CN112898075B - Metal organic frame fertilizer and solid phase synthesis method thereof - Google Patents

Abstract

The invention relates to a metal organic frame fertilizer and a solid phase synthesis method thereof, which react solid reactants consisting of metal node materials, organic joint materials and counter ion materials at normal temperature to synthesize a frame through mechanochemical reaction, thereby obtaining the novel slow release fertilizer of metal organic frames. The method can realize solid-phase synthesis of the metal organic frame fertilizer under low heat, and the prepared metal organic frame fertilizer has better nutrient slow release performance.

Description

Metal organic framework fertilizer and its solid-phase synthesis method

technical field

The invention belongs to the technical field of fertilizer manufacturing, and particularly relates to a metal organic framework fertilizer and a solid-phase synthesis method thereof.

Background technique

With the growth of the world's population, the issue of food security has become more and more important, and how to maintain the harmony and balance between agricultural production, soil and environment is a topic of current concern. Continuous large-scale food production and unreasonable fertilizer application have brought many problems to soil and environment, such as lack of trace elements ^[1] , soil acidification ^[2] , groundwater pollution and air pollution problems ^[3] , etc. When dealing with these problems, the scientific application of chemical fertilizers may be one of the most feasible, convenient and effective methods. Focusing on the core issue of how to improve the utilization rate of fertilizers, new fertilizers and their green synthesis methods have become a research hotspot at home and abroad in recent years.

Metal-organic frameworks are coordination polymers with metal ions or ion clusters as nodes and organic ligands. By using different ligands, they can form different framework structures, and at the same time form ultra-high porosity and specific surface area. Therefore, metal organic frameworks are widely used in gas adsorption and separation, heterogeneous catalysis, photocatalysis, chemical sensing, proton conduction, biomedicine and other fields ^[4] .

The common synthesis methods of metal organic frameworks are: slow evaporation method, solvothermal synthesis method, microwave synthesis method, electrochemical synthesis method, ultrasonic chemical synthesis method and mechanochemical synthesis method, most of which are liquid phase synthesis; among them, mechanochemical synthesis method The method is a faster and easier solid-phase synthesis method ^[5] . Mechanochemical synthesis, that is, the direct absorption of mechanical energy to initiate or maintain chemical synthesis reactions ^[6-7] , has potential advantages such as large-scale production, high quantitative yields, avoiding large amounts of solvents and high temperatures ^[8] . One of the most important techniques in mechanochemical synthesis is solvent-free synthesis, usually using hydrated metal salts as raw materials, and the coordination water is released after grinding ^[9] .

Previous studies have preliminarily confirmed the potential of metal-organic frameworks as fertilizer carriers ^[10-15] . The synthesis methods used in the existing research are all hydrothermal synthesis methods with urea as the structure-directing agent. During the reaction, the urea is decomposed and attached to the inside of the frame in the form of ammonium ions. The required reaction temperature is above 100 °C, and the autogenous pressure is High, and time-consuming, low yield (mostly between 10% and 20%), the mother liquor needs to be recycled, and the product needs to be separated and dried; the above points will further increase the synthesis of metal organic frameworks as fertilizers and processing costs.

references

[1]A,K.M.,A,G.I.,A,D.S.,A,M.M.,B,K.M.,&C,W.K.,et al.(0).Controlledrelease micronutrient fertilizers for precision agriculture–a review.ence of The Total Environment,712 .

[2] Hao, T., Zhu, Q., Zeng, M., Shen, J., & Vries, W.D.. (2020). Impacts of nitrogen fertilizer type and application rate on soil acidification rate under a wheat-maize double cropping system. Journal of Environmental Management, 270, 110888.

[3] Chen, J., Lu, S., Zhang, Z., Zhao, X., Li, X., & Ning, P., et al. (2017). Environmentally friendly fertilizers: a review of materials used and their effects on the environment.ence of the Total Environment, 613-614.

[4] Jiao, L., Seow, J.Y.R., Skinner, W.S., Wang, Z.U., & Jiang, H.L.. (2019). Metal–organic frameworks: structures and functional applications. MaterialsToday, 27, 43-68.

[5] Dey, C., Kundu, T., Biswal, B.P., Mallick, A., & Banerjee, R.. (2014). Crystalline metal-organic frameworks (mofs): synthesis, structure and function. Acta Crystallographica, 70( 1), 3-10.

(2017).Mechanochemistry:a force ofsynthesis.Acs Cent,3(1),13-19.[6] Do, JL, & Tomislav

(2017). Mechanochemistry: a force of synthesis. Acs Cent, 3(1), 13-19.

[7] Tan, D., & García, Felipe. (2019). Main group mechanochemistry: from curiosity to established protocols. Chemical Society Reviews.

[8] Tanaka, S.. (2020). Mechanochemical synthesis of mofs. Metal-Organic Frameworks for Biomedical Applications, 197-222.

[9] Amery, N.A., Abid, H.R., Al-Saadi, S., Wang, S., & Liu, S.. (2020). Facile directions for synthesis, modification and activation of mofs. Materials Today Chemistry, 17, 100343.

[10] Anstoetz, M., Clark, M.W., & Yee, L.H.. (2017). Response surfaceoptimisation of an oxalate–phosphate–amine metal–organic framework (opa-mof) ofiron and urea. Journal of Inorganic and Organometallic Polymers and Materials , 27(4), 996-1013.

[11] Anstoetz, M., Rose, T.J., Clark, M.W., Yee, L.H., Raymond, C.A., & Vancov, T.. (2015). Novel applications for oxalate-phosphate-amine metal-organic-frameworks (opa-mofs ): can an iron-based opa-mof be used as slow-releasefertilizer? .PLOS ONE, 10(12), e0144169.

Yasmin de Guzman,Conato,M.T.,&Payawan,L.M..(2018).Facile fabrication of a potential slow-release fertilizerbased on oxalate-phosphate-amine metal-organic frameworks(opa-mofs).MaterialsScience Forum,936,14-19.[12] Usman, KAS, Buenviaje, SC,

Yasmin de Guzman, Conato, MT, & Payawan, LM. (2018). Facile fabrication of a potential slow-release fertilizer based on oxalate-phosphate-amine metal-organic frameworks (opa-mofs). Materials Science Forum, 936, 14-19.

[13] Wu, K., Du, C., Ma, F., Shen, Y., & Zhou, J.. (2019). Optimization of metal–organic(citric acid) frameworks for controlled release of nutrients. RSC Adv , 9(55), 32270-32277.

[14] Wu, K.; Du, C.; Ma, F.; Shen, Y.; Liang, D.; & Zhou, J.. (2019). Degradation of Metal-Organic Framework Materials as Controlled-Release Fertilizers in CropFields .Polymers, 11,947.

[15] Wu Ke, Du Changwen, Shen Yazhen, Ma Fei. (2019). A preliminary study on the application of new metal organic framework (mof) fertilizers on rice. Journal of Plant Nutrition and Fertilizers, 25(12).

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a metal organic framework fertilizer and a solid-phase synthesis method thereof.

In order to realize the above-mentioned technical purpose, the present invention adopts the following technical scheme,

A solid-phase synthesis method of a metal organic framework fertilizer, wherein a framework is synthesized from mixed solid-phase reactants by mechanical action at normal temperature;

The solid-phase reactant raw material is composed of metal node material, organic link material and counter ion material;

The solid-phase reactant raw material contains elements P, Fe, and one of elements N and K.

Further, the metal organic framework is synthesized by using iron salt as metal node material, oxalic acid as organic linker material, and ammonium ion or potassium ion as counter ion.

Further, the ammonium ion or potassium ion exists in the solid-phase reactant raw material in the form of phosphate.

Further, the solid-phase reactant raw materials are put into a ball mill for grinding reaction to synthesize the metal organic framework.

Further, the reaction conditions are: grinding at 600-700 rpm for 10-15 minutes; preferably grinding for 12 minutes. 600-700 rpm is conducive to the solid-phase reaction to obtain sufficient mechanical energy in the middle and late stages of the reaction, which can effectively improve the yield and shorten the reaction time.

Further, the grinding method is intermittent grinding. Intermittent grinding is beneficial to the dissipation of heat energy generated in the high-speed grinding process, and at the same time, it is beneficial for the reactants to fully react and improve the yield.

Further, for each grinding cycle of intermittent grinding, grinding time: pause time = 2:1; preferably, each cycle is ground for 2 minutes, with a pause of 1 minute.

Further, after the solid-phase reactant mixing reaction is completed, the product is dried at 40°C-135°C.

Further, the reactant feeding molar ratio is iron ion: counter ion: oxalic acid=1:4-8:1-2; preferably 1:4:1.

The present invention uses a mechanochemical method to synthesize a new metal organic framework under the condition of low thermal solid phase, and supports ammonium, phosphorus, potassium and iron as plant nutrients.

Another object of the present invention is to provide a metal organic framework fertilizer, which uses iron salts as metal node materials, oxalic acid as organic linker materials, and ammonium ions or potassium ions as counter ions to form the metal organic framework.

Further, the molar ratio of each component in the metal organic framework fertilizer is: iron ion: counter ion: oxalic acid=1:4-8:1-2; preferably 1:4:1.

In the invention, under the condition of room temperature or near room temperature, the iron salt is used as the inorganic part, the oxalic acid is used as the organic linker, and the ammonium ion or potassium ion is used as the counter ion, and the metal organic framework fertilizer is efficiently synthesized. Through elemental composition analysis, the framework contains nutrient elements N, K, P, Fe. Through the hydrostatic cultivation test, the metal organic framework fertilizer of the present invention has high nutrient content and good slow release performance.

Description of drawings

Figure 1 is a graph of percent (%) nutrient release from the products of the Example.

Figure 2 is an X-ray powder diffractogram of Example products.

