene reaction kettle for sealing reaction; s4: taking out the mixed solution in the reaction kettle, cooling to room temperature, and pouring out supernatant liquor; s5: washing the cooled mixed solution with deionized water and centrifugally dewatering; the invention can obviously inhibit the growth of the germs at the roots of the plants, and the bacteriostasis time is long. Meanwhile, the raw materials used in the invention have low cost and simple process, are easy to put into industrial production, have no toxicity when being used in trace amount, and can increase the nutrient content in soil.

Description

Preparation method of soil additive component containing copper metal compound
Technical Field
The invention relates to the field of soil treatment, in particular to a preparation method of a soil additive component containing copper metal compounds.
Background
With the increasingly severe global desertification and desertification situations, less and less land can be cultivated. In China, the contradiction of more people and less land is more prominent, continuous cropping cultivation is the only method for solving the problem, but the continuous cropping diseases such as soil-borne diseases and the like cause large-area yield reduction and no yield of crops. The incidence rate of continuous cropping diseases is generally 10-30%, and plants are usually withered to cause seedling shortage and ridge breaking; the morbidity can reach 80-90% when the disease is serious, even the death and the failure in the whole garden are caused, and the disease is a destructive disease. Continuous cropping diseases become important topics for attention and research of agricultural experts and broad farmers, but have not been developed with great breakthrough for a long time.
The trace element requirements of different crops are different. If crops are planted by continuous cropping, the short-plate trace elements in the field can be further reduced, and the incidence rate of the nutrient deficiency disease is increased by a lot compared with the incidence rate of the common plots. And if continuous cropping is carried out for three or more years, the nutrient deficiency disease is more obvious. In addition, continuous cropping of individual crops can secrete some organic acids, which are combined with trace mineral ions to form complexes, thereby causing worsening of the deficiency disease.
Due to continuous cropping, ova and germs of field crops can fall into the field, and the field environment is also suitable for growth of germs and ova at the moment, so that the continuous cropping planted field is easy to explode to cause diseases and insect pests. Especially, commercial crops such as hot pepper, watermelon, eggplant, tomato and the like are easy to suffer from diseases such as root rot and the like after continuous cropping. The same kind or same family of crops are continuously planted for three or more years in the same land, and are called 'continuous cropping' in the cultivation science. Continuous cropping is an important reason for weak growth potential, reduced yield, increased disease and reduced quality of many crops.
Disclosure of Invention
The invention aims to provide a preparation method of a soil additive component containing copper metal compounds, and aims to solve the problems of nutrient element unbalance, soil toxicity accumulation and germ reproduction of the existing planting field.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing a soil additive component containing copper metal compounds specifically comprises a method for synthesizing CuS nano particles;
the synthesis method of the CuS nano-particles comprises the following manufacturing steps:
s1: adding copper sulfate pentahydrate and polyvinylpyrrolidone into water for dissolving to prepare a solution A;
s2: dissolving sodium thiosulfate pentahydrate in water to prepare a solution B;
s3: uniformly mixing the solution A and the solution B, and transferring the mixture into a 100mL polytetrafluoroethylene reaction kettle for sealing reaction;
s4: taking out the mixed solution in the reaction kettle, cooling to room temperature, and pouring out supernatant liquor;
s5: washing the cooled mixed solution with deionized water and centrifugally dewatering;
s6: and finally, putting the particles into an oven for drying to obtain black CuS nano particles.
In one alternative: in the step S1, the dosage of the copper sulfate pentahydrate is 5mmol, the dosage of the polyvinylpyrrolidone is 6-10 mg, and the dosage of the water is 60 mL.
In one alternative: in step S2, the amount of hydrated sodium thiosulfate used is 10mmol, and the amount of water used is 20 mL.
In one alternative: in the step S3, the temperature of the mixed solution in the reaction kettle is 180 ℃, and the time is kept for 5-6 h.
In one alternative: in step S5, the number of times of centrifugation of the mixed solution is three.
In one alternative: in step S6, the temperature of the mixture in the oven was 45 ℃.
