CN-121673303-B - Copper-tungsten polyoxometalate, preparation method thereof and application thereof in agricultural sterilization field

CN121673303BCN 121673303 BCN121673303 BCN 121673303BCN-121673303-B

Abstract

The invention belongs to the technical field of agricultural sterilization active ingredients, and particularly relates to a copper-tungsten polyoxometalate, a preparation method thereof and application thereof in the field of agricultural sterilization. The Cu-W-POMs of the copper-tungsten polyoxometallate compound have excellent bactericidal activity, can effectively inhibit pathogenic bacteria of cucumber fusarium wilt, and have good inhibition effects on pathogenic bacteria of crop diseases such as soybean seed rot, pear black spot, apple anthracnose and the like, and particularly can be used for preparing agricultural bactericides for preventing and controlling crop diseases such as cucumber fusarium wilt and the like in the aspect of preventing and controlling cucumber fusarium wilt.

Inventors

SHI FUMEI
ZHANG QIUFENG
QIAO QINGHAI
Yi Shangyu
SUN ZHIHONG

Assignees

聊城大学

Dates

Publication Date: 20260505
Application Date: 20260209

Claims (7)

1. The application of the copper-tungsten polyoxometalate compound or the composition thereof in the field of agricultural sterilization is characterized in that the copper-tungsten polyoxometalate compound or the composition is used for preparing an agricultural bactericide; the molecular formula of the copper-tungsten polyoxometalate compound is C 48 H 32 Cu 2 N 8 O 40 W 12 , the copper-tungsten polyoxometalate compound is monoclinic, the space group is P21/C, the unit cell parameters are a= 26.18881 (12) A, b= 11.83944 (4) A, c= 23.40596 (11) A, alpha=90 degrees, beta= 113.7335 degrees and gamma=90 degrees, the XRD diffraction of the compound has characteristic peaks at 2 theta of 8.2+/-0.2 degrees, 25.7+/-0.2 degrees, 35.7+/-0.2 degrees and 48.5+/-0.2 degrees, the microscopic morphology of the compound is a cuboid structure, and the particle size of the compound is 200-500nm; The composition comprises an active dose of the copper-tungsten polyoxometalate compound and a carrier accepted in the field of pesticides; The carrier accepted in the field of pesticide is selected from solid carriers and liquid carriers, wherein the solid carriers are selected from fine powder or particles of kaolin, diatomite, synthetic hydrated silicon oxide, bentonite, fubasami clay, acid clay, talcum, ceramic, sericite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silicon dioxide, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea or ammonium chloride; The liquid carrier is selected from water, methanol, ethanol, acetone, methyl ethyl ketone, hexane, cyclohexane, kerosene, light oil, soybean oil or cottonseed oil.
2. The use of a copper-tungsten polyoxometalate compound or a composition thereof according to claim 1 in the field of agricultural sterilization, wherein the agricultural fungicide inhibits pathogenic bacteria selected from the group consisting of cucumber fusarium wilt, soybean phomopsis, apple anthracnose and pear black spot.
3. The use of the copper-tungsten polyoxometalate compound or the composition thereof in the field of agricultural sterilization according to claim 1, wherein the preparation method of the copper-tungsten polyoxometalate compound comprises the following steps: S1-preparing a dodecatungstic acid salt cluster precursor solution, namely dissolving ammonium metatungstate hydrate in water, stirring at 60-70 ℃ for 10-20 min until solid is completely dissolved, slowly adding acid liquor to adjust the pH to 1.8-2.2, and then continuously stirring for 20-40 min to obtain a pale yellow precursor solution, wherein the dosage ratio of the ammonium metatungstate hydrate to the water is 0.2-0.4 g:10-15 ml; s2-introducing copper salt and organic ligand, namely sequentially adding copper salt, phenanthroline and adipic acid into the precursor liquid obtained in the step S1, keeping the temperature of 60-70 ℃ and continuously stirring until a blue-green stable solution is obtained, wherein the molar ratio of the phenanthroline, the adipic acid and the copper salt is 1-3:1; S3-hydrothermal reaction, namely regulating the pH value of the blue-green solution obtained in the step S2 to 3.8-4.2, transferring the blue-green solution into a high-pressure reaction kettle, and heating the solution to 150-170 ℃ for reaction for 90-100 hours to obtain a suspension; s4-purifying, namely separating a precipitation part from the suspension obtained in the step S3, and washing and drying to obtain a dark green rod-shaped monocrystal product.
4. The application of the copper-tungsten polyoxometallate compound or the composition thereof in the field of agricultural sterilization according to claim 3, wherein in S1, the stirring speed is 250-350 r/min, and the acid liquor is hydrochloric acid with the concentration of 5-7 mol/L.
5. Use of a copper-tungsten polyoxometalate compound or a combination thereof according to claim 3 in the field of agricultural sterilization, wherein in S2 the copper salt is copper chloride.
6. The application of the copper-tungsten polyoxometallate compound or the composition thereof in the field of agricultural sterilization, according to claim 3, wherein in S3, the filling degree of a solution in the high-pressure reaction kettle is 75-85%; and in the reaction heating stage, the heating rate is 4-6 ℃ per minute, and the cooling rate is 8-12 ℃ per minute after the reaction is finished.
7. Use of a copper-tungsten polyoxometalate compound or a combination thereof according to claim 3 in the field of agricultural sterilization, wherein in S4 the precipitation fraction is separated by filtration or centrifugation, and the obtained precipitation fraction is washed with water and ethanol in sequence and then dried, wherein the drying means include but are not limited to negative pressure drying, heat radiation drying or drying in a complex manner.

