Preparation method of cobalt-based metal organic framework material and application of composite material of cobalt-based metal organic framework material in electric sensing

Abstract

The invention discloses a preparation method of a nickel-based metal organic framework material and application of the nickel-based metal organic framework material in electric sensing, a porous metal organic framework material is obtained by self-assembly in a mixed solution of organic ligands 9, 10-anthracenedioic acid (H2ADC), 2, 4, 6-tris (4-pyridyl)-1, 3, 5-triazine (TPT), cobalt nitrate, deionized water, N, N-dimethylacetamide (DMA) and HBF4, and the nickel-based metal organic framework material is applied to electric sensing. The synthesized material is assembled into a three-electrode system for testing epinephrine and uric acid electric sensing. The preparation method has the advantages that the metal organic framework material is simple in synthesis process, high in crystal purity and high in yield; the structure is novel, and the porosity is large. Through experimental test data analysis, the Co-MOF has excellent epinephrine and uric acid electric sensing activity, and the composite material ABamp is doped with acetylene black (AB); co-MOF (1: 1) has more excellent epinephrine and uric acid electric sensing activity.

Description

Technical Field

[0001] The present invention relates to a novel metal organic framework material (Co-MOF) formed with 9,10-anthracene dioic acid (H2ADC) as a main ligand, 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPT) as a co-ligand and transition metal nickel as a metal center. The Co-MOF exhibits excellent adrenaline and uric acid electrical sensing activities through the preparation of catalyst electrode material tests. Meanwhile, the Co-MOF is compounded with acetylene black to obtain a heterogeneous composite material (AB&Co-MOF). The heterogeneous composite material exhibits even more excellent adrenaline and uric acid electrical sensing activities through the preparation of catalyst electrode material tests. Background Art

[0002] As people's quality of life improves, various new diseases are emerging, including diabetes. The level of uric acid in the blood is the only criterion for clinical diagnosis of diabetes. Adrenaline, as an essential hormone for our human body, can be used for cardiopulmonary resuscitation, etc., and plays a very important role in medical clinics. Therefore, the research on adrenaline and uric acid sensors has attracted much attention.

[0003] MOFs metal organic framework materials are considered to be an extremely important electrocatalyst due to their unique structure, such as high specific surface area, adjustable pore size, adjustable pore size, and diversified chemical composition. In recent years, the application of MOF in the field of biosensing has attracted much attention. It is precisely because of the high porosity and versatility of MOF that it has become an ideal material in the field of biosensing. By utilizing these characteristics of MOF, more efficient and sensitive biosensors can be developed, providing more reliable tools for fields such as biomedical research and disease diagnosis. Summary of the invention

[0004] The present invention provides a method for synthesizing a cobalt-based metal organic framework material (Co-MOF) using an organic ligand 9,10-anthracene dioic acid (H2ADC) as a main ligand, 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPT) as a secondary ligand, and transition metal cobalt as a metal center. The general chemical formula is C 14 CoN2O 4.33 H 0.17 .

[0005] Weigh the organic ligand 9,10-anthracene dioic acid (H2ADC), 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPT), cobalt nitrate, deionized water, N,N-dimethylacetamide (DMA), HBF4 (HBF4 mass concentration is 30-37%), and evenly disperse the mixed solution by ultrasonic dispersion. Then seal it, and conduct the solvent thermal reaction under the conditions of 120-140℃ for 20-24 hours. Then, cool it to room temperature at a uniform speed to obtain pink hexagonal nut block crystals (Co-MOF). The material is vacuum dried to prepare electrode materials to test the electrical sensing performance of adrenaline and uric acid. At the same time, weigh the same mass of Co-MOF and acetylene black (AB) synthesized by us and place them in an agate mortar. After mechanical grinding, add ethanol, ultrasonically disperse them in an ultrasonicator, vacuum dry them at 80℃, grind them, collect the samples, and obtain the composite material AB&Co-MOF (1:1) of Co-MOF.

[0006] The molar ratio of the organic ligand 9,10-anthracene dioic acid (H2ADC), 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPT) and cobalt nitrate is 1:1:4, and the volume ratio of deionized water, N,N-dimethylacetamide (DMA) and HBF4 is 5:10-15:1. The solvent thermal reaction conditions are 120°C and the reaction time is 24 hours.

[0007] Another technical solution of the present invention is to prepare a cobalt-based metal organic framework material with a chemical formula of C according to the above method. 14 CoN2O 4.33 H 0.17 The crystalline material belongs to the hexagonal system, the space group is P-31c, and the unit cell parameters are: α=90°, β=90°, γ=120°, a=16.8961(2)Å, b=16.8961(2)Å, c=15.2308(2)Å. The nickel-based metal organic framework material is used as an electrocatalyst in the electrical sensing of adrenaline and uric acid.

[0008] The electrocatalytic material also includes a nickel-based metal organic framework material with a chemical formula of C 14 CoN2O 4.33 H 0.17 The material is a composite material of a crystalline material and acetylene black (AB), wherein the mass ratio of the crystalline material to the acetylene black (AB) is 1:1. The room temperature involved in the present invention refers to the ambient temperature under normal pressure.

[0009] Another technical solution of the present invention is to provide an electric sensor material, comprising the nickel-based metal organic framework material.

[0010] The electrical sensor material also includes acetylene black.

[0011] The crystal synthesized in the present invention is measured by using a small molecule single crystal X-ray diffractometer of Rigaku Co., Ltd. of Japan. The Mo Kα rays monochromatized by a graphite monochromator are used to measure the diffraction intensity and unit cell parameters at 293K. The collected data are subjected to empirical absorption correction by using a scanning technique. The obtained results are analyzed by a direct method using the Shelxtl-97 program and corrected by the full matrix least squares method. The crystallographic data are shown in Crystal Parameter Table 1.

[0012] Table 1 Crystallographic parameters BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 : Stacking diagram of the crystalline metal organic framework material Co-MOF synthesized in Example 3.

[0014] Figure 2 : XRD spectrum of Co-MOF prepared in Example 3.

[0015] Figure 3 : Scanning (SEM) images of the Co-MOF prepared in Example 4 and the composite material AB&Co-MOF (1:1) prepared in Example 6.

[0016] Figure 4 : A bar graph of the Co-MOF prepared in Example 4 and its composite material AB&Co-MOF (1:1) prepared in Example 6 with and without the addition of 0.2 mM adrenaline solution.

[0017] Figure 5 : A bar chart of the Co-MOF prepared in Example 4 and its composite material AB&Co-MOF (1:1) prepared in Example 6 with and without the addition of 0.2 mM uric acid solution.

[0018] Figure 6 : The optimal pH value diagram of the composite material AB&Co-MOF (1:1) prepared in Example 5 was verified in the presence of 0.2 mM adrenaline solution and 0.2 mM uric acid solution.

[0019] Figure 7 : DPV curve of the Co-MOF prepared in Example 5 when different concentrations of adrenaline were continuously added into 0.1M pH=7 PBS solution.

[0020] Figure 8 :and Figure 7 The linear relationship between adrenaline concentration and current density of the corresponding material Co-MOF in 0.1M pH=7 PBS solution.

[0021] Fig. 9 : DPV curve of AB&Co-MOF (1:1) prepared in Example 5 with continuous addition of different concentrations of adrenaline in 0.1M pH=7 PBS solution.

[0022] Fig.10 :and Fig. 9 The linear relationship between adrenaline concentration and current density of the corresponding material AB&Co-MOF (1:1) in 0.1M pH=7 PBS solution.

[0023] Fig.11 : DPV curve of Co-MOF prepared in Example 5 when different concentrations of uric acid are continuously added into 0.1M pH=7 PBS solution. Fig.12 :and Fig.11 The linear relationship between uric acid concentration and current density of the corresponding material Co-MOF in 0.1M pH=7 PBS solution.

[0024] Fig.13 : DPV curve of AB&Co-MOF (1:1) prepared in Example 5 with continuous addition of different concentrations of uric acid in 0.1M pH=7 PBS solution. Fig.14 :and Fig.13 The linear relationship between uric acid concentration and current density of the corresponding material AB&Co-MOF (1:1) in 0.1M pH=7 PBS solution. DETAILED DESCRIPTION

[0025] Example 1 0.025mmol 9,10-anthracenediacid (H2ADC), 0.025mmol tpt, 0.1mmol cobalt nitrate, 1ml deionized water and 2ml N,N-dimethylacetamide (DMA) were weighed in equal amounts and added into 10 10ml glass vials respectively. Each reaction was ultrasonicated for 30min and placed in a 120℃ oven for constant temperature reaction for 48h, and then cooled to room temperature at a constant rate of 2-3℃ / h. All 10 glass vials had turbid liquid and no crystals were produced.

[0026] Example 2 0.025mmol 9,10-anthracenediacid (H2ADC), 0.025mmol tpt, 0.1mmol cobalt nitrate, 1ml deionized water, 2ml N,N-dimethylformamide (DMA) were weighed in equal amounts, and 0.05-0.55ml (i.e. 0.05ml, 0.1ml, 0.15ml, 0.25ml, 0.3ml, 0.35ml, 0.4ml, 0.45ml, 0.5ml, 0.55ml) of 37% HBF4 was added to each vial respectively, and added to 10 10ml glass vials respectively. Each reaction was ultrasonically treated for 30min and placed in a 120℃ oven for constant temperature reaction for 24h, and then cooled to room temperature at a uniform rate of 2-3℃ / h. All 10 glass vials contained transparent clear liquid, and no crystals were produced.

[0027] Example 3 0.025mmol 9,10-anthracenediacid (H2ADC), 0.025mmol tpt, 0.1mmol cobalt nitrate, 1ml deionized water, 3ml N,N-dimethylacetamide (DMA) were weighed in equal amounts, and 0.05-0.55ml (i.e. 0.05ml, 0.1ml, 0.15ml, 0.25ml, 0.3ml, 0.35ml, 0.4ml, 0.45ml, 0.5ml, 0.55ml) of 37% HBF4 was added to each vial, and added to 10 10ml glass vials respectively. Each reaction was ultrasonicated for 30min and placed in a 120℃ oven for constant temperature reaction for 24h, and then cooled to room temperature at a uniform rate of 2-3℃ / h. Pink crystals were generated in the vials with 0.15ml and 0.2ml HBF4 added, and the crystals in the vial with 0.15ml HBF4 added were the most regular and had the highest yield. Depend on Figure 2 It can be seen that the powder diffraction peak of the prepared sample is highly consistent with the diffraction peak of Co-MOF simulated by single crystal data. The obtained sample is Co-MOF material, and the crystallographic parameters are shown in Table 1.

[0028] Example 4 The porous crystalline metal organic framework material sample (Ni-MOF) collected in Example 3 was evenly ground with an agate mortar, and 4 mg was weighed into a 2 ml sample tube, 1.2 ml of anhydrous ethanol, 0.6 ml of deionized water and 0.2 ml of naphthol were added. After ultrasonication for 60 min, 5 μl of the dispersion was aspirated with a pipette and applied to the polished glassy carbon electrode surface to test the electrochemical detection of adrenaline and uric acid sensing performance. The CV curve was scanned in 0.1 M pH = 7 PBS solution until it was stable, and then the CV curve of adrenaline and uric acid electrical sensing was tested.

[0029] Example 5 5 mg of the porous crystalline metal organic framework material synthesized in Example 3 and 5 mg of the conductive material acetylene black (AB) were placed in an agate mortar and ground for 15 minutes to obtain a composite material of Co-MOF and AB (AB&Co-MOF). 4 mg of the ground sample was weighed into a 2 ml sample tube, 1.2 ml of anhydrous ethanol, 0.6 ml of deionized water and 0.2 ml of naphthol were added, and after ultrasonication for 30 minutes, 5 μl of the dispersion was drawn with a pipette and applied to the polished glassy carbon electrode surface to test the sensing performance of electrochemical detection of adrenaline and uric acid.

[0030] The Co-MOF and AB&Co-MOF (1:1) materials synthesized by the above method were tested for adrenaline and uric acid electrosensing. The experimental results showed that AB&Co-MOF (1:1) had a higher sensitivity of 2123.9μA μM in the electrochemical detection of adrenaline. −1 cm −2 The linear range is 0~3050 μM, and the detection limit is 0.096μM (S / N = 3). The sensitivity of pure Co-MOF electrochemical detection of adrenaline is 162.3μA μM −1 cm −2 , the linear range is 0~1600μM, and the detection limit is 2.05 μM (S / N = 3). It can be seen that the composite material AB&Co-MOF (1:1) formed after Co-MOF is compounded with acetylene black has greatly improved electrical sensing performance compared with Co-MOF, the linear range is increased by 1.9 times, and the sensitivity is increased by 13.1 times; the composite material AB&Co-MOF (1:1) has a high sensitivity of 2215 μA μM in electrochemical detection of uric acid −1 cm −2 , the linear range is 0~3000μM, while the sensitivity of pure Co-MOF to uric acid is 79.9μA μM −1 cm −2 , the linear range is 0~ 1700 μM. It can be seen that the composite material AB&Co-MOF (1:1) formed after Co-MOF is compounded with acetylene black has greatly improved electrical sensing performance compared with Co-MOF, the linear range is increased by 1.76 times, and the sensitivity is increased by 27.7 times. The electrical sensing performance of the composite material has been greatly improved. This shows that the addition of acetylene black (AB) increases the conductivity of the material, accelerates the electron transmission capacity, and makes our Co-MOF material have better and more excellent electrical sensing detection performance.

Claims

1. A method for preparing a cobalt-based metal organic framework material, characterized in that: The steps are as follows: adding organic ligand 9,10-anthracene dioic acid, 2,4,6-tri(4-pyridyl)-1,3,5-triazine and cobalt metal salt to a mixed solution of water, N,N-dimethylacetamide and HBF4, and obtaining a preparation method of a cobalt-based metal organic framework material through a solvent thermal reaction.

2. The method for preparing a nickel-based metal organic framework material according to claim 1, characterized in that: The molar ratio of 9,10-anthracene dioic acid, 2,4,6-tris(4-pyridyl)-1,3,5-triazine and cobalt metal salt is 1:1:3-4; the volume ratio of water, N,N-dimethylacetamide (DMA) and HBF4 is 5:10-15:

1.

3. The method for preparing a nickel-based metal organic framework material according to claim 1 or 2, characterized in that: The solvent thermal reaction conditions are 120-140°C and the reaction time is 20-24 hours.

4. The nickel-based metal organic framework material prepared by the method according to any one of claims 1 to 3, characterized in that: The chemical formula of nickel-based metal organic framework materials is C 14 CoN2O 4.33 H 0.17 The crystalline material belongs to the hexagonal crystal system, the space group is P-31c, and the unit cell parameters are: α=90°, β=90°, γ=120°, a=16.8961(2)Å, b=16.8961(2)Å, c=15.2308(2)Å.

5. Use of the cobalt-based metal organic framework material according to claim 4 as an electrocatalyst in adrenaline and uric acid electrical sensing.

6. The use according to claim 5, wherein the material further comprises a nickel-based metal organic framework material having a chemical formula of C 14 CoN2O 4.33 H 0.17 The material is a composite of crystalline material and acetylene black.

7. An electrical sensor material, characterized in that: It comprises the nickel-based metal organic framework material as described in claim 4.

8. The electrical sensor material according to claim 7, characterized in that The material also includes acetylene black.

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