In one alternative: in step S6, the time of the mixed liquid in the drying box is 6-12 h.
Compared with the prior art, the invention has the following advantages:
the fertilizer contains trace element copper, can effectively promote substance conversion in soil, and improves the utilization rate of the fertilizer, thereby supplementing nutrients missing in the soil; meanwhile, the copper ion-free antibacterial agent exists in a solvent in the form of copper ions, the nano copper particles with positive charges are contacted with bacteria with negative charges and the like through charge attraction, the nano copper particles enter bacterial cells, cell walls of the bacteria are broken, cell sap flows outwards, and the bacteria are killed; the nano copper particles entering the cells can react with protease and the like in bacterial cells to denature and inactivate the protease, so that the bacteria are killed; the nano copper as a semiconductor has stable property and strong absorption to near infrared light, and can simultaneously achieve the antibacterial effect by exciting surface plasma resonance.
Drawings
FIG. 1 is a graph showing the effect of copper sulfide nanoparticles on bacterial growth according to the present invention.
FIG. 2 is a graphical representation of the effect of copper oxide nanoparticles on bacterial growth in accordance with the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments; in the drawings or the description, the same reference numerals are used for similar or identical parts, and the shape, thickness or height of each part may be enlarged or reduced in practical use. The examples are given solely for the purpose of illustration and are not intended to limit the scope of the invention. Any obvious modifications or variations can be made to the present invention without departing from the spirit or scope of the present invention.
The first embodiment is as follows:
in one embodiment, as shown in fig. 1, a method for preparing a soil additive composition containing a copper metal compound according to the present invention specifically includes a method for synthesizing CuS nanoparticles;
the synthesis method of the CuS nano-particles comprises the following manufacturing steps:
5mmol of copper sulfate pentahydrate (CuSO)4·5H2O) and 6mg polyvinylpyrrolidone (PVP) were added to 60mL of water and dissolved, and 10mmol of sodium thiosulfate pentahydrate (Na) was taken2S2O3·5H2O) is dissolved in 20mL of water, the 2 parts of solution are mixed uniformly and then transferred into a 100mL polytetrafluoroethylene reaction kettle to be sealed, the temperature is kept at 180 ℃ for 5h, after the reaction is finished, the mixed solution is taken out and cooled to the room temperature, supernatant liquid is poured out, washed by deionized water and centrifuged for 3 times, and finally the mixture is put into a 45 ℃ oven to be dried for 6h, so that black CuS nano particles are obtained.
Example two:
a method for preparing a soil additive component containing copper metal compounds specifically comprises a method for synthesizing CuS nano particles;
the synthesis method of the CuS nano-particles comprises the following manufacturing steps:
5mmol of copper sulfate pentahydrate (CuSO)4·5H2O) and 8mg polyvinylpyrrolidone (PVP) were added to 60mL of water and dissolved, and 10mmol of sodium thiosulfate pentahydrate (Na) was taken2S2O3·5H2O) dissolved in 20mL of waterAnd (3) uniformly mixing the 2 parts of solution, transferring the mixture into a 100mL polytetrafluoroethylene reaction kettle, sealing, keeping the temperature at 180 ℃ for 5.5 hours, taking out the mixed solution after the reaction is finished, cooling to room temperature, pouring out supernatant, washing with deionized water, centrifuging for 3 times, and finally drying in a 45 ℃ oven for 10 hours to obtain black CuS nanoparticles.
Example three:
a method for preparing a soil additive component containing copper metal compounds specifically comprises a method for synthesizing CuS nano particles;
the synthesis method of the CuS nano-particles comprises the following manufacturing steps:
5mmol of copper sulfate pentahydrate (CuSO)4·5H2O) and 10mg polyvinylpyrrolidone (PVP) were added to 60mL of water and dissolved, and 10mmol of sodium thiosulfate pentahydrate (Na) was taken2S2O3·5H2O) is dissolved in 20mL of water, the 2 parts of solution are mixed uniformly and then transferred into a 100mL polytetrafluoroethylene reaction kettle to be sealed, the temperature is kept at 180 ℃ for 6h, after the reaction is finished, the mixed solution is taken out and cooled to the room temperature, supernatant liquid is poured out, washed by deionized water and centrifuged for 3 times, and finally the mixture is placed into a 45 ℃ oven to be dried for 12h, so that black CuS nano particles are obtained.
