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

Abstract

The application discloses a preparation method of a nickel-based metal organic framework material and application of the material in electric sensing, and utilizes a mixed solution of organic ligands 9,10-anthracene diacid (H2ADC), 2,4,6-tris (4-pyridyl) -1,3,5-triazine (TPT), cobalt nitrate, deionized water, N, N-dimethylacetamide (DMA) and HBF4 to obtain a porous metal organic framework material through self-assembly, and the synthesized material is assembled into a three-electrode system to test electric sensing of adrenaline and uric acid. The metal organic framework material has the advantages of simple synthesis process, high crystalline purity, high yield, novel structure and high porosity. Through analysis of experimental test data, it is found that the Co-MOF has superior electric sensing activity of adrenaline and uric acid, and the composite material AB&Co-MOF (1:1) after doping of acetylene black (AB) has superior electric sensing activity of adrenaline and uric acid.

Description

TECHNICAL FIELD

[0001] The present application relates to a novel metal organic framework material (Co-MOF) formed by taking 9,10-anthracene diacid (H2ADC) as a main ligand, 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPT) as an auxiliary ligand, and transition metal nickel as a metal center. The Co-MOF shows excellent adrenalin and uric acid electrochemical sensing activity when tested by preparing a catalyst electrode material. Meanwhile, the Co-MOF is compounded with acetylene black to obtain a heterojunction composite material (AB&Co-MOF), which shows more excellent adrenalin and uric acid electrochemical sensing activity when tested by preparing a catalyst electrode material. BACKGROUND

[0002] With the increasing quality of people's material life, various new diseases have also emerged, one of which is diabetes. The uric acid level in the blood is the only standard for clinically diagnosing diabetes. Adrenalin, as an essential hormone for our human body, can be used for cardiopulmonary resuscitation and the like, and plays a very important role in medical clinical applications. Therefore, the research on adrenalin and uric acid sensors has attracted much attention.

[0003] MOFs metal organic framework materials are considered as an extremely important electrocatalyst due to their unique structure, such as high specific surface area, tunable pore size, and diversified chemical composition. In recent years, the application of MOFs in the field of biosensing has attracted much attention. Due to the high porosity and multifunctionality of MOFs, they have become ideal materials in the field of biosensing. By utilizing these characteristics of MOFs, more efficient and sensitive biosensors can be developed, which can provide more reliable tools for biomedical research and disease diagnosis. SUMMARY

[0004] The present application provides a synthesis method of a cobalt-based metal organic framework material (Co-MOF) formed by taking organic ligand 9,10-anthracene diacid (H2ADC) as a main ligand, 2,4,6-tris(4-pyridyl)-1,3,5-triazine (TPT) as an auxiliary ligand, and transition metal cobalt as a metal center. The chemical general formula is C 14 CoN2O 4.33 H 0.17 .

[0005] The mixed solution of organic ligand 9,10-anthracene diacid (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%) is uniformly ultrasonically dispersed, sealed, and then subjected to a solvothermal reaction under the condition of 120-140 DEG C for 20-24 hours, and then uniformly cooled to room temperature to obtain a pink hexagonal nut block crystal (Co-MOF). Vacuum drying is performed to obtain an electrode material for testing the electrochemical sensing performance of adrenaline and uric acid. At the same time, equal mass of the Co-MOF synthesized by the application and acetylene black (AB) are placed in a marver, mechanically ground, added with ethanol, ultrasonically dispersed in an ultrasonic instrument, vacuum dried at 80 DEG C, and ground to collect the sample, so as to obtain the composite material AB&Co-MOF (1:1) of the Co-MOF.

[0006] The molar ratio of the organic ligand 9,10-anthracene diacid (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 solvothermal reaction condition is 120 DEG C, and the reaction time is 24 hours.

[0007] Another technical solution of the application is to prepare a cobalt-based metal organic framework material with a chemical molecular formula of C 14 CoN2O 4.33 H 0.17 The crystal of the crystal material belongs to a hexagonal system, and the space group is P-31c, and the cell parameters are: alpha=90 DEG, beta=90 DEG, gamma=120 DEG, a=16.8961 (2) angstrom, b=16.8961 (2) angstrom, and c=15.2308 (2) angstrom. The nickel-based metal organic framework material is used as an electrocatalyst in the application of adrenaline and uric acid electrochemical sensing.

[0008] The electrocatalytic material further comprises a nickel-based metal organic framework material with a chemical molecular formula of C 14 CoN2O 4.33 H 0.17 The material after the crystal material and acetylene black (AB) are compounded, wherein the mass ratio of the crystal material and acetylene black (AB) is 1:1. The room temperature in the application refers to the ambient temperature under normal pressure.

