CN107238650B - A kind of two dimension and its is applied nickel cobalt bimetallic MOFs nanometer sheet in glucose detection - Google Patents
A kind of two dimension and its is applied nickel cobalt bimetallic MOFs nanometer sheet in glucose detection Download PDFInfo
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- CN107238650B CN107238650B CN201710432608.5A CN201710432608A CN107238650B CN 107238650 B CN107238650 B CN 107238650B CN 201710432608 A CN201710432608 A CN 201710432608A CN 107238650 B CN107238650 B CN 107238650B
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- nickel cobalt
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
Abstract
The invention discloses the applications in a kind of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet and its glucose detection.The present invention mainly passes through one step hydro thermal method from bottom to top and has synthesized two-dimentional nickel cobalt bimetallic MOFs nanometer sheet in the substrates such as nanoporous acupuncture needle, carbon paper, gold plaque, and it is applied to no enzyme type electrochemical glucose sensor as electrode, the relatively traditional ball polyhedral MOFs material of two dimension MOFs nanometer sheet material has the more active sites of exposure, the advantages that synergistic effect and higher quality charge transport ability of nickel and cobalt, to effectively raise its glucose sensing performance.
Description
Technical field
The invention belongs to biosensor technique field, in particular to a kind of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet and its Portugal
Application in grape sugar detection.
Background technique
It is most important for the diagnosis of diabetes and control to improve the performance without enzyme type glucose biological sensor.Two-dimentional material
Material is due to having many advantages, such as that biggish specific surface area, more active sites, faster mass transport can have higher catalysis
Activity.Currently, being concentrated mainly on graphene, transition gold about application study of the two-dimensional material on no enzyme type glucose sensor
Belong on the materials such as sulfide, metal oxide, layered double hydroxide, and is directly to metal ion or metal cluster
Node and organic ligand bridge to form metal-organic framework (MOFs) material with periodic network structure as electrode material
Being almost absent as glucose sensor, the synthesis pattern of present MOFs are confined to ball-type mostly, hexahedron, octahedron,
On the polyhedrons such as dodecahedron, wherein two dimension MOFs is seldom synthesized, and it is even more few for doing glucose sensing application with two-dimentional MOFs
See.The synthesis of present two dimension MOFs mainly using top-down method or adds the method for structure directing agent to close with down-top
At, these synthetic method low yields, cumbersome, and the structure of destructible MOFs.The purpose of the present invention is be directed to existing skill
The deficiency of art provides and a kind of prepare simple down-top method and be prepared for New Two Dimensional nickel cobalt bimetallic MOFs Nano sheet material
Material, and it is applied to electrochemical glucose sensor.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet and
Application in its glucose detection.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of two dimension nickel cobalt bimetallic MOFs nanometer sheet is led to
Following steps are crossed to be prepared:
(1) 0.8724g Nickelous nitrate hexahydrate and 0.8731g cabaltous nitrate hexahydrate are dispersed in the deionization of 100mL
In water, nickel cobalt metal mixed salt solution is obtained；
(2) 0.4348g amino terephthalic acid (TPA) is dissolved in 20mL n,N dimethylformamide (DMF), obtains organic match
Liquid solution；
(3) solution that the solution and 1mL step 2 for taking 6mL step 1 to prepare respectively are prepared, is transferred to after mixing and is placed with 5mL
In the 25mL reaction kettle of DMF, and 6h is reacted at 120 DEG C, obtains purple product；
(4) it after cleaning the purple product reacted in step 3 with ethyl alcohol, and is dried in vacuo at 60 DEG C, obtains two
Tie up nickel cobalt bimetallic MOFs nanometer sheet.
A kind of application of the two dimension nickel cobalt bimetallic MOFs nanometer sheet in examination of glucose concentration, the application are as follows: will be two-dimentional
Nickel cobalt bimetallic MOFs nanometer sheet is carried on nano-porous gold wire surface, detects to concentration of glucose.
Further, the two-dimentional nickel cobalt bimetallic MOFs nanometer sheet is carried on the acupuncture needle surface by the following method:
Organic ligand solution described in nickel cobalt metal mixed salt solution described in 6mL and 1mL is mixed, with 5mL DMF and porous acupuncture needle 120
Hydro-thermal reaction 6h is carried out at DEG C；After cleaning, the acupuncture needle of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet load is obtained.
The beneficial effects of the present invention are: the present invention has obtained two-dimentional nickel cobalt bimetallic MOFs by simple one step hydro thermal method
Nanometer sheet material can be applied to electrochemical glucose sensor using electrode prepared by the material.In terms of preparation, this method
It is prepared using down-top method, with easy to operate with traditional top-down method compared with, without adding structure directing
The advantages that agent.In terms of catalytic activity, the two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material synthesized, than existing most of balls
Type and polyhedron MOFs material have bigger specific surface area, more active sites, which also has the collaboration of nickel and cobalt
Effect, to improve the sensing capabilities to glucose.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram piece of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material prepared by the present invention
(SEM)。
Fig. 2 is the power spectrum picture (EDS) of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material prepared by the present invention.
Fig. 3 is two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material prepared by the present invention in 0.1M NaOH electrolyte
4mM glucose is not added and adds the cyclic voltammogram of 4mM glucose.
Fig. 4 a is two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material prepared by the present invention in 0.1M NaOH electrolyte
The constantly I-T curve of addition glucose, operating voltage: 0.5V.Fig. 4 b corresponds to the calibration curve of the I-T curve of Fig. 4 a.
Specific embodiment
Below with reference to embodiment the invention will be further described technical solution of the invention, these embodiments cannot
It is not understood as the limitation to technical solution.
Embodiment 1: the present embodiment prepares two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material, specifically includes the following steps:
(1) 0.8724g Nickelous nitrate hexahydrate and 0.8731g cabaltous nitrate hexahydrate are dispersed in the deionization of 100mL
In water, nickel cobalt metal mixed salt solution is obtained；
(2) 0.4348g amino terephthalic acid (TPA) is dissolved in 20mL n,N dimethylformamide (DMF), obtains organic match
Liquid solution；
(3) it takes mixed solution obtained in 6mL step 1 and 1mL step 2 to be transferred to respectively and is placed with 5mL DMF and one is received
In the 25mL reaction kettle of meter Duo Kong acupuncture needle, and 6h is reacted at 120 DEG C, obtains purple product on nanoporous acupuncture needle；
(4) it after cleaning the purple product reacted in step 3 with ethyl alcohol, and is dried in vacuo at 60 DEG C, obtains two
Tie up nickel cobalt bimetallic MOFs nanometer sheet.
Fig. 1 is the scanning electron microscope diagram (SEM) of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material prepared by the present invention,
It as can be seen from the figure is that two-dimentional nickel cobalt bimetallic MOFs nanometer sheet homogeneous vertical is grown in porous gold substrate, nanometer sheet diameter
About 100nm or so.
Fig. 2 is the power spectrum picture of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material prepared by the present invention, can from figure
Material prepared contains Ni, Co, C, N, O element out, and each element keeps certain pattern, NiCo layered complementary type point
Cloth illustrates two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material.In addition, the XRD of nickel cobalt bimetallic MOFs nanometer sheet and theoretical mould
Quasi- XRD coincide very much, and further synthesized material is nickel cobalt bimetallic MOFs.
Embodiment 2: the present embodiment uses prepared two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material as glucose biological
The application of sensor, key step are as follows:
A, respectively to be modified with the gold electrode of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet as working electrode, Pt piece is to electricity
Pole, SCE are reference electrode, are assembled into three-electrode electro Chemical system and are tested；
B, when cyclic voltammetry, electrochemical window is selected as 0V~0.6V, and sweeping speed is 50mV/s；I-T curve voltage is selected as
0.5V, background current constantly add different glucose solution with liquid-transfering gun and serum carry out after 10min reaches stable state
Mixing test obtains current-responsive value i.e. staircase curve and calibration curve under different concentration of glucose；
Fig. 3 is two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material prepared by the present invention in 0.1M NaOH electrolyte
4mM glucose is not added and adds the cyclic voltammogram of 4mM glucose, it is seen that being added after glucose, MOFs nanometer sheet
Material oxidation peak current obviously increases, and illustrates that this material has good catalytic effect to glucose, can be used as glucose sensor
Electrode material uses.
Fig. 4 a is two-dimentional nickel cobalt bimetallic MOFs nanometer sheet material prepared by the present invention in 0.1M NaOH electrolyte
The constantly I-T curve of addition glucose, operating voltage: 0.5V.Fig. 4 b corresponds to the calibration curve of the I-T curve of Fig. 4 a.From
It can be seen that in figure, the sensitivity of the electrode is 370 μ AmM-1, the response time be less than 1s, the range of linearity be 6 μM of -8.9mM, detection pole
It is limited to 1 μM.
In addition, being respectively synthesized hexahedron (A), octahedron (B), dodecahedron (C) structure according to art-disclosed techniques
Nickel cobalt bimetallic MOFs material；Then by hexahedron (A), octahedra (B), dodecahedron (C) structure nickel cobalt bimetallic
MOFs material respectively modifies gold electrