CN117924736A - MOF material for complex fertilizer, preparation method and application - Google Patents
MOF material for complex fertilizer, preparation method and application Download PDFInfo
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- CN117924736A CN117924736A CN202410120938.0A CN202410120938A CN117924736A CN 117924736 A CN117924736 A CN 117924736A CN 202410120938 A CN202410120938 A CN 202410120938A CN 117924736 A CN117924736 A CN 117924736A
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- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000003337 fertilizer Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 5
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- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 3
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- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-N 0.000 claims description 4
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- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims 1
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
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- Fertilizers (AREA)
Abstract
The invention provides a MOF material for a complex fertilizer, a preparation method and application. The MOF material has a structure that M 1M2(CACEB);M1、M2 independently represents one of Ca 2+、Zn2+、Mn2+、Mg2+、Cu2+、Fe2+ and divalent rare earth elements; CACEB represents a compound having a centrosymmetric structure; the compound has four carboxyl groups, two benzene rings and two secondary amine groups; m 1、M2 is linked to the carboxyl group, respectively. The MOF material provided by the invention has excellent permeability and wettability, can provide trace elements for crops, simultaneously promote the absorption of trace elements by crop root systems, improve the symptoms of plants and achieve the effect of increasing income.
Description
Technical Field
The invention relates to the technical field of fertilizers, in particular to a MOF material for a complex fertilizer, a preparation method and application.
Background
How to maintain harmony and balance among agricultural production, soil and environment is a topic of current interest. Continuous large-scale grain production and unreasonable fertilizer application present problems to the soil and environment, such as trace element starvation, soil acidification, groundwater pollution and air pollution problems, and in response to these problems, scientific application of fertilizer may be one of the most operable, convenient and efficient methods. Around the core problem, the research and development of novel fertilizers or auxiliary agents becomes a research hot spot at home and abroad in recent years.
The trace elements such as calcium, iron, zinc, manganese, boron, molybdenum and the like are mostly components of enzymes or coenzyme for promoting photosynthesis, respiration, substance conversion and the like in plants, and are very active in plants. When a certain trace element in the soil for providing plant nutrient elements is insufficient, the plant can be in a 'lack condition', so that the yield of crops is reduced, the quality is reduced, and even the particles are not harvested when serious. In this case, trace element fertilizer is applied, so that a very obvious income increasing effect is often achieved.
Commonly used trace element fertilizers, such as: calcium sulfate, manganese sulfate, zinc sulfate and the like have the common defects that the calcium sulfate, the manganese sulfate, the zinc sulfate and the like are easy to react with phosphate and borate in soil to generate substances which are difficult to ionize, crops cannot absorb the substances, the utilization rate is low, and fertilizer waste and even environmental pollution are easy to cause. The stability problem of the trace element fertilizer is to be solved.
Until the 20 th century complex fertilizer is developed in China, the fertilizer efficiency is obviously higher than that of inorganic salt. The common ligands are mainly EDTA series, amino acids, humic acid and lignin. The problem that metal trace element fertilizers are easy to antagonize with phosphates and borates can be solved through chelating reaction of coordination compounds and metal elements, but EDTA (ethylene diamine tetraacetic acid) complex fertilizers are high in price, the molecular weight of humic acid is large, the coordination capacity is poor, the effect of lignin on metal ions is poor, trace elements cannot be completely absorbed by plants, and even crop poisoning can occur when the trace elements are used excessively.
Therefore, a trace element complex material which can be efficiently matched with trace elements, is easy to ionize, has strong stability and strong universality is needed.
Disclosure of Invention
The invention aims to: the invention aims to provide an MOF material for a complex fertilizer, a preparation method and application thereof, so as to solve the problems of poor effect and low stability of ligands and metal ions of the existing complex fertilizer.
The technical scheme of the invention is as follows:
in one aspect, the application provides a MOF material for a complex fertilizer, the MOF material having a structure of M 1M2 (CACEB);
m 1、M2 each independently represents Ca 2+、Zn2+、Mn2+、Mg2+、Cu2+、Fe2+ or one of divalent rare earth elements;
CACEB represents a compound having a centrosymmetric structure; the compound has four carboxyl groups, two benzene rings and two secondary amine groups;
M 1、M2 is linked to the carboxyl group, respectively.
Preferably, each of said M 1、M2 independently represents one of Ca 2+、Zn2+、Mn2+.