[0009] Another technical solution of the application is to provide an electrochemical sensor material, which comprises the nickel-based metal organic framework material.

[0010] The electrochemical sensor material further comprises acetylene black.

[0011] The crystal synthesized in this invention was structured using a small-molecule single-crystal X-ray diffractometer from Rigaku Corporation, Japan. Mo Kα rays monochromated by a graphite monochromator were used to measure diffraction intensity and cell parameters at 293 K. The collected data were empirically absorbed and corrected using scanning techniques. The results were analyzed directly using the Shelxtl-97 program and corrected using the full matrix least squares method. The resulting crystallographic data are shown in Table 1, which contains crystal parameters.

[0012] Table 1 Crystallographic Parameters

[0013] Attached Figure Description

[0014] Figure 1 : This is a packing diagram of the crystalline metal-organic framework material Co-MOF synthesized in Example 3.

[0015] Figure 2 : XRD pattern of Co-MOF prepared in Example 3.

[0016] Figure 3 : This is a scanned image (SEM) of the Co-MOF prepared in Example 4 and the composite material AB & Co-MOF (1:1) prepared in Example 6.

[0017] Figure 4 : Bar graphs of Co-MOF prepared in Example 4 and its composite material AB&Co-MOF (1:1) prepared in Example 6 with and without 0.2 mM adrenaline solution.

[0018] Figure 5 : Bar graphs of Co-MOF prepared in Example 4 and its composite material AB&Co-MOF (1:1) prepared in Example 6 with and without 0.2mM uric acid solution.

[0019] Figure 6 The optimal pH value 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.

[0020] Figure 7 : This is the DPV curve of the Co-MOF prepared in Example 5 with different concentrations of adrenaline added continuously to 0.1M pH=7 PBS solution.

[0021] Figure 8 :and Figure 7 The corresponding linear relationship between adrenaline concentration and current density of the Co-MOF material in 0.1M pH=7 PBS solution.

[0022] Figure 9 DPV plot of AB&Co-MOF (1:1) made in Example 5 in 0.1M pH=7 PBS solution with continuous addition of different concentrations of epinephrine.

[0023] Figure 10 : with Figure 9 Linear relationship plot of epinephrine concentration vs. current density for the corresponding material AB&Co-MOF (1:1) in 0.1M pH=7 PBS solution.

[0024] Figure 11 DPV plot of Co-MOF made in Example 5 in 0.1M pH=7 PBS solution with continuous addition of different concentrations of uric acid.

[0025] Figure 12 : with Figure 11 Linear relationship plot of uric acid concentration vs. current density for the corresponding material Co-MOF in 0.1M pH=7 PBS solution.

[0026] Figure 13 DPV plot of AB&Co-MOF (1:1) made in Example 5 in 0.1M pH=7 PBS solution with continuous addition of different concentrations of uric acid.

[0027] Figure 14 : with Figure 13 Linear relationship plot of uric acid concentration vs. current density for the corresponding material AB&Co-MOF (1:1) in 0.1M pH=7 PBS solution. DETAILED DESCRIPTION

[0028] Example 1

[0029] 0.025 mmol of 9,10-anthracene dicarboxylic acid (H2ADC), 0.025 mmol of tpt, 0.1 mmol of cobalt nitrate, 1 ml of deionized water, 2 ml of N,N-dimethylacetamide (DMA) were weighed in equal amounts into 10 10-ml glass vials, each reaction was ultrasonically treated for 30 min and then placed in an oven at 120°C for constant temperature reaction for 48 h, and then cooled to room temperature at a uniform rate of 2-3°C / h, and 10 glass vials were all turbid liquids, and no crystals were produced.

[0030] Example 2

[0031] Equally weighed 0.025 mmol 9,10-anthracene diacid (H2ADC), 0.025 mmol tpt, 0.1 mmol cobalt nitrate, 1 ml of deionized water, 2 ml of N, N-dimethylformamide (DMA), and then 0.05-0.55 ml (i.e. 0.05 ml, 0.1 ml, 0.15 ml, 0.25 ml, 0.3 ml, 0.35 ml, 0.4 ml, 0.45 ml, 0.5 ml, 0.55 ml) of 37% HBF4 with a mass concentration were added into each vial, respectively, into 10 10 ml glass vials, each reaction was ultrasonicated for 30 min and then added into a 120°C oven for constant temperature reaction for 24 h, and then cooled to room temperature at a uniform speed of 2-3°C / h, and the 10 glass vials were all transparent clear solutions without crystal generation.

