CN113603548B

CN113603548B - Manganese element foliar spray fertilizer and preparation method thereof

Info

Publication number: CN113603548B
Application number: CN202110945779.4A
Authority: CN
Inventors: 吴洪洪; 李召虎; 刘家浩; 顾江江; 胡金; 吴晗; 曹菲菲
Original assignee: Huazhong Agricultural University
Current assignee: Huazhong Agricultural University
Priority date: 2021-08-17
Filing date: 2021-08-17
Publication date: 2022-11-04
Anticipated expiration: 2041-08-17
Also published as: CN113603548A

Abstract

The invention provides a manganese element foliar spray fertilizer and a preparation method thereof. The method comprises the following steps: the nano-enzyme analogue is a manganese-based oxide nano-material or colloid containing the manganese-based oxide nano-material. Compared with the prior art, the invention has the beneficial effects that: the manganese-based oxide nano enzyme mimic similar to cellular antioxidant enzyme is adopted, the salt tolerance and drought tolerance of crops can be improved at the concentration of 150-2000 mg/L, the manganese-based oxide nano enzyme mimic is compounded with a surfactant with the volume percentage of 0.04-0.06%, when the manganese-based oxide nano enzyme mimic is sprayed on the leaf surface at the later stage, the manganese-based oxide nano enzyme mimic helps the crops enter a leaf surface channel, and the manganese-based oxide nano enzyme mimic and the surfactant are matched for use, so that the biological index of the crops planted under the condition of high salt can be improved.

Description

Manganese element foliar spray fertilizer and preparation method thereof

Technical Field

The invention belongs to the field of agriculture, and particularly relates to a manganese element foliar spray fertilizer and a preparation method thereof.

Background

The soil salinization is a serious problem affecting agricultural production and ecological environment, and under the conditions that crops in the salinized land are generally difficult to grow, and the population is continuously increased and the cultivated land area is gradually reduced, the improvement of the utilization rate of the salinized land is an important way for relieving the soil pressure.

At present, various products are developed and applied to crop management to improve the salt tolerance of plants, and the method is one of the methods for realizing agricultural development of salinized land. The manganese element is one of the essential trace elements of crops, and researches show that the manganese element plays an important role in improving the salt tolerance of plants, and the chestnut Wen Xia finds that the manganese element promotes the active oxygen scavenging capability of a matrix in the research on the effect of improving the salt tolerance of soybeans. Based on the above, the prior art improves the salt tolerance of crops by applying fertilizers containing manganese elements. However, the existing fertilizer containing manganese element exists in the form of manganese sulfate or manganese chloride, high-content sulfate radicals and chloride ions exist in most salinized soil, and if the sulfate radicals and the chloride ions are introduced again in the process of providing the manganese element, the salinization degree of the soil is inevitably increased, so that the development of a new manganese-based material without salinization anions is very important.

Disclosure of Invention

In order to solve the technical problems, the invention provides a manganese element foliar spray fertilizer and a preparation method thereof.

The specific technical scheme is as follows:

the difference of the manganese element foliar spray fertilizer is that the fertilizer comprises the following components:

the nano-enzyme analogue is a manganese-based oxide nano-material or colloid containing the manganese-based oxide nano-material;

in the foliage spray fertilizer, the concentration of the nano pseudoenzyme is 150 mg/L-2000 mg/L, and the surfactant is Silwet L-77 or TritonX-100.

Further, the manganese-based oxide nano material is fibrous or spherical and is subjected to surface modification by polyacrylic acid, polyetherimide or sodium oleate.

Further, the manganese-based oxide nano material is spherical and is subjected to surface modification by polyacrylic acid or polyetherimide.

Further, the volume percentage of the surfactant is 0.04-0.06%.

Further, in the colloid, the concentration of the manganese-based oxide nano material is 5 g/L-7 g/L, and the dispersion solvent is water.

Further, the concentration of the nano-mimetic enzyme is 200 mg/L-500 mg/L.

The preparation method of the manganese foliar spray fertilizer is characterized in that the manganese foliar spray fertilizer is obtained by mixing the nano-mimic enzyme with the surfactant.