The metal elements represented by M 1、M2 may be the same or different, for example, when M 1 is represented by Ca 2+, M 2 may be represented by Ca 2+, zn 2+ or Mn 2+, and the present application is not limited to whether the metal elements represented by M 1 and M 2 are the same or different.
In some embodiments, the metal elements represented by M 1、M2 are the same, and each of them represents one of Ca 2+、Zn2+、Mn2+、Mg2+、Cu2+、Fe2+ and a divalent rare earth element; preferably, said M 1、M2 are all identical representing one of Ca 2+、Zn2+、Mn2+.
In some embodiments, the CACEB is the product of reacting 4,4' -stilbenedicarboxylic acid with an amino acid.
In some embodiments, the amino acid is selected from one or more of glycine (Gly), alanine (Ala), valine (Val), leucine (Lue), isoleucine (Ile), serine (Ser), threonine (Thr), cysteine (Cys), methionine (Met), aspartic acid (Asp), glutamic acid (Glu), asparagine (Asn), glutamine (gin), lysine (Lys), arginine (Arg), histidine (His), proline (Pro), phenylalanine (Phe), tyrosine (Tyr), tryptophan (Trp). The grafted amino acid can make the permeability and wettability of the MOF material better, promote the absorption of crop root systems, and has synergistic effect on water-soluble fertilizers.
Preferably, the amino acid is selected from one or more of glycine, leucine, phenylalanine, threonine; further preferably, the amino acid is phenylalanine. The pi bond on the phenylalanine makes the complex formed by the phenylalanine and metal ions more stable, and reduces the loss of trace elements.
In another aspect, the application also provides a method for preparing the MOF material, comprising:
step 1: adding 4,4' -stilbenedicarboxylic acid (CDOA) and strong base into deionized water, and mixing until pH is alkaline; adding amino acid, and heating for reaction; after the reaction is finished, regulating the pH to be acidic, and extracting and washing to obtain a compound A;
Step 2: adding potassium hydroxide into deionized water, and stirring while adding to obtain alkali liquor; then adding the compound A, stirring uniformly, heating and preserving heat; after the heat preservation is finished, adding the precursors of M 1 and/or M 2, and continuing to preserve the heat; and standing for precipitation after heat preservation is finished, washing, centrifuging and drying the precipitate to obtain the MOF material.
In the step 1, the effect of adding strong alkali is to protect the carboxyl on the 4,4' -diphenylethylene dicarboxylic acid, avoid the reaction with amino acid, and ensure that the amino group on the amino acid can perform Michael addition reaction with double bond.
In the step 2, the concentration of potassium hydroxide in the alkali liquor is 1-5mol/L.
In the above step 2, 1mol of the compound A was added per 1L of the lye.
In the step 2, the heating and the heat preservation are carried out, the heating temperature is 60-70 ℃, and the heat preservation time is 1-5h.
In the step 2, the ratio of the total added molar amount of the precursor of M 1 and/or M 2 to the added molar amount of the compound A is 1-1.2:1.
In step 2 above, the precursors of M 1 and/or M 2 are represented as a mixture of sulfates and oxides of M 1 and/or M 2. Specifically, when M 1 and M 2 are the same, using Ca 2+ as an example, the precursors of M 1 and/or M 2 are denoted as calcium sulfate and calcium oxide; when M 1 and M 2 are different, and taking M 1 as Ca 2+,M2 and Zn 2+ as an example, the precursors of M 1 and/or M 2 are expressed as a mixture of calcium sulfate, calcium oxide, zinc sulfate and zinc oxide. The above selections are for example only, and the derivation of other metal ions for M 1 and/or M 2 is likewise within the scope of the application.
More specifically, in the precursor of each metal element, the ratio of the addition molar amounts of the sulfate and the oxide is 4 to 5:1-2. Specifically, when M 1 and M 2 are the same, taking Ca 2+ as an example, the precursors of M 1 and/or M 2 are calcium sulfate and calcium oxide, and the ratio of the added molar amounts of calcium sulfate and calcium oxide is 4-5:1-2; when M 1 and M 2 are different, taking M 1 as Ca 2+,M2 and Zn 2+ as an example, and the precursors of M 1 and/or M 2 are respectively calcium sulfate, calcium oxide, zinc sulfate and zinc oxide, the ratio of the added molar amounts of the calcium sulfate to the calcium oxide is 4-5:1-2, the ratio of the addition molar quantity of zinc sulfate to zinc oxide is also 4-5:1-2. The above selections are merely examples, and when M 1 and/or M 2 select other metal ions, the ratio of the added amounts is derived according to the above rules, and the present application is also within the scope of the present application.