[0032] Example 3

[0033] Equally weighed 0.025 mmol 9,10-anthracene diacid (H2ADC), 0.025 mmol tpt, 0.1 mmol cobalt nitrate, 1 ml of deionized water, 3 ml of N, N-dimethylacetamide (DMA), and then 0.05-0.55 ml (i.e. 0.05 ml, 0.1 ml, 0.15 ml, 0.25 ml, 0.3 ml, 0.35 ml, 0.4 ml, 0.45 ml, 0.5 ml, 0.55 ml) of 37% HBF4 with a mass concentration were added into each vial, respectively, into 10 10 ml glass vials, each reaction was ultrasonicated for 30 min and then added into a 120°C oven for constant temperature reaction for 24 h, and then cooled to room temperature at a uniform speed of 2-3°C / h, and the 10 glass vials were all transparent clear solutions without crystal generation. Figure 2 It can be seen that the powder diffraction peak of the prepared sample is highly consistent with the diffraction peak of the Co-MOF simulated from single crystal data, and the obtained sample is a Co-MOF material, and the crystallographic parameters are shown in Table 1.

[0034] Example 4

[0035] After the porous crystalline metal organic framework material sample (Ni-MOF) collected in Example 3 was ground uniformly in a maroon mortar, 4 mg of the 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 ultrasonic treatment for 60 min, 5 μl of the dispersion liquid was taken by a pipette and coated on the surface of a polished glassy carbon electrode, and the sensing performance for detecting adrenaline and uric acid was tested, and then the CV curve was scanned in a 0.1M pH=7 PBS solution until it was stable, and then the CV curve for detecting adrenaline and uric acid was tested.

[0036] Example 5

[0037] The Co-MOF synthesized in Example 3 and the conductive substance acetylene black (AB) 5 mg were placed in an agate mortar and ground for 15 min to obtain a composite material of Co-MOF and AB (AB&Co-MOF). After grinding, 4 mg of the 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 ultrasonic treatment for 30 min, 5 μl of the dispersion was taken and coated on the surface of a polished glassy carbon electrode, and the sensing performance for electrochemical detection of adrenaline and uric acid was tested.

[0038] The Co-MOF and AB&Co-MOF (1:1) materials synthesized by the above method were subjected to electrochemical sensing tests for adrenaline and uric acid, and the experimental results showed that the sensitivity of AB&Co-MOF (1:1) was higher in the electrochemical detection of adrenaline, which was 2123.9 μA μM −1 cm −2 , the linear range was 0~3050 μM, and the detection limit was 0.096 μM (S / N = 3). The sensitivity of pure Co-MOF in the electrochemical detection of adrenaline was 162.3 μA μM −1 cm −2 , the linear range was 0~1600 μM, and the detection limit was 2.05 μM (S / N = 3). It can be seen that the composite material AB&Co-MOF (1:1) formed by the composite of Co-MOF and acetylene black has greatly improved electrochemical sensing performance compared with Co-MOF, with an increase of 1.9 times in the linear range and an increase of 13.1 times in the sensitivity; the sensitivity of the composite material AB&Co-MOF (1:1) in the electrochemical detection of uric acid was higher, which was 2215 μA μM −1 cm −2 , and the linear range was 0~3000 μM, while the sensitivity of pure Co-MOF in the sensing of uric acid was 79.9 μA μM −1 cm −2 , and the linear range was 0~1700 μM. It can be seen that the composite material AB&Co-MOF (1:1) formed by the composite of Co-MOF and acetylene black has greatly improved electrochemical sensing performance compared with Co-MOF, with an increase of 1.76 times in the linear range and an increase of 27.7 times in the sensitivity. The electrochemical sensing performance of the composite material has greatly improved. This shows that the addition of acetylene black (AB) increases the conductivity of the material and accelerates the electron transport capacity, so that our Co-MOF material has better and excellent electrochemical sensing performance.

Claims

1. A cobalt-based metal-organic framework material characterized in that, A cobalt-based metal organic framework material has a chemical formula of C 14 CoN2O 4.33 H 0.17 The crystal of the crystal material belongs to a hexagonal system, a space group is P-31c, and cell parameters are: alpha=90°, beta=90°, gamma=120°, a=16.8961(2)Å, b=16.8961(2)Å, and c=15.2308(2)Å.

2. Use of the cobalt-based metal-organic framework material according to claim 1 as an electrocatalyst for the electro-sensing of adrenaline and uric acid.

3. Use of the material obtained by compounding the cobalt-based metal-organic framework material according to claim 1 with acetylene black as an electrocatalyst for the electro-sensing of adrenaline and uric acid.

4. An electrical sensor material, characterized in that The cobalt-based metal-organic framework material according to claim 1.

5. The electrical sensor material of claim 4, wherein, The material also comprises acetylene black.

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