CN116217947B - Two-dimensional isomorphic metal organic framework material, preparation method thereof and application thereof in electrochemical detection of glucose - Google Patents
Two-dimensional isomorphic metal organic framework material, preparation method thereof and application thereof in electrochemical detection of glucose Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 45
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 33
- 239000008103 glucose Substances 0.000 title claims abstract description 33
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 29
- 238000000835 electrochemical detection Methods 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 claims abstract description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000013110 organic ligand Substances 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000006230 acetylene black Substances 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002178 crystalline material Substances 0.000 claims description 6
- 239000010411 electrocatalyst Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- IZLWRQIVKBKOME-UHFFFAOYSA-N 2-[3,5-bis(1H-imidazol-2-yl)phenyl]-1H-imidazole Chemical compound C1=CNC(C=2C=C(C=C(C=2)C=2NC=CN=2)C=2NC=CN=2)=N1 IZLWRQIVKBKOME-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 30
- 238000012360 testing method Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000011521 glass Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000013141 crystalline metal-organic framework Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 206010012601 diabetes mellitus Diseases 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
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- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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Abstract
The invention relates to a two-dimensional isomorphic metal organic framework material, a preparation method thereof and application thereof in electrochemical detection of glucose, wherein 1,3, 5-triisoimidazolyl benzene (TIB) is used as an organic ligand, nickel nitrate or cobalt perchlorate is used as a metal salt, two isomorphic metal organic framework materials (Ni-TIB and Co-TIB) are prepared in deionized water, N-Dimethylformamide (DMF) and mixed solution with 37% HBF 4 by means of solvothermal reaction, two MOFs with chemical formulas of C30H24N14NiO6,C100H60Cl20Co3.3N40O60. respectively show excellent glucose electrical sensing activity in terms of catalyst electrode material preparation test, and simultaneously the two MOFs are compounded to obtain heterogeneous composite materials (AB/Ni-TIB and AB/Co-TIB) which show more excellent glucose electrical sensing activity in catalyst electrode material preparation test.
Description
Technical Field
The invention relates to the technical field of metal-organic frame materials, in particular to a two-dimensional isomorphic metal-organic frame material, a preparation method thereof and application thereof in electrochemical detection of glucose.
Background
With the increasing quality of life of human substances, various new diseases are also accompanied, diabetes is one of them, and glucose level in blood is the only standard for clinical diagnosis of diabetes, so the research of glucose sensors is attracting attention. Electrochemical glucose sensors have been rapidly developed in recent years, and among many electrochemical glucose sensors, non-enzymatic glucose sensors are increasingly gaining attention due to their low cost, high stability and high sensitivity, and many materials such as metals, metal oxides and polymers have been used as glucose sensing electrode materials.
MOFs metal organic framework materials are based on their unique structure, such as: the nano-material has extremely high specific surface area, coordinated pore diameter, pore channel size adjustability, skeleton component diversity and the like, is considered to be an extremely important electrocatalyst and is paid attention to, and the application of the nano-material prepared by taking MOFs as a template in the electrochemical field has been widely reported.
In recent years, metal Organic Frameworks (MOFs) have been widely used in the field of electrochemical sensing as a non-enzymatically catalyzed catalyst. MOFs have large specific surface area and oxidation-reduction energy, provide rich active sites for the electrocatalytic action of glucose, and can be used as an enzyme catalyst for electrochemical detection of glucose.
Disclosure of Invention
The invention provides a two-dimensional isomorphic metal organic framework material, a preparation method thereof and application thereof in electrochemical detection of glucose, wherein 1,3, 5-triisoimidazolyl benzene (TIB) is used as a ligand, transition metal nickel or cobalt is used as a metal center to form the metal organic framework material (Ni-TIB and Co-TIB), and the material is used for preparing a catalyst electrode material and shows excellent glucose electrical sensing activity during testing.
The technical scheme of the invention is that the two-dimensional isomorphic metal organic framework material is C 30H24N14NiO6 crystalline material or C 100H60Cl20Co3.3N40O60 crystalline material; and the crystal of the crystalline material belongs to a trigonal system, the space group is P-31c, and the unit cell parameters are as follows: α=90°, β=90°, γ=120°,
The invention also relates to a preparation method of the two-dimensional isomorphic metal organic framework material, which comprises the following specific steps: 1,3, 5-triimidazolyl benzene (TIB) is taken as an organic ligand, nickel nitrate or cobalt perchlorate is taken as metal salt, and the metal organic framework material is obtained by adding the metal organic framework material into a mixed solution of deionized water, N-Dimethylformamide (DMF) and 37% HBF 4 in mass concentration through solvothermal reaction.
Further, the molar ratio of organic ligand to metal salt was 1:4.