Further, the method for the foliar spray application of the manganese element also comprises the preparation of nano enzyme mimic, wherein the nano enzyme mimic is obtained after mixing divalent manganese salt or a solution containing the divalent manganese salt with a dispersion liquid, carrying out hydrothermal reaction under the condition of containing oxygen and purifying.

Further, the dispersion liquid is ethanol or a mixed liquid of ethanol and ethylene glycol or a mixed liquid of a modified surfactant and water.

Further, the preparation of the nano-mimetic enzyme also comprises the following steps: the dispersion liquid is ethanol or a mixed liquid of ethanol and glycol, after hydrothermal reaction, the dispersion liquid is mixed with a modified surfactant and then ultrasonic treatment is carried out to obtain the nano-mimic enzyme, wherein the modified surfactant is sodium oleate.

Further, the dispersion liquid is a mixed liquid of a modified surfactant and water, a divalent manganese salt or a solution containing the divalent manganese salt is mixed with the dispersion liquid, and then the mixture is dripped into a precipitator solution to carry out hydrothermal reaction, wherein the modified surfactant is polyacrylic acid or polyetherimide.

Further, the step of synthesizing the nanophase quasiptase comprises the following steps:

step S1, mixing a divalent manganese salt solution with a surfactant solution to obtain a system A solution;

and S2, dripping the solution of the system A into a precipitant solution, carrying out hydrothermal reaction under the condition of oxygen, and purifying to obtain the nano-mimetic enzyme.

Further, the concentration of the divalent manganese salt solution is 0.8-1.2 mol/L, the concentration of the surfactant solution is 800-1000 g/L, and the volume ratio of the divalent manganese salt solution to the surfactant solution is 1: (1.5-2.5); the precipitator is ammonia water, the purification is carried out by adopting a dialysis method, and the volume ratio of the solution of the system A to the ammonia water is 1: (1.5-2.5).

Further, in the reaction system, the mass ratio of the divalent manganese to the surfactant is 1: (0.8-1.2).

Further, the hydrothermal reaction is carried out for 20 to 36 hours at a temperature of between 100 and 150 ℃.

Compared with the prior art, the invention has the beneficial effects that:

(1) The manganese-based oxide nano enzyme mimic similar to cellular antioxidant enzyme is adopted, the salt tolerance and drought tolerance of crops can be improved at the concentration of 150-2000 mg/L, the manganese-based oxide nano enzyme mimic is compounded with Silwet L-77 or TritonX-100 surfactant, and the manganese-based oxide nano enzyme mimic is helpful for entering a leaf surface channel when sprayed on the leaf surface at the later stage, and can improve the biological index when planted under the condition of high salt by matching the manganese-based oxide nano enzyme mimic and the leaf surface active agent.

(2) After the manganese-based oxide nano-pseudo-enzyme is modified by polyacrylic acid, polyetherimide or sodium oleate, the water solubility is improved, and the biological index of planting under the condition of high salt can be further improved when the manganese-based oxide nano-pseudo-enzyme is used; wherein, the colloid type nanometer enzyme imitating effect of the spherical manganese-based oxide nanometer material modified by polyacrylic acid or polyetherimide is the most excellent.

(3) In the leaf fertilizer, when the concentration of the nano pseudoenzyme is 200 mg/L-500 mg/L, the plant grows more robustly when planted under the condition of high salt.

(4) When the surfactant is Silwet L-77 and TritonX-100, the surfactant and the nano-mimic enzyme are mutually matched, so that the nano-mimic enzyme can smoothly enter through holes of leaf surfaces, wherein the surfactant is Silwet L-77, and the condition of entering the leaf surfaces is optimal.

(5) After a divalent manganese solution and a dispersion liquid containing a polymer modified surfactant solution and water are mixed, the particle size and morphology of the modified surfactant solution are regulated and controlled in a hydrothermal reaction to obtain spherical manganese-based oxide nano colloid with good dispersibility.

(6) The yield of the product can be further improved by dropping the system containing the divalent manganese salt and the dispersion liquid into the precipitant solution.

(7) When the precipitator is ammonia water, the divalent manganese ions can form manganese hydroxide, and then the manganese hydroxide is oxidized into a mixture of the di-and trivalent manganese oxides by oxygen in the air.