In another aspect, the application also provides the use of the MOF material in a plant trace element deficient land.
Preferably, the application comprises the use of a MOF material for the complexing fertilizer in combination with an EDTA complexing fertilizer.
More preferably, the structure of the EDTA complex fertilizer is selected from one of the formula I or the formula II;
When the structure of the EDTA complex fertilizer is shown as a formula I, M represents Ca 2+、Zn2+、Mn2+、Mg2+、Cu2+ or one of divalent rare earth elements; n represents one of NH 4+、K+;
When the structure of the EDTA complex fertilizer is shown as a formula II, M represents one of Fe 3+ and trivalent rare earth elements; n represents one of NH 4+、K+.
More preferably, the structure of the EDTA complex fertilizer is shown in a formula I, M represents one of Ca 2+、Zn2+、Mn2+, and N represents K +.
The beneficial effects are that:
The MOF material provided by the invention has excellent permeability and wettability, can be used as a single crop compound fertilizer or can be matched with other fertilizers, can provide trace elements for crops, can promote the absorption of trace elements by crop root systems, improves the symptoms of plants, and achieves the effect of increasing income.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
The chemical reagents used in the invention are all common commercial analytical pure unless specified.
Example 1
Step 1: 1mol of 4,4' -diphenylethylene dicarboxylic acid and KOH were added to 1L of deionized water and mixed until pH=9; adding 2.2mol glycine, and heating at 40 ℃ for reaction for 5 hours; after the reaction is finished, regulating the pH to 6, and extracting and washing to obtain a compound A;
Step 2: adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then adding 1mol of compound A, uniformly stirring, and heating at 90 ℃ for 1h; after the heat preservation is finished, 0.8mol of calcium sulfate and 0.4mol of calcium oxide are added, and the heat preservation is continued for 1h; cooling to room temperature after heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material Ca 2 (CACEB-Gly).
Example 2
Step 1: 1mol of 4,4' -diphenylethylene dicarboxylic acid and KOH were added to 1L of deionized water and mixed until pH=9; adding 2.2mol leucine, and heating at 40 ℃ for reaction for 5 hours; after the reaction is finished, regulating the pH to 6, and extracting and washing to obtain a compound A;
Step 2: adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then adding 1mol of compound A, uniformly stirring, and heating at 90 ℃ for 1h; after the heat preservation is finished, 0.8mol of calcium sulfate and 0.4mol of calcium oxide are added, and the heat preservation is continued for 1h; and cooling to room temperature after the heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material Ca 2 (CACEB-Luc).
Example 3
Step 1: 1mol of 4,4' -diphenylethylene dicarboxylic acid and KOH were added to 1L of deionized water and mixed until pH=9; 2.2mol phenylalanine is added, and the mixture is heated at 40 ℃ for reaction for 5 hours; after the reaction is finished, regulating the pH to 6, and extracting and washing to obtain a compound A;
Step 2: adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then adding 1mol of compound A, uniformly stirring, and heating at 90 ℃ for 1h; after the heat preservation is finished, 0.8mol of calcium sulfate and 0.4mol of calcium oxide are added, and the heat preservation is continued for 1h; cooling to room temperature after heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material Ca 2 (CACEB-Phe).
Example 4
Step 1: 1mol of 4,4' -diphenylethylene dicarboxylic acid and KOH were added to 1L of deionized water and mixed until pH=9; 2.2mol threonine is added, and the mixture is heated at 40 ℃ to react for 5 hours; after the reaction is finished, regulating the pH to 6, and extracting and washing to obtain a compound A;
Step 2: adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then adding 1mol of compound A, uniformly stirring, and heating at 90 ℃ for 1h; after the heat preservation is finished, 0.8mol of calcium sulfate and 0.4mol of calcium oxide are added, and the heat preservation is continued for 1h; cooling to room temperature after heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material Ca 2 (CACEB-Thr).