Effect of CuS nanoparticles on bacterial growth experiments:
respectively adding 50mL of nutrient broth into 2 conical flasks with the same size, adding 20mL of PBS phosphate buffer solution, and grouping into No. 1 and No. 2; taking 5mL of CuS dispersion liquid with the concentration of 1000mg/mL into a No. 1 conical flask, taking No. 2 as a blank sample, sterilizing at 121 ℃ for later use, taking 0.5mL of escherichia coli diluted to a certain multiple into the cooled culture solution, shaking and dispersing, taking 3mL of escherichia coli, measuring the absorbance at 600nm, and taking 3mL of the escherichia coli at intervals of 1-2 hours;
as shown in the attached figure 1, the experimental group added with the CuS nano-particles has good bacteriostatic effect along with the increase of the experimental time;
experimental effect of CuS nanoparticles on pepper growth:
on the basis of conventional fertilization on crops, the fertilizer is applied at 1500kg/hm2The amount of the CuS soil additive component is applied. Copper sulfide for hot pepper andcompared with the method without applying copper sulfide, the yield is increased by 13245.0kg/hm2The growth rate is 26.3%; therefore, the CuS nano particles have a good soil improvement effect in the practical application process.
The preparation method of the soil additive component containing the copper metal compound also comprises the Cu in addition to the synthesis method of the CuS nano particles2-xS (x is more than or equal to 0 and less than or equal to 1) nanoparticle synthesis method;
the Cu2The method for synthesizing the-xS (x is more than or equal to 0 and less than or equal to 1) nano particles comprises the following steps:
a1: adding 40-4000 mg of copper oxide into 5-1000 mL of sodium sulfide solution (0.004-0.4M), keeping at 120 ℃ for 10h, and carrying out hydrothermal treatment on the mixed solution;
a2: preparation of Cu2-xS nanoparticles.
A method for preparing a soil additive component containing copper metal compounds comprises a method for synthesizing CuO nanoparticles in addition to the above method for synthesizing CuS nanoparticles;
the synthesis method of the CuO nano-particles comprises the following steps:
b1: weighing 1.2g of copper acetate in a 500mL beaker, adding 200mL of distilled water, and stirring until the copper acetate is basically dissolved;
b2: further, 1.56g of sodium peroxide (Na) was weighed2O2) Slowly adding 200mL of distilled water into a 200mL beaker, and stirring until the distilled water is completely dissolved;
b3: then, dropwise adding the two mixed solutions into a copper acetate solution to generate blue precipitates;
b4: placing the blue precipitate into a 500mL beaker, magnetically stirring at a constant temperature for 6h, and carrying out vacuum filtration on the generated brownish black solution for 15 min;
b5: distilled water is added in the suction filtration process, so that the product is purer;
b6: and finally, placing the product in a petri dish, performing electric heating constant-temperature air blast drying at 60 ℃ for 6 hours, grinding the product into powder and bagging for later use.
Experiment on the influence of CuO nanoparticles on bacterial growth:
respectively adding 50mL of nutrient broth into 2 conical flasks with the same size, adding 20mL of PBS phosphate buffer solution, and grouping into No. 1 and No. 2; taking 5mL of copper oxide dispersion liquid with the concentration of 1000mg/mL into a No. 1 conical flask, taking a No. 2 sample as a blank sample, and sterilizing at 121 ℃ for later use; then 0.5mL of escherichia coli diluted to a certain multiple is taken to be placed in the cooled culture solution, shaking and dispersing are carried out, and 3mL of escherichia coli is taken to measure absorbance at 600 nm; then taking 3mL of absorbance every 1-2 hours;
as shown in fig. 2, the experimental group added with CuO nanoparticles has a good bacteriostatic effect.
The above description is only for the specific embodiments of the present disclosure, but the scope of the present disclosure is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present disclosure, and all the changes or substitutions should be covered within the scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be subject to the protection scope of the claims.