Further, the volume ratio of deionized water, N-Dimethylformamide (DMF) and 37% HBF 4 by mass concentration in the mixed solution is 2:4:0.6-1.
Further, the solvothermal reaction condition is 100 ℃ and the reaction time is 48 hours.
The invention also relates to application of the two-dimensional isomorphic metal organic framework material as an electrocatalyst in the aspect of glucose electrical sensing.
The invention also relates to a composite material prepared from the two-dimensional isomorphic metal organic frame material and acetylene black, wherein the mass ratio of the two-dimensional isomorphic metal organic frame material to the acetylene black is 1:1.
The invention also relates to a preparation method of the composite material, which comprises the following specific steps: weighing and mixing the metal organic frame material and Acetylene Black (AB), adding ethanol after mechanical grinding, carrying out ultrasonic dispersion, and carrying out vacuum drying and grinding at 80-100 ℃ to obtain the composite material of the metal organic frame material and the acetylene black.
The invention also relates to application of the composite material prepared from the two-dimensional isomorphic metal organic framework material and acetylene black as an electrocatalyst in the aspect of glucose electrical sensing.
The invention has the beneficial effects that:
According to the invention, 1,3, 5-triimidazolyl benzene (TIB) is used as an organic ligand, nickel nitrate or cobalt perchlorate is used as metal salt, two isomorphic metal organic frame materials (Ni-TIB and Co-TIB) are prepared in a mixed solution of deionized water, N-Dimethylformamide (DMF) and 37% HBF 4 by means of solvothermal reaction, two MOFs with chemical formulas of C30H24N14NiO6,C100H60Cl20Co3.3N40O60. respectively show excellent glucose electrical sensing activity in the aspect of catalyst electrode material preparation test, and simultaneously, the two MOFs are compounded to obtain heterogeneous composite materials (AB/Ni-TIB and AB/Co-TIB), and the heterogeneous composite materials show more excellent glucose electrical sensing activity in the catalyst electrode material preparation test.
Drawings
Fig. 1: three-dimensional packing diagram of crystalline metal organic framework material (Ni-TIB) synthesized in example 4.
Fig. 2: three-dimensional packing diagram of crystalline metal organic framework material (Co-TIB) synthesized in example 8.
Fig. 3: XRD patterns of Ni-TIB prepared in example 4 were obtained.
Fig. 4: XRD spectrum for Co-TIB prepared in example 8.
Fig. 5: fourier infrared spectra of the Ni-TIB and Co-TIB prepared in examples 4 and 8 and the composite materials (AB/Ni-TIB and AB/Co-TIB) prepared in examples 10 and 11.
Fig. 6: time-current profile for continuous addition of glucose at different concentrations to 0.1M NaOH solution for AB/Ni-TIB prepared in example 10.
Fig. 7: material AB/Ni-TIB corresponding to fig. 6 shows a linear relationship between glucose concentration and current density in 0.1M NaOH solution.
Fig. 8: stability test chart for 500 cycles of CV circulation in 0.1M NaOH solution for AB/Ni-TIB prepared in example 10.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
0.025Mmol of 1,3, 5-triisoimidazolyl benzene (TIB), 0.1mmol of nickel nitrate, 1ml of deionized water and 2ml of N, N-Dimethylformamide (DMF) are weighed in equal amounts, respectively added into 3 glass vials of 10ml, each reaction is respectively subjected to ultrasonic treatment for 30min and then added into a baking oven of 120 ℃ for constant temperature reaction for 36h, and cooled to room temperature at a constant speed of 2-3 ℃/h, and the 3 glass vials are all turbid liquids and no crystals are produced.
Example 2
0.025Mmol of 1,3, 5-triisoimidazolyl benzene (TIB), 0.1mmol of nickel nitrate, 2ml of deionized water and 1ml of N, N-Dimethylformamide (DMF) are weighed in equal amounts, respectively added into 3 glass vials of 10ml, each reaction is respectively ultrasonically treated for 30min and added into a baking oven of 120 ℃ for constant temperature reaction for 36h, and cooled to room temperature at a constant speed of 2-3 ℃/h, and the 3 glass vials are all turbid solutions and no crystals are produced.
Example 3
0.025Mmol of 1,3, 5-triisoimidazolyl benzene (TIB), 0.1mmol of nickel nitrate, 1ml of deionized water and 2ml of N, N-Dimethylformamide (DMF) are weighed in equal amounts, then 0.05-0.5ml (namely 0.05ml, 0.1ml, 0.2ml, 0.3ml, 0.4ml and 0.5 ml) of 37% HBF 4 is added into each small bottle respectively, the mixture is added into 6 glass small bottles of 10ml respectively, each reaction is respectively subjected to ultrasonic treatment for 30min and then is added into an oven of 120 ℃ for constant temperature reaction for 36h, the temperature is reduced to room temperature at a constant speed of 2-3 ℃/h, and the 6 glass small bottles are transparent clear liquid and no crystal is produced.