Example 5
Step 1: 1mol of 4,4' -diphenylethylene dicarboxylic acid and KOH were added to 1L of deionized water and mixed until pH=9; adding 2.2mol glycine, and heating at 40 ℃ for reaction for 5 hours; after the reaction is finished, regulating the pH to 6, and extracting and washing to obtain a compound A;
Step 2: adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then adding 1mol of compound A, uniformly stirring, and heating at 90 ℃ for 1h; after the heat preservation is finished, 0.8mol of zinc sulfate and 0.4mol of zinc oxide are added, and the heat preservation is continued for 1h; and cooling to room temperature after heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material Zn 2 (CACEB-Gly).
Example 6
Step 1: 1mol of 4,4' -diphenylethylene dicarboxylic acid and KOH were added to 1L of deionized water and mixed until pH=9; adding 2.2mol glycine, and heating at 40 ℃ for reaction for 5 hours; after the reaction is finished, regulating the pH to 6, and extracting and washing to obtain a compound A;
Step 2: adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then adding 1mol of compound A, uniformly stirring, and heating at 90 ℃ for 1h; after the heat preservation is finished, adding 0.8mol of manganese sulfate and 0.4mol of manganese oxide, and continuing to preserve the heat for 1h; cooling to room temperature after heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material Mn 2 (CACEB-Gly).
Example 7
Step 1: 1mol of 4,4' -diphenylethylene dicarboxylic acid and KOH were added to 1L of deionized water and mixed until pH=9; adding 2.2mol glycine, and heating at 40 ℃ for reaction for 5 hours; after the reaction is finished, regulating the pH to 6, and extracting and washing to obtain a compound A;
Step 2: adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then adding 1mol of compound A, uniformly stirring, and heating at 90 ℃ for 1h; after the heat preservation is finished, 0.4mol of manganese sulfate, 0.2mol of manganese oxide, 0.4mol of calcium sulfate and 0.2mol of calcium oxide are added, and the heat preservation is continued for 1h; and cooling to room temperature after heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material CaMn (CACEB-Gly).
Comparative example 1
Adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then 1mol of 4,4' -diphenylethylene dicarboxylic acid is added, and the mixture is heated and kept at 90 ℃ for 1 hour after being stirred uniformly; after the heat preservation is finished, 0.8mol of calcium sulfate and 0.4mol of calcium oxide are added, and the heat preservation is continued for 1h; and cooling to room temperature after the heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material Ca 2 (SDAA).
Comparative example 2
Adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then 1mol of 1, 2-tetra (4-carboxystyrene) ethylene is added, and the mixture is heated and kept at 90 ℃ for 1 hour after being stirred uniformly; after the heat preservation is finished, 0.8mol of calcium sulfate and 0.4mol of calcium oxide are added, and the heat preservation is continued for 1h; and cooling to room temperature after heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material Ca 2 (TCPE).
Comparative example 3
Adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then adding 1mol of ethylenediamine tetraacetic acid, uniformly stirring, and heating at 90 ℃ for 1h; after the heat preservation is finished, 0.8mol of calcium sulfate and 0.4mol of calcium oxide are added, and the heat preservation is continued for 1h; cooling to room temperature after heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material Ca 2 (EDTA).
Comparative example 4
Adding 2mol of KOH into 2L of deionized water, and stirring while adding to obtain alkali liquor; then adding 1mol of ethylenediamine tetraacetic acid, uniformly stirring, and heating at 90 ℃ for 1h; after the heat preservation is finished, 0.4mol of zinc sulfate and 0.2mol of zinc oxide are added, and the heat preservation is continued for 1 hour; cooling to room temperature after heat preservation is finished, standing for precipitation, washing, centrifuging and drying the precipitate to obtain the MOF material ZnK 2(EDTA),ZnK2 (EDTA) with the structure shown in the formula I-1.
Test experiment:
Selecting a test field near the economic development area of Qingzhou city in Weifang, shandong, planting corn, dividing the test field into 12 parts with equal area, simultaneously respectively applying the same amount of each material into the 11 parts of test fields, taking the other part of test fields as a blank control group, respectively taking soil to perform fertilizer efficiency measurement while sowing corn, and measuring the yield after corn harvesting, wherein the data are as follows:
TABLE 1
As shown in the table, the MOF material provided by the application can provide trace elements for plants when used as a complex fertilizer in the land lacking the trace elements of the plants, the average fertility of the soil in the corn growth period is far greater than that of the land without the MOF material, meanwhile, the disease occurrence rate is reduced, and the corn yield is finally improved.