Claims (7)

1. A method for preparing a soil additive component containing a copper metal compound is characterized by comprising a method for synthesizing CuS nano particles;
the synthesis method of the CuS nano-particles comprises the following manufacturing steps:
s1: adding copper sulfate pentahydrate and polyvinylpyrrolidone into water for dissolving to prepare a solution A;
s2: dissolving sodium thiosulfate pentahydrate in water to prepare a solution B;
s3: uniformly mixing the solution A and the solution B, and transferring the mixture into a 100mL polytetrafluoroethylene reaction kettle for sealing reaction;
s4: taking out the mixed solution in the reaction kettle, cooling to room temperature, and pouring out supernatant liquor;
s5: washing the cooled mixed solution with deionized water and centrifugally dewatering;
s6: and finally, putting the particles into an oven for drying to obtain black CuS nano particles.
2. The method as claimed in claim 1, wherein the copper sulfate pentahydrate is 5mmol, the polyvinylpyrrolidone is 6-10 mg, and the water is 60mL in step S1.
3. The method of claim 1, wherein in step S2, the hydrated sodium thiosulfate in 10mmol and the water in 20mL are used.
4. The method of claim 1, wherein the temperature of the mixture in the reaction kettle is 180 ℃ and the time for the mixture to react is 5-6 hours in step S3.
5. The method according to claim 1, wherein the mixed solution is centrifuged three times in step S5.
6. The method of claim 1, wherein the temperature of the mixed solution in the oven is 45 ℃ in step S6.
7. The method of claim 6, wherein in step S6, the time of the mixture in the oven is 6-12 hours.
CN202210079196.2A 2022-01-24 2022-01-24 Preparation method of soil additive component containing copper metal compound Pending CN114195182A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502773A (en) * 2011-11-23 2012-06-20 陕西科技大学 Preparation method of annular self assembled copper sulfide hollow spheres
CN103638950A (en) * 2013-12-16 2014-03-19 北京科技大学 CuS nanosheet photocatalytic material and preparation method thereof
CN111559756A (en) * 2020-06-04 2020-08-21 陕西理工大学 Light absorption enhanced spherical CuS submicron material and preparation method thereof
CN111689513A (en) * 2019-03-14 2020-09-22 可隆科技特有限公司 Method for synthesizing nano copper sulfide powder by using plasma
CN112028110A (en) * 2020-09-15 2020-12-04 贵州理工学院 Nano sheet copper sulfide material, preparation method and application
CN112569895A (en) * 2020-10-30 2021-03-30 徐州瑞鑫新材料研究院有限公司 Preparation method of organic anionic dye adsorbent with high adsorption capacity, product and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502773A (en) * 2011-11-23 2012-06-20 陕西科技大学 Preparation method of annular self assembled copper sulfide hollow spheres
CN103638950A (en) * 2013-12-16 2014-03-19 北京科技大学 CuS nanosheet photocatalytic material and preparation method thereof
CN111689513A (en) * 2019-03-14 2020-09-22 可隆科技特有限公司 Method for synthesizing nano copper sulfide powder by using plasma
CN111559756A (en) * 2020-06-04 2020-08-21 陕西理工大学 Light absorption enhanced spherical CuS submicron material and preparation method thereof
CN112028110A (en) * 2020-09-15 2020-12-04 贵州理工学院 Nano sheet copper sulfide material, preparation method and application
CN112569895A (en) * 2020-10-30 2021-03-30 徐州瑞鑫新材料研究院有限公司 Preparation method of organic anionic dye adsorbent with high adsorption capacity, product and application thereof

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Title
M.SARANYA: "Hydrothermal Synthesis of CuS Nanostructures with Different Morphology", 《JOURNAL OF NANO RESEARCH》, vol. 18, pages 334 - 51 *
张妮伟: "CuS半导体纳米盘合成及光学性能研究", 《湖北大学学报》, vol. 42, no. 1 *
徐磊: "纳米硫化铜近红外吸收材料", 《光学学报》, vol. 33, no. 1 *

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