Example 4
0.025Mmol of 1,3, 5-triisoimidazolyl benzene (TIB), 0.1mmol of nickel nitrate, 1ml of deionized water and 2ml of N, N-Dimethylformamide (DMF) are weighed in equal amounts, 0.05-0.5ml (namely 0.05ml, 0.1ml, 0.2ml, 0.3ml, 0.4ml and 0.5 ml) of 37% HBF 4 is added into each of the vials respectively, the mixture is added into 6 glass vials of 10ml respectively, each reaction is respectively subjected to ultrasonic treatment for 30min and then is added into an oven of 100 ℃ for constant temperature reaction for 48h, the mixture is cooled to room temperature at a constant speed of 2-3 ℃/h, light blue crystals are generated in the vials of 0.3ml, 0.4ml and 0.5ml HBF 4, and the crystals of the vials of 0.5ml HBF 4 are the most regular and the yield is the highest. As can be seen from fig. 3, the powder diffraction peak of the prepared sample is highly consistent with the diffraction peak of Ni-TIB simulated by single crystal data, and the obtained sample is the Ni-MOF material, and the crystallographic parameters are shown in table 1.
Example 5
Equal amounts of 0.025mmol of 1,3, 5-triisoimidazolyl benzene (TIB), 0.1mmol of cobalt perchlorate, 1ml of deionized water, 2ml of N, N-Dimethylformamide (DMF) were weighed and added into 3 glass vials of 10ml respectively, each reaction was sonicated for 30min and put into an oven of 120℃for a constant temperature reaction for 36h, and cooled to room temperature at a constant speed of 2-3℃per hour, and the 3 glass vials were all cloudy solutions, all no crystals were produced.
Example 6
Equal amount of 0.025mmol of 1,3, 5-triisoimidazolyl benzene (TIB), 0.1mmol of cobalt perchlorate, 2ml of deionized water and 1ml of N, N-Dimethylformamide (DMF) are respectively added into 3 glass vials of 10ml, each reaction is respectively ultrasonically treated for 30min and added into a baking oven of 120 ℃ for constant temperature reaction for 36h, the temperature is reduced to room temperature at a constant speed of 2-3 ℃/h, and 3 glass vials are all turbid liquid and no crystal is produced.
Example 7
0.025Mmol of 1,3, 5-triisoimidazolyl benzene (TIB), 0.1mmol of cobalt perchlorate, 1ml of deionized water and 2ml of N, N-Dimethylformamide (DMF) are weighed in equal amounts, then 0.05 to 0.5ml (namely 0.05ml, 0.1ml, 0.2ml, 0.3ml, 0.4ml and 0.5 ml) of 37 percent HBF 4 is added into each small bottle respectively, the mixture is added into 6 glass small bottles of 10ml respectively, each reaction is respectively subjected to ultrasonic treatment for 30min and is added into an oven of 120 ℃ for constant temperature reaction for 36h, the temperature is reduced to room temperature at a constant speed of 2 to 3 ℃/h, and the 6 glass small bottles are transparent clear liquid and no crystal is produced.
Example 8
0.025Mmol of 1,3, 5-triisoimidazolyl benzene (TIB), 0.1mmol of cobalt perchlorate, 1ml of deionized water and 2ml of N, N-Dimethylformamide (DMF) are weighed in equal amounts, 0.05-0.5ml (namely 0.05ml, 0.1ml, 0.2ml, 0.3ml, 0.4ml and 0.5 ml) of 37% HBF 4 are added into each of the vials respectively, 6 10ml glass vials are added respectively, each reaction is subjected to ultrasonic treatment for 30min and then added into a 100 ℃ oven for constant temperature reaction for 48h, and cooled to room temperature at a constant speed of 2-3 ℃/h, orange crystals are generated in the vials of 0.3ml, 0.4ml and 0.5ml HBF 4, wherein the crystals of the vials added with 0.5ml HBF4 dropwise are the most regular and the yield is the highest. As can be seen from FIG. 4, the powder diffraction peak of the prepared sample is highly consistent with the diffraction peak of the Co-MOF simulated by the single crystal data, and the obtained sample is the Co-TIB material, and the crystallographic parameters are shown in Table 1.
The crystals synthesized in example 4 and example 8 were subjected to structural measurement using a small molecular single crystal X-ray diffractometer from Rigaku corporation, diffraction intensity and cell parameters were measured using Mo kα rays monochromatized with a graphite monochromator at 293K, and the collected data was subjected to empirical absorption correction by scanning techniques, and the obtained results were analyzed by direct method using Shelxtl-97 procedure and corrected by full matrix least square method to obtain the crystallographic data as shown in table 1.
TABLE 1 Crystal parameter Table
Example 9
Samples of porous crystalline metal organic framework materials (Ni-TIB or Co-TIB) collected in examples 4 and 8 were uniformly ground by an agate mortar, respectively, 4mg was weighed into 2ml sample tubes, 1.2ml absolute ethyl alcohol, 0.6ml deionized water and 0.2ml naphthol were added, after 60min of ultrasound, 4 μl of dispersion was sucked by a pipette and coated on the surface of the polished glassy carbon electrode, the sensing performance of the electrochemical detection glucose was tested, and after the CV curve was scanned to be stable in 0.1M NaOH solution, the CV curve of the glucose electrical sensing was tested.
The Ni-TIB and Co-TIB synthesized by the method are subjected to glucose electric induction test, and the sensitivity of the material Ni-TIB is higher, so that the MOF material is more suitable for the test of electrochemical detection of glucose.
Example 10
5Mg of the porous crystalline metal organic framework material synthesized in the example 4 and 5mg of the conductive substance Acetylene Black (AB) are placed in an agate mortar and ground for 15min, and then the composite material (AB/Ni-TIB) of Ni-TIB and AB is obtained. Weighing 4mg of the ground sample into a 2ml sample tube, adding 1.2ml of absolute ethyl alcohol, 0.6ml of deionized water and 0.2ml of naphthol, carrying out ultrasonic treatment for 30min, sucking 4 μl of dispersion liquid by a pipette, coating the dispersion liquid on the surface of a polished glassy carbon electrode, and testing the sensing performance of the electrochemical detection glucose.
Example 11
5Mg of the porous crystalline metal organic framework material synthesized in the example 8 and 5mg of the conductive substance Acetylene Black (AB) are placed in an agate mortar and ground for 15min, so that a Co-TIB and AB composite material (AB/Co-TIB) can be obtained. Weighing 4mg of the ground sample into a 2ml sample tube, adding 1.2ml of absolute ethyl alcohol, 0.6ml of deionized water and 0.2ml of naphthol, carrying out ultrasonic treatment for 30min, sucking 4 μl of dispersion liquid by a pipette, coating the dispersion liquid on the surface of a polished glassy carbon electrode, and testing the sensing performance of the electrochemical detection glucose.
The Ni-TIB, co-TIB, AB/Ni-TIB and AB/Co-TIB materials synthesized by the method are subjected to glucose electric sensing test, and experimental results show that the sensitivity of AB/Ni-TIB in four cases of materials in electrochemical detection of glucose is higher than 2.499 mu A mu M-1cm < -2 >, the linear range is 10-4000 mu M, and the detection limit is 0.08 mu M (S/N=3). Compared with two pure MOFs, the glucose electric susceptibility of the composite material is greatly improved. The materials were tested as shown in figures 6-8.
Claims (5)
1. A two-dimensional isomorphic metal organic framework material characterized by: the material is C 30H24N14NiO6 crystalline material or C 100H60Cl20Co3.3N40O60 crystalline material; and the crystal of the crystalline material belongs to a trigonal system, the space group is P-31c, and the unit cell parameters are as follows: α=90°, β=90°, γ=120°, a= 11.3365 (2) a, b= 11.3365 (2) a, c= 15.2070 (4) a; when the material is prepared, 1,3, 5-tri-imidazolyl benzene is used as an organic ligand, nickel nitrate or cobalt perchlorate is used as metal salt, and the metal salt is added into a mixed solution of deionized water, N-dimethylformamide and 37% HBF 4 in mass concentration, and a metal organic frame material is obtained through solvothermal reaction; wherein the molar ratio of the organic ligand to the metal salt is 1:4; deionized water, N-dimethylformamide and 37% HBF 4 in mass concentration are mixed in a volume ratio of 2:4:0.6-1; the solvothermal reaction condition is 100 ℃ and the reaction time is 48 hours.
2. Use of the two-dimensional isomorphic metal organic framework material of claim 1 as an electrocatalyst for glucose electrical sensing.
3. The composite material prepared from the two-dimensional isomorphic metal organic framework material and acetylene black according to claim 1, which is characterized in that: the mass ratio of the two-dimensional isomorphic metal organic framework material to the acetylene black is 1:1.
4. A method of preparing a composite material according to claim 3, comprising the specific steps of: and (3) weighing the metal organic frame material and acetylene black, mixing, adding ethanol after mechanical grinding, performing ultrasonic dispersion, and performing vacuum drying at 80-100 ℃ and grinding to obtain the composite material of the metal organic frame material and the acetylene black.
5. The use of the composite material prepared from the two-dimensional isomorphic metal organic framework material and acetylene black as described in claim 3 as an electrocatalyst in glucose electrical sensing.
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