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CN-121609930-B - Copper-based coordination polymer, preparation method and application thereof in nitrogen fertilizer synergism

CN121609930BCN 121609930 BCN121609930 BCN 121609930BCN-121609930-B

Abstract

The invention belongs to the technical field of fertilizer synergism, and particularly relates to a copper-based coordination polymer, a preparation method and application thereof in nitrogen fertilizer synergism, wherein the method comprises the following steps of synthesizing N 1 ,N 4 -bis (3-pyridyl) -2-butenamide by using 3-aminopyridine and fumaric acid as raw materials; and then synthesizing the N 1 ,N 4 -bis (3-pyridyl) -2-butenamide and CuCl 2 ·2H 2 O as well as 5-nitroisophthalic acid into a novel copper-based coordination polymer [ Cu (3-bbpa) (5-NIPA) ] -H 2 O by a hydrothermal method, wherein the novel copper-based coordination polymer is blue fine crystals. The copper-based coordination polymer prepared by the invention can synchronously target the active center of urease and the functional unit of nitrifying microorganism, and the three-dimensional network structure of the copper-based coordination polymer not only enhances the stability of the material in soil, but also realizes double blocking of nitrogen conversion key enzyme through multi-site synergism.

Inventors

  • ZHANG LEI
  • ZHOU XINWANG
  • WANG LINGLI
  • ZHANG LILI
  • DUAN WENLONG
  • SHI XIAOYU
  • ZHANG SHUANG
  • LUAN JIAN

Assignees

  • 中国科学院沈阳应用生态研究所

Dates

Publication Date
20260512
Application Date
20260203

Claims (7)

  1. 1. A method for preparing a copper-based coordination polymer, comprising the steps of: Step 1, synthesizing N 1 ,N 4 -bis (3-pyridyl) -2-butenamide by using 3-aminopyridine and fumaric acid as raw materials; Step 2, synthesizing a copper-based coordination polymer [ Cu (3-bbpa) (5-NIPA) ] H 2 O which is blue fine crystal by using N 1 ,N 4 -bis (3-pyridyl) -2-butenamide and CuCl 2 ·2H 2 O as well as 5-nitroisophthalic acid through a hydrothermal method; step 2 comprises the following specific steps: Step 201, putting CuCl 2 ·2H 2 O and N 1 ,N 4 -bis (3-pyridyl) -2-butenamide and 5-nitroisophthalic acid into a hydrothermal kettle; step 202, adding sodium hydroxide solution into a hydrothermal kettle, and then adding distilled water into the hydrothermal kettle; Step 203, placing the hydrothermal kettle into a baking oven to be fired to obtain blue fine crystals, washing the blue fine crystals with distilled water, and carrying out suction filtration and drying to obtain the copper-based coordination polymer [ Cu (3-bbpa) (5-NIPA) ] -H 2 O; In step 201, the molar ratio of CuCl 2 ·2H 2 O to N 1 ,N 4 -bis (3-pyridyl) -2-butenamide to 5-nitroisophthalic acid is 2:1:1.5; In step 202, the concentration of sodium hydroxide solution is 0.025mol/mL, the volume ratio of sodium hydroxide solution to distilled water is 1:2, and in step 203, the hydrothermal kettle is put into a 130 ℃ oven to be fired for 4 days.
  2. 2. The method for preparing a copper-based coordination polymer according to claim 1, wherein the step 1 comprises the following specific steps: step 101, slowly adding 3-aminopyridine dissolved in pyridine solution into pyridine solution of fumaric acid, and stirring at room temperature; Step 102, dropwise adding triphenyl phosphite into the mixed liquid obtained in the step 101, heating and refluxing, standing overnight at room temperature until solid is separated out, carrying out suction filtration, recrystallizing with ethanol, and drying in air to obtain powdery solid, namely N 1 ,N 4 -bis (3-pyridyl) -2-butenamide.
  3. 3. The method for producing a copper-based coordination polymer according to claim 2, wherein the molar ratio of 3-aminopyridine, fumaric acid, and triphenyl phosphite is 2:1:1.
  4. 4. The method for producing a copper-based coordination polymer according to claim 2, wherein in step 101, 30min is stirred, and in step 102, triphenyl phosphite is added dropwise to 15 min after completion of step 101, and 10 h is heated and refluxed.
  5. 5. The copper-based coordination polymer prepared by the method according to any one of claims 1 to 4, wherein the crystal form belongs to a triclinic system as measured by an X-ray single crystal diffraction experiment, and the space group is P-1.
  6. 6. The use of a copper-based coordination polymer according to claim 5 for the synergism of nitrogen fertilizers, characterized in that it is added to the nitrogen fertilizer as a fertilizer additive to inhibit the soil urease and nitrifying bacteria activity.
  7. 7. The use according to claim 6, wherein the nitrogen fertilizer is urea.

