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CN-121988390-A - MOFs-based porous LaNiO3Perovskite nano enzyme and preparation and application thereof

CN121988390ACN 121988390 ACN121988390 ACN 121988390ACN-121988390-A

Abstract

The invention belongs to the technical field of novel functional materials and biochemical sensing detection, and particularly relates to MOFs-based porous LaNiO 3 perovskite nano enzyme, and preparation and application thereof. According to the invention, MOFs is used as a precursor, and the crystal phase and the porous structure of LaNiO 3 are synchronously realized through a pyrolysis process, so that the material has the high catalytic activity of perovskite and the substrate enrichment capacity of the porous structure, and the problem of uneven dispersion of active sites of the catalytic material is solved. And MOFs derived LaNiO 3 perovskite catalyst is simultaneously applied to two detection modes of colorimetry and gel for the first time, the rapid macroscopic qualitative and quantitative analysis of nitrite is realized by a colorimetry method, the portability and long-term storage stability of a detection system are realized by a gel rule through carrier solidification, the limitation of a single detection method on scene suitability is broken through, the dual requirements of accurate detection and on-site rapid screening in a laboratory are met, the detection limit is low, the anti-interference capability is strong, the catalytic activity is stronger, the stability is higher, and the adaptation scene is wider.

Inventors

  • ZHU XIXI
  • WANG YUENING
  • HU LULU
  • ZHAO HUI
  • GAO ZHONGZHENG
  • WU TAO
  • GONG BO

Assignees

  • 山东科技大学

Dates

Publication Date
20260508
Application Date
20251219

Claims (10)

  1. 1. The preparation method of MOFs-based porous LaNiO 3 perovskite nano enzyme is characterized by comprising the following steps of: (1) Providing a first solution comprising at least one lanthanide metal salt and at least one metal nickel salt, and a second solution comprising at least one multidentate carboxylic acid organic ligand, mixing the second solution with the first solution, and performing a solvothermal reaction to form MOFs metal-organic framework precursors; (2) Calcining the precursor in an inert atmosphere or an air atmosphere to obtain a LaNiO 3 -MOF nano enzyme catalyst; (3) Dissolving a LaNiO 3 -MOF nano enzyme catalyst in water, adding natural polysaccharide hydrogel after ultrasonic dispersion to form a mixed solution, contacting the mixed solution with a divalent or trivalent metal solution, and performing a crosslinking reaction to form hydrogel particles coated with the LaNiO 3 -MOF nano enzyme catalyst.
  2. 2. The preparation method of the MOFs-based porous LaNiO 3 perovskite nano enzyme is characterized in that the lanthanide metal salt comprises at least one of lanthanum nitrate, lanthanum chloride and lanthanum acetate, the metal nickel salt comprises at least one of nickel nitrate, nickel chloride and nickel acetate, the polydentate carboxylic acid organic ligand comprises at least one of trimesic acid, pyromellitic acid and terephthalic acid, and the organic solvent used by the first solution and/or the second solution is a polar aprotic solvent, and the polar aprotic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
  3. 3. The preparation method of the MOFs-based porous LaNiO 3 perovskite nano enzyme is characterized in that the molar ratio of lanthanide metal salt to metal nickel salt is 1:1, the volume ratio of lanthanide metal salt to organic solvent is 1 mmol:15-20 mL, and the volume ratio of the mass of the polydentate carboxylic acid organic ligand to the volume ratio of the organic solvent in the second solution is 1 g:150-180 mL.
  4. 4. The preparation method of MOFs-based porous LaNiO 3 perovskite nano enzyme is characterized by further comprising stirring the mixed solution at room temperature for 0.1-2 hours after mixing the first solution and the second solution and before solvothermal reaction, wherein the stirring speed is 400-800 rpm, the solvothermal reaction temperature is 140-180 ℃, and the reaction time is 12-48 hours; And naturally cooling after the reaction is finished, centrifuging for 2-3 times by using ethanol or water, and drying at 60-80 ℃ overnight.
  5. 5. The preparation method of MOFs-based porous LaNiO 3 perovskite nano enzyme according to claim 1, wherein the calcination treatment is carried out in an air atmosphere, the calcination temperature is 500-900 ℃, the calcination time is 2-8 hours, and the temperature rising rate is 1-5 ℃ per minute.
  6. 6. The preparation method of MOFs-based porous LaNiO 3 perovskite nano-enzyme according to claim 1, wherein in the step (3), the natural polysaccharide hydrogel precursor is at least one of sodium alginate, chitosan and hyaluronic acid, the metal ions in the divalent or trivalent metal solution are Ca2+, al3+ or Fe3+, and the solution is a nitrate or chloride salt of Ca2+, al3+ or Fe3+.
  7. 7. The preparation method of the MOFs-based porous LaNiO 3 perovskite nano-enzyme is characterized in that the metal solution is CaCl 2 solution with the concentration of 1g/100mL, the mass ratio of the nano-enzyme catalyst to the volume of water and the mass ratio of the natural polysaccharide hydrogel to the volume of water are 1 mg/10 mL/100 mg, and the volume ratio of the mixed solution to the CaCl 2 solution is 1:1.
  8. 8. The preparation method of MOFs-based porous LaNiO 3 perovskite nano enzyme is characterized in that in the step (3), the mixed solution is placed in an oil bath pot at 80 ℃ and is fully stirred for 1-2 hours, and the mixed solution is taken out and placed at room temperature and is stirred for 8-12 hours; And washing the obtained gel ball with distilled water for 2-5 times, drying to remove water, and putting the gel ball into HAc-NaAc buffer solution with pH of=4 for standby.
  9. 9. A LaNiO 3 -MOF nano-enzyme catalyst or gel sphere prepared by the method for preparing MOFs-based porous LaNiO 3 perovskite nano-enzyme according to any one of claims 1-8.
  10. 10. Use of the LaNiO 3 -MOF nanoenzyme catalyst of claim 9 in colorimetric detection or gel detection of gel spheres.