Drawings

FIG. 1 is the TEM appearance test result of the nano-mimetic enzyme material of example 1;

FIG. 2 shows the valence state detection result of X-ray photoelectron spectroscopy of the nano-mimetic enzyme material according to example 1;

FIG. 3 is a TEM appearance test chart of example 4;

FIG. 4 is a graph representing the particle size of example 4;

FIG. 5 shows the case of foliar spray application of example 6, example 13 and comparative example 2 to the foliage;

FIG. 6 shows the dry and wet weight of plants foliar-sprayed with example 6, example 11 and example 12;

FIG. 7 shows the growth of plants foliar-sprayed with comparative example 1, example 6 and examples 8 to 10;

FIG. 8 is a graph of excess reactive oxygen species scavenging by plants using the foliar spray application of example 6;

FIG. 9 shows the drought tolerance test of plants using the foliar spray fertilizer of example 6.

Detailed Description

The present invention is further described in detail below with reference to specific examples so that those skilled in the art can more clearly understand the present invention.

The following examples are provided only for illustrating the present invention, and are not intended to limit the scope of the present invention. All other embodiments obtained by a person skilled in the art based on the specific embodiments of the present invention without any inventive step are within the scope of the present invention.

In the examples of the present invention, all the raw material components are commercially available products well known to those skilled in the art, unless otherwise specified; in the examples of the present invention, unless otherwise specified, all technical means used are conventional means well known to those skilled in the art.

In the present invention, the raw materials involved are described below:

polyacrylic acid: sigma, MW-1800;

sodium oleate: adamax corporation, AR;

silwet L-77: a company of origin leaf;

ammonia water: 32% of commercially available ammonia water.

Example 1

The embodiment provides a colloidal nano-mimetic enzyme and a preparation method thereof, which specifically comprise the following operations:

step S1: mixing MnSO ₄ .H ₂ O0.425 g in 2.5mL of purified water, 4.5g of polyacrylic acid (weight average molecular weight 1800) in 5mL of purified water; mixing the manganese sulfate solution and the polyacrylic acid solution, and mixing for 15 minutes at 2500rpm on a vortex instrument to obtain a system A solution;

step S2: the mixed solution was added dropwise to 15mL of ammonia water, and stirred on a magnetic stirrer at 500rpm for 24 hours; putting the stirred solution into a 50mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 24 hours; and (3) subpackaging the solution after reaction in 2mL centrifuge tubes, centrifuging at 4000g for 1 hour at normal temperature, taking the supernatant, dialyzing for 24 hours by using a dialysis bag (MW 3500), and changing water every 8 hours to obtain the colloid containing the nano manganese-based oxide. FIG. 1 is a graph showing the lattice structure of a complex of manganese tetraoxide (Sun Y, yu Z, wang W, et al. Selective gas detection using Mn) ₃ O ₄ /WO ₃ composites as a sensing layer[J]The lattice of Beilstein Journal of Nanotechnology,2019,10 (1): 1423-1433.) was consistent and subsequently tested after lyophilization to determine a concentration of 6g/L of nano-manganese-based oxide.

The phenotype was observed, and the result is shown in FIG. 1, which is apparent as a spherical form.

The nano particle size detection is carried out on the nano particle size, and the particle size is as follows: 5.60 +/-0.98 nm

The valence state is detected, and the result is shown in fig. 2, which shows that the nanomaterial contains bivalent, trivalent and tetravalent manganese. The yield is as follows: 10.2 percent

Example 2

The embodiment provides a solid type nano-mimetic enzyme, which is prepared by the following specific steps:

step S2: the mixed solution was added dropwise to 15mL of 30wt% aqueous ammonia, and stirred on a magnetic stirrer at 500rpm for 24 hours; putting the stirred solution into a 50mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 24 hours; and (3) subpackaging the reacted solution in 2mL centrifuge tubes, centrifuging at 4000g normal temperature for 1 hour, taking the supernatant, dialyzing for 24 hours by using a dialysis bag (MW 3500), and changing water every 8 hours to obtain the colloid containing the nano manganese-based oxide.

And step S3: and freeze-drying the colloid containing the nano manganese-based oxide to obtain the solid nano manganese-based oxide.