Description

Copper-tungsten polyoxometalate, preparation method thereof and application thereof in agricultural sterilization field Technical Field The invention belongs to the technical field of agricultural sterilization active ingredients, and particularly relates to a copper-tungsten polyoxometalate, a preparation method thereof and application thereof in the field of agricultural sterilization. Background The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art. China is the main cucumber producing country and consuming country worldwide, the cucumber planting area is stabilized to be more than 100 ten thousand hectares in recent years, the total yield breaks through 6000 ten thousand tons, and the cucumber planting method is one of important crops for guaranteeing domestic vegetable market supply and supporting facility agriculture development. However, the disease problem severely restricts the healthy development of the cucumber industry, wherein cucumber fusarium wilt is one of the most serious soil-borne fungus diseases, the disease is initiated by fusarium oxysporum cucumber specialization, the incidence rate of continuous cropping planting plots can reach 30% -50%, serious plots even are in harvest, diseased plants show vascular bundle browning and whole plant wilting, the yield loss is increased by 20%, the commodity quality of the cucumber is reduced, and obvious threat is formed to vegetable farmer income and vegetable supply chain stability. At present, the control measures of cucumber fusarium wilt mainly comprise agricultural control, physical control and medicament control, wherein the agricultural control (such as crop rotation and stubble cutting and grafting of disease-resistant stocks) is limited by a planting mode and land conditions, is difficult to popularize in a large area in intensive facility cultivation, the physical control (such as soil disinfection) has high cost and complex operation and is easy to destroy soil microecology, the medicament control is still the most dependent means in the current production, and conventional bactericides such as carbendazim, hymexazol and the like are commonly used, but the medicament resistance of pathogenic bacteria is obviously enhanced after long-term single use, the field control effect is reduced to below 50% from more than 80% in the initial stage, and meanwhile, part of medicaments have residual overstandard risks and do not meet the development requirements of green agriculture. Polyoxometallate (POM) is a kind of inorganic functional material with adjustable structure, and has excellent oxidation-reduction activity and broad antibacterial spectrum, so that the Polyoxometallate (POM) is attracting attention in the field of agricultural bactericides. However, the existing agricultural POM compounds have the defects of insufficient targeted antibacterial activity (poor specificity for cucumber fusarium wilt), weak preparation stability (less than 7 days in field duration), and the like, and are difficult to meet the actual control requirements of cucumber fusarium wilt. Disclosure of Invention Aiming at the problems in the prior art, the invention aims to provide an active ingredient which has stable structure, good environmental compatibility and antibacterial activity. In order to achieve the technical aim, the invention provides the copper-tungsten polyoxometalate compound which has good bactericidal activity, can well inhibit cucumber fusarium wilt, soybean phomopsis, pear black spot and apple anthracnose, can be used for preparing an agricultural bactericide for preventing and controlling plant diseases, and has important significance in solving the problem of cucumber fusarium wilt prevention and control and promoting green agricultural development. According to the technical effects, the invention provides the following technical scheme: In a first aspect, a copper-tungsten polyoxometalate compound is provided, having a molecular formula of C 48H32Cu2N8O40W12, a monoclinic system, a space group of P21/C, and unit cell parameters of a= 26.18881 (12) a, b= 11.83944 (4) a, c= 23.40596 (11) a, α=90°, β= 113.7335 °, γ=90°. The copper-tungsten polyoxometallate compound in the first aspect is called Cu-W-POMs for short, wherein a Keggin-type tungsten polyoxometallate cluster W 12O40 in the molecular formula of the compound is taken as a basic building unit, and is combined with Cu (C 12H8N2)2 coordination unit through coordination bond and then further forms a one-dimensional chain-shaped supermolecular structure along an a axis through hydrogen bond action, wherein the Keggin-type W 12O40 oxometallate cluster is taken as a first active site, has stronger redox capability, can destroy pathogenic bact