Meanwhile, the MOF material provided by the application is provided with the amino acid fragment, so that the absorption of crop root systems can be effectively promoted. As can be seen from a comparison of example 1 with comparative examples 1-3, in the land to which the MOF material Ca 2 (SDAA) having no amino acid fragment was added, the corn yield was inferior to that of the land to which Ca 2 (CACEB-Gly) was added. However, the Ca 2 (TCPE) material provided in the reference 2 has a symmetrical structure with a plurality of benzene rings, and is more difficult to ionize when combined with metal elements than the MOF material provided in the present application, and the crops cannot obtain corresponding trace elements, so that the yield is improved but is inferior to that of the example 1.
The MOF material provided by the application can be mixed for use, and simultaneously provides various microelements for crops, so that the symptoms of plants are improved, and the effect of increasing income is achieved. The EDTA complex can be added together to achieve unexpected synergistic effect, so that the fertilizer efficiency and yield of the land are further improved.
The present invention is capable of other and further embodiments and its several details are capable of modification and variation in light of the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The MOF material for the complex fertilizer is characterized in that the MOF material has a structure of M 1M2 (CACEB);
m 1、M2 each independently represents Ca 2+、Zn2+、Mn2+、Mg2+、Cu2+、Fe2+ or one of divalent rare earth elements;
CACEB represents a compound having a centrosymmetric structure; the compound has four carboxyl groups, two benzene rings and two secondary amine groups;
M 1、M2 is linked to the carboxyl group, respectively.
2. The MOF material for a complex fertilizer according to claim 1, wherein the metal elements represented by M 1、M2 are different.
3. The MOF material for a complex fertilizer according to claim 1, wherein the metal elements represented by M 1、M2 are the same.
4. The MOF material for a complex fertilizer according to claim 1, wherein CACEB is a product of a reaction of 4,4' -stilbenedicarboxylic acid with an amino acid.
5. The MOF material for a complex fertilizer according to claim 1, wherein the amino acid is one or more selected from glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, aspartic acid, glutamic acid, asparagine, glutamine, lysine, arginine, histidine, proline, phenylalanine, tyrosine, tryptophan; preferably, the amino acid is selected from one or more of glycine, leucine, phenylalanine, threonine; more preferably, the amino acid is phenylalanine.
6. The method for preparing the MOF material for a complex fertilizer according to any one of claims 1 to 5, comprising the steps of:
Step 1: adding 4,4' -diphenylethylene dicarboxylic acid and strong alkali into deionized water, and mixing until the pH is alkaline; adding amino acid, and heating for reaction; after the reaction is finished, regulating the pH to be acidic, and extracting and washing to obtain a compound A;
Step 2: adding potassium hydroxide into deionized water, and stirring while adding to obtain alkali liquor; then adding the compound A, stirring uniformly, heating and preserving heat; after the heat preservation is finished, adding the precursors of M 1 and/or M 2, and continuing to preserve the heat; and standing for precipitation after heat preservation is finished, washing, centrifuging and drying the precipitate to obtain the MOF material.
7. The method for producing MOF material for a complex fertilizer according to claim 6, wherein in step 2, the ratio of the total molar amount of the precursors of M 1 and/or M 2 to the molar amount of the compound a added is 1 to 1.2:1.
8. The method for producing MOF material for a complex fertilizer according to claim 6, wherein the precursor of M 1 and/or M 2 is represented by a mixture of sulfate and oxide of M 1 and/or M 2; the ratio of the added molar amounts of the sulfate and the oxide is 4-5:1-2.
9. Use of the MOF material for a complex fertilizer according to any one of claims 1 to 5 in a land lacking plant trace elements.
10. The use of the MOF material for a complex fertilizer according to claim 9, comprising mixing the MOF material for a complex fertilizer with EDTA complex fertilizer; the structure of the EDTA complex fertilizer is selected from one of a formula I or a formula II;
When the structure of the EDTA complex fertilizer is shown as a formula I, M represents Ca 2+、Zn2+、Mn2+、Mg2+、Cu2+ or one of divalent rare earth elements; n represents one of NH 4+、K+;
When the structure of the EDTA complex fertilizer is shown as a formula II, M represents one of Fe 3+ and trivalent rare earth elements;
n represents one of NH 4+、K+.
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