Example 3

The embodiment provides a solid type nanometer mimic enzyme, which comprises the following specific preparation steps:

2g of manganese acetate and 100mL of ethanol are magnetically stirred uniformly, reacted in a hydrothermal kettle at 120 ℃ for 24h, centrifuged at 10000rpm and 5min, washed for 3 times and dried in vacuum for 24h to obtain brown solid.

The appearance of the strain is detected, and the phenotype of the strain shows a spherical shape.

The particle size of the product is 6.0nm by particle size detection.

Example 4

The embodiment provides a colloidal nano-mimetic enzyme and a preparation method thereof, which specifically comprises the following steps:

step A1, magnetically stirring 2g of manganese acetate, 50mL of ethanol and 50mL of ethylene glycol uniformly, reacting in a hydrothermal kettle at 120 ℃ for 24h, centrifuging at 10000rpm for 5min, washing for 3 times, and then drying in vacuum for 24h to obtain brown solid, thus obtaining the nano manganese-based oxide matrix.

And A2, mixing the nano manganese-based oxide matrix with sodium oleate for 10min, and performing ultrasonic modification for 10 min. And step A3, directly dialyzing for 12h by using a MW3500 dialysis bag. The appearance of the sample is detected, and the result is shown in figure 3, and the phenotype is fibrous;

the particle size was measured, and as a result, the length was 400nm and the width was 6.0nm, as shown in FIG. 4.

Example 5

The embodiment provides a colloidal type nano-mimetic enzyme and a preparation method thereof, which specifically comprise the following operations:

step S1: mixing MnSO ₄ .H ₂ O0.425 g was dissolved in 2.5mL of pure water, and 4.5g of polyacrylic acid (weight average molecular weight: 1800) was dissolved in 5mL of pure waterPerforming the following steps; mixing the manganese sulfate solution and the polyacrylic acid solution, and mixing for 15 minutes at 2500rpm on a vortex instrument to obtain a system A solution;

step S2: 15mL of 30wt% aqueous ammonia was added dropwise to the mixed solution, and stirred on a magnetic stirrer at 500rpm for 24 hours; putting the stirred solution into a 50mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 24 hours; and (3) subpackaging the reacted solution in 2mL centrifuge tubes, centrifuging at 4000g normal temperature for 1 hour, taking the supernatant, dialyzing for 24 hours by using a dialysis bag (MW 3500), and changing water every 8 hours to obtain the colloid containing the nano manganese-based oxide. And then the concentration of the nano manganese-based oxide is 3.2g/L by testing after freeze-drying.

The phenotype of the strain is observed, and the appearance shows a spherical shape.

The nano particle size detection is carried out on the nano particle size, and the particle size is as follows: 6.0 +/-0.54 nm. The yield was: 6 percent of

Examples 6 to 10

Embodiments 6 to 10 provide a foliar spray fertilizer and a preparation method, the preparation method specifically including the steps of:

after mixing the nano-mimic enzyme prepared in example 1, silwet L-77 and water, a foliar spray fertilizer was obtained, in which the concentration of the nano-mimic enzyme was as shown in table 1 in terms of volume percentage to the Silwet L-77.

TABLE 1 concentration of Nanomorphic enzymes from examples 6 to 10 as a percentage by volume of Silwet L-77

Example 11

The embodiment provides a foliar spray fertilizer and a preparation method thereof, and the foliar spray fertilizer is specifically prepared as follows:

after mixing the nano-mimic enzyme prepared in example 3, silwet L-77 and water, a foliar spray fertilizer was obtained, in which the concentration of the nano-mimic enzyme was 200mg/L and the volume percentage of the Silwet L-77 was 0.05%.

Example 12

after mixing the nano-mimic enzyme prepared in example 4, silwet L-77 and water, a foliar spray fertilizer was obtained, wherein the concentration of the nano-mimic enzyme was 200mg/L and the volume percentage of the Silwet L-77 was 0.05%.

Example 13

the foliar spray fertilizer was obtained by mixing the nanophase quasipeptide prepared in example 1, triton x-100 and water. In the foliage spray fertilizer, the concentration of the nano pseudoenzyme is 200mg/L, and the volume percentage of TritonX-100 is 0.05%.

Comparative example 1

The comparative example provides a foliar spray fertilizer and a preparation method, and the specific preparation method is as follows:

the foliar spray fertilizer was obtained by mixing the NanoTorulopsis prepared in example 1, silwet L-77 and water.

In the foliage spray fertilizer, the concentration of the nano-mimetic enzyme is 50mg/L, and the volume percentage of Silwet L-77 is 0.05%.

Comparative example 2

the foliar spray fertilizer was obtained by mixing the nanophase quasipeptide prepared in example 1, SDS and water. In the foliage spray fertilizer, the concentration of the nano-mimic enzyme is 50mg/L, and the volume percentage of SDS is 0.05%.

Example 14

This example provides water solubility experiments of the nanopastes of examples 1, 3 and 4, in the following specific operations:

after the nano-mimetic enzyme of example 1 was allowed to stand for 1 hour, it was observed whether or not it precipitated.

The solid particles of example 2 were dispersed in water at a dispersion concentration consistent with that of example 1, and then left to stand for 1 hour to see whether or not they removed the precipitate.

10mg of the nanomaterial of example 3 was dispersed in 3mL of pure water, and then left to stand for 1 hour, and then it was observed whether or not precipitation occurred.

After 1mL of the colloid of example 4 was dispersed in 3mL of pure water and then allowed to stand for 1 hour, it was observed whether or not precipitation occurred.

After the nano-mimetic enzyme of example 5 was allowed to stand for 1 hour, it was observed whether or not precipitation occurred

The test results are shown in table 1.

TABLE 1 Water solubility test of the nanomaterials of the examples and comparative examples

Nano material	Dispersibility	Sedimentation conditions
			Example 1	Dispersible	Whether or not
Example 2	Dispersible	Whether or not
			Example 3	Can not be dispersed	--
Example 4	Dispersible	Is that
			Example 5	Dispersible	Whether or not

From the results in table 1, it is understood that the manganese-based oxide nanomaterial is water-dispersible after the surface of the manganese-based oxide nanomaterial is modified with a surfactant component; when the shape is spherical, the spherical particles can exist stably in an aqueous dispersion. Furthermore, when the manganese-based oxide nano material is spherical and the surface of the manganese-based oxide nano material is modified with a high-molecular surfactant, the dispersity of the manganese-based oxide nano material is optimal.

Example 15

This example provides the effect of foliar spray fertilizers prepared in examples 6-13 and comparative examples 1-3 on the salt tolerance of plants by the following specific operations:

(1) The foliar spray fertilizers of example 6, example 13 and comparative example 2 were applied to the leaves of cotton seedlings in different two-leaf periods, respectively, and the fluorescence intensity of mesophyll cells was observed using a confocal microscope after incubation for 3 hours in the dark using a mixed solution of a surfactant and clear water as a control. The entry conditions of different nano-mimetic enzymes are tested by adopting a fluorescence test, and the results are shown in fig. 5, and the results show that the nano-mimetic enzymes of the examples 6 and 13 enter the leaves, while the foliar spray fertilizer of the comparative example 1 does not enter the leaves; and the effect of the nano-mimic enzyme in the leaf fertilizer of the embodiment 6 entering the leaves is the most excellent.

Meanwhile, in the present example, a single colloidal nanopaste of example 1 was used to act on the leaf surface, and it was found that the nanopaste cannot enter the leaf surface because individual globules are formed on the leaf.

(2) The foliar spray fertilizers of example 6, example 11 and example 12 were applied to the leaves of cotton seedlings at different leaf stages, respectively, and a set of the foliar spray fertilizers was applied to 0.05v/v% Silwet L-77 alone as a control and incubated in the dark for 3 hours. The seedlings are subjected to salt stress by using 200mM NaCl, after 5 days of treatment, the whole plant is weighed, then the fresh weight is removed, the water is removed at 105 ℃ for 40min, and the plant is dried at 85 ℃ to balance weight. The wet weight and the dry weight of the cotton are shown in fig. 6, and the results show that compared with the cotton coated with Silwet L-77, the fresh weight and the dry weight of the cotton coated with the foliar spray fertilizer of the embodiment of the invention are higher than those of the cotton not coated with the cotton, which indicates that the foliar spray fertilizer of the invention can improve the salt tolerance of the cotton, and further, after the foliar spray fertilizer is prepared by the nano-pseudoenzyme modified by the surfactant, the salt tolerance of the cotton is further improved, wherein the colloidal nano-pseudoenzyme containing the spherical manganese-based oxide nano-material modified by polyacrylic acid has the most excellent effect.

(3) The foliar spray fertilizers prepared in example 6, example 8 to example 10 and comparative example 1 were applied to the leaves of cotton seedlings in different two leaf periods, respectively, and a set of controls without foliar spray fertilizers was set, and the growth results are shown in fig. 7, which shows that the plants using the foliar spray fertilizer of the present invention grew more robustly than those using no foliar spray fertilizer and those containing only 50mg/L of the nanomimic enzyme, and further, the growth conditions of the plants were excellent when the concentration of the nanomimic enzyme was 200mg/L to 500mg/L.

(4) The plant can remove excessive active oxygen and enhance potassium ion (K) of plant cell ⁺ ) Retention of (D) and sodium ion (Na) ⁺ ) Thereby improving the salt tolerance of the plant; therefore, the embodiment of detecting the capability of the foliar spray fertilizer for removing the active oxygen of the plants comprises the following specific steps: the foliar spray fertilizer of example 6 was applied to leaves of cotton seedlings in two-leaf stage, only Silwet L-77 was applied as a control group, incubated in the dark for 3 hours, the seedlings were subjected to salt stress using 200mM NaCl, after 5 days of treatment, small round pieces having a diameter of about 2mM were punched from the second true leaves using a punch, incubated in a H2DCF probe for 30 minutes, and the fluorescence intensity was observed using a confocal laser microscope. H2DCF is oxidized by active oxygen to generate fluorescence, and the higher the fluorescence is, the higher the content of the active oxygen is. As a result, as shown in FIG. 8, the fluorescence intensity of the leaves after the foliar spray application was significantly weaker than that of the leaves without the foliar spray application, indicating that the foliar spray application scavenges excessive accumulation of active oxygen in the leaves.

Example 16

This example provides an experiment of the impact of foliar spray fertilizers on drought tolerance of plants, and the specific operations are as follows:

example 6 was foliar spray applied to leaves of two-leaf stage cotton seedlings, while a group of controls coated with Silwet L-77 alone was set and incubated in the dark for 3 hours. After the dark treatment, cotton was subjected to osmotic stress using 15% (W/V) PEG (MW 6000). After 7 days of treatment, the cotton phenotype is shown in FIG. 9, and the results show that the cotton applied with the foliar spray fertilizer of example 6 has the effect of improving the drought tolerance of plants because only the control group of Silwet L-77 is used.

It should be noted that the above examples are only for further illustration and description of the technical solution of the present invention, and are not intended to further limit the technical solution of the present invention, and the method of the present invention is only a preferred embodiment, and is not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The manganese element foliar spray fertilizer is characterized by comprising the following components:

the nano-enzyme analogue is colloid containing manganese-based oxide nano-materials;

in the foliar spray fertilizer, the concentration of the nano-mimic enzyme is 150 mg/L-2000 mg/L, and the surfactant is Silwet L-77;

the manganese-based oxide nano material is fibrous and is modified by sodium oleate;

the preparation method of the nano-pseudo enzyme comprises the steps of mixing divalent manganese salt or a solution containing the divalent manganese salt with a dispersion liquid, carrying out hydrothermal reaction under the condition of oxygen, mixing with sodium oleate, carrying out ultrasonic treatment, and finally carrying out dialysis purification to obtain the nano-pseudo enzyme;

the dispersion liquid is a mixed liquid of ethanol and glycol;

the hydrothermal reaction is carried out for 20-36 hours at the temperature of 100-150 ℃.

2. The foliar spray fertilizer of claim 1 wherein the surfactant is present in an amount of 0.04% to 0.06% by volume.

3. The elemental manganese foliar spray fertilizer of claim 1, wherein the concentration of the manganese-based oxide nanomaterial in the colloid is 5g/L to 7g/L.

4. The elemental manganese foliar spray fertilizer of claim 5363 of any one of claims 1~3 wherein the concentration of the nanophase quasiase is 200mg/L to 500mg/L.

5. The method of preparing a foliar spray fertilizer of manganese of any of claims 1~4 wherein the foliar spray fertilizer of manganese is obtained by mixing the nanopastemidase with the surfactant.