Description

MOFs-based porous LaNiO 3 perovskite nano enzyme and preparation and application thereof Technical Field The invention belongs to the technical field of novel functional materials and biochemical sensing detection, and particularly relates to MOFs-based porous LaNiO 3 perovskite nano enzyme, and preparation and application thereof. Background Currently, the detection method of nitrite mainly depends on ion chromatography (as a national standard arbitration method), photometry (such as classical griss reagent colorimetry and its modification), electrochemical method, fluorescence analysis method and the like. These technologies, while mature, each face challenges. For example, ion chromatography relies on large instruments and is complex to operate, traditional photometry has to be improved in sensitivity, selectivity or antijamming capability, and some methods (such as the use of alpha-naphthylamine) involve carcinogenic reagents, electrochemical and fluorescence methods are highly sensitive but are susceptible to interference from complex matrices and sometimes inadequate in stability or reproducibility. The detection method is constructed based on Prussian blue composite nano-enzyme by taking nitrite as a detection target. By taking MI-100 (Fe) as a carrier, prussian blue grows on the surface of the carrier in situ, PB@MIL-100 (Fe) composite nano enzyme is constructed, and Adenosine Triphosphate (ATP) is modified on the surface of PBMIL-100 (Fe) to form a novel composite nano enzyme PB@MIL-100 (Fe) @ATP. By utilizing the diazotization reaction principle between nitrite and tetramethyl benzidine (TMB), and taking composite nano enzyme PB@MIL-100 (Fe) @ATP as catalytic enzyme, a ratio colorimetric method is constructed to realize qualitative and quantitative detection of nitrite. The following key defects exist in the current nitrite detection technology and material design field, and the development of high-performance sensing technology is restricted: (1) The complex nano-enzyme preparation has high complexity and large scale difficulty. PB (Prussian blue), MIL-100 (Fe) and ATP (adenosine triphosphate) are compounded by accurately controlling dispersibility, loading capacity and interfacial binding force, aggregation or component shedding is easily caused by multi-step reaction, ATP is used as a biological molecule, hydrolysis can occur under the conditions of solvent and temperature for material synthesis, uniformity of a composite structure is affected, and low-cost large-scale preparation is difficult to realize. (2) The material has insufficient stability and limited storage and use. MIL-100 (Fe) is easy to collapse in a framework under a humid environment or acid-base condition, so that catalytic active sites are lost, ATP is easy to be degraded by microorganisms, is sensitive to temperature and illumination, can cause the activity attenuation of complex enzyme after long-term storage, has weaker interfacial acting force between PB and MIL-100 (Fe), and can cause component stripping by ions and organic matters in a detection system, so that the catalytic stability is reduced. (3) The detection time may be long and may not meet the requirements of rapid detection. The catalytic kinetics rate of the composite nano-enzyme is slow, and long-time incubation (20 minutes) is required to achieve stable ratio signals. (4) The biological compatibility and safety risk ATP is used as a biological molecule, if the biological molecule is remained in food or environment after detection, microorganism propagation can be possibly caused, PB is low in toxicity, but the biological accumulation under the nanoscale is not clear, and environmental safety hidden danger can exist in large-scale application. To overcome the above limitations, the core innovation in the sensing field is focused on developing new high performance sensing materials, especially functional materials that can efficiently convert target recognition events into readable signals (e.g., color changes, fluorescence response). In this context, two classes of material systems are of interest: MOFs are crystalline porous materials formed by self-assembly of metal nodes and organic ligands, and have the unique advantages of high specific surface area, adjustable pores, designable structure, easiness in functionalization and the like. In the sensing field, MOFs are both excellent precursor templates and direct active sensing platforms. Perovskite oxides, because of their unique crystal structure, tunable electronic structure, abundant oxygen vacancies, and good (electro) catalytic activity, present great potential in the fields of energy conversion and catalysis. Studies have shown that the specific surface area and the exposure degree of active sites of perovskite oxides can be significantly improved by introducing a hierarchical pore structure (such as a mesoporous-mesoporous structure), thereby greatly improving the performance of the perovskite oxides i