Description

Copper-based coordination polymer, preparation method and application thereof in nitrogen fertilizer synergism Technical Field The invention belongs to the technical field of fertilizer synergism, and particularly relates to a copper-based coordination polymer, a preparation method and application thereof in nitrogen fertilizer synergism. Background The coordination polymer (Coordination Polymers, CPs) is a periodic network structure material formed by self-assembling metal ions and organic ligands through coordination bonds, and has the characteristics of structural designability, high specific surface area, adjustable pore channel structure, good chemical stability and the like. Novel bifunctional inhibitors of copper-based coordination polymers are designed and applied based on the structural controllability and functional modifiable nature of the coordination polymer. By accurately regulating and controlling metal types, ligand structures and synthesis conditions, functional materials with specific geometric configuration, electronic properties and stability can be obtained, and an ideal molecular platform is provided for developing efficient and targeted agricultural inhibitors. Copper ions serve as central metals and play a key role in the inhibitor, on one hand, the copper ions have high affinity to functional groups such as thio groups, amino groups and the like of the active center of urease, and can inhibit the catalytic activity of enzyme through competitive coordination, and on the other hand, the copper ions can interfere with the metabolic process of ammonia oxidizing microorganisms, and nitrification inhibition is realized by destroying the integrity of cell membranes or inhibiting key enzyme functions. Compared with free copper ions, the copper species immobilized in the form of coordination polymer has higher stability and controllable release, can obviously reduce the free concentration of copper ions in soil, and reduces environmental risks while ensuring inhibition efficiency. Conventional inhibitors are mostly aimed at a single process (such as inhibiting urease only or nitrifying only), and the whole process regulation of nitrogen conversion is difficult to realize. Therefore, the development of the copper-based coordination polymer with specific topological structure and functional site is not only hopeful to break through the bottleneck of single-function limitation of the existing inhibitor, but also can provide an innovative material foundation for realizing the efficient utilization of nitrogen fertilizer and the green sustainable development of agriculture. Disclosure of Invention In order to solve the technical problems, the invention provides a copper-based coordination polymer, a preparation method and application thereof in nitrogen fertilizer synergism, and long-acting inhibition can be carried out on urea hydrolysis and ammonium oxidation processes simultaneously by integrating structural stability, metal activity and slow release characteristics to form a synergism mechanism. The material has good soil suitability and environmental compatibility while maintaining high inhibition activity, and has definite application potential and industrial value in the aspects of refining nitrogen management, reducing fertilizer loss and reducing agricultural non-point source pollution. The invention is realized in such a way that a preparation method of a copper-based coordination polymer is provided, which comprises the following steps: Step 1, synthesizing N 1,N4 -bis (3-pyridyl) -2-butenamide by using 3-aminopyridine and fumaric acid as raw materials; And 2, synthesizing a novel copper-based coordination polymer [ Cu (3-bbpa) (5-NIPA) ] H 2 O of N 1,N4 -bis (3-pyridyl) -2-butenamide and CuCl 2·2H2 O as well as 5-nitroisophthalic acid by a hydrothermal method, wherein the novel copper-based coordination polymer is blue fine crystals. Preferably, the step 1 includes the following specific steps: step 101, slowly adding 3-aminopyridine dissolved in pyridine solution into pyridine solution of fumaric acid, and stirring at room temperature; Step 102, dropwise adding triphenyl phosphite into the mixed liquid obtained in the step 101, heating and refluxing, standing overnight at room temperature until solid is separated out, carrying out suction filtration, recrystallizing with ethanol, and drying in air to obtain powdery solid, namely N 1,N4 -bis (3-pyridyl) -2-butenamide. Further preferably, the molar ratio of 3-aminopyridine, fumaric acid, and triphenyl phosphite is 2:1:1. Further preferably, in step 101, 30 min is stirred, in step 102, triphenyl phosphite is added dropwise to 15 min after completion of step 101, and 10 h is heated and refluxed. Preferably, the step 2 includes the following specific steps: Step 201, putting CuCl 2·2H2 O and N 1,N4 -bis (3-pyridyl) -2-butenamide and 5-nitroisophthalic acid into a hydrothermal kettle; step 202, adding sodium hydroxide solution into a hydro