Detailed ways

The main material models used in the examples are as follows:

Planetary super ball mill Puluerisette 7, FRISCH, Germany;

ICAP-OES UK Thermo Fisher Company.

Example 1

Weigh 0.02 moles of ferric chloride, 0.04 moles of diammonium hydrogen phosphate, and 0.02 moles of oxalic acid, place them in an agate ball mill, and grind them at 600 rpm using a planetary super ball mill. Pause for 1 minute every 2 minutes, and grind 6 times in total. 12 minutes; the mixture was taken out and put into an evaporating dish, dried at 60° C., and finally the dried mixture was washed, filtered and dried to obtain the product.

Determination method of nutrient sustained-release characteristics: accurately weigh 1.5g of the product into a ground-mouth reagent bottle, add 50mL of deionized water, pour out the solution every 7 days and add 50mL of deionized water again; use indophenol blue colorimetry to determine Ammonia nitrogen content, available phosphorus, available potassium and available iron content were determined by ICAP-OES.

The yield of Example 1 is 33%-34%, and the nutrient content of the prepared product is as follows: N, 4-5.5%, P, 14-16%, Fe, 18-19%;

Through the hydrostatic incubation test, the cumulative release rate of the product prepared in Example 1 within 21 days is about N, 40%, P, 14%, Fe, 4%.

Example 2

Weigh 0.02 moles of ferric chloride, 0.04 moles of dipotassium hydrogen phosphate, and 0.02 moles of oxalic acid, place them in an agate ball mill, and grind them at 700 rpm using a planetary super ball mill. Pause for 1 minute every 2 minutes, and grind 6 times in total. 12 minutes; the mixture was taken out and put into an evaporating dish, dried at 60° C., and finally the dried mixture was washed, filtered and dried to obtain the product.

The yield of Example 2 is 33% to 34%, and the nutrient content of the prepared product is as follows: K, 12-13%, P, 14-15%, Fe, 15-16%;

Through the hydrostatic incubation test, the cumulative release rate of the product prepared in Example 1 within 21 days is about K, 23%, P, 12%, Fe, 5%.

Example 3

The only difference from Example 1 is that the feeding amounts are: 0.02 moles of ferric chloride, 0.02 moles of diammonium hydrogen phosphate, and 0.02 moles of oxalic acid. The dried mixture was washed, filtered and dried. The yield of Example 3 was lower than 0.1%, indicating that the proportion of counter ions was too low to obtain the target product.

Example 4

The only difference from Example 1 is that the feeding amounts are: 0.02 moles of ferric chloride, 0.06 moles of diammonium hydrogen phosphate, and 0.02 moles of oxalic acid.

The yield rate prepared in Example 4 is 5% to 8%, and the nutrient content of the prepared product is as follows: N, 2.5-5%, P, 11-13%, Fe, 18-19%.

Example 5

The only difference from Example 1 is that the mixture was taken out and put into an evaporating dish, dried at 135° C., and finally the dried mixture was washed, filtered and dried to obtain the product.

The yield of Example 5 is 42%-43%, and the nutrient content of the prepared product is as follows: N, 4-5.5%, P, 14-16%, Fe, 18-19%.

Example 6

The only difference from Example 2 is that the feeding amounts are: 0.02 moles of ferric chloride, 0.06 moles of dipotassium hydrogen phosphate, 0.02 moles of oxalic acid, and 0.04 moles of urea. product is obtained.

The yield of Example 6 is 33%-34%, and the nutrient content of the prepared product is as follows: N, 0.1-0.2%, K, 12-13%, P, 11-12%, Fe, 15-16%;

Through the hydrostatic incubation test, the cumulative release rate of the product prepared in Example 5 within 21 days is about K, 16%, P, 16%, Fe, 5%.

Claims (5)

1. a solid-phase synthesis method of metal organic framework fertilizer, is characterized in that, at normal temperature, solid-phase reactant raw material is put into ball mill grinding reaction, and the solid-phase reactant of mixing is made to synthesize metal organic framework; The solid-phase reactant raw material is composed of metal node material, organic link material and counter ion material; the metal organic framework is synthesized by using iron salt as metal node material, oxalic acid as organic link material, and ammonium ion or potassium ion as counter ion; The grinding method is intermittent grinding; The reactant feeding molar ratio is iron ion: counterion: oxalic acid=1:4-8:1-2; The reaction conditions are: 600~700 rpm; grinding time is 10~15 minutes; each grinding cycle of intermittent grinding, grinding time: pause time = 2:1; Dry at -135℃. 2. The method according to claim 1, wherein the grinding time is 12 minutes. 3. The method according to claim 1, wherein grinding is performed for 2 minutes per cycle, with a pause of 1 minute. 4. The method according to claim 1, wherein the molar ratio of reactants is iron ion: counter ion: oxalic acid=1:4:1. 5. The metal organic framework fertilizer prepared by the method of any one of claims 1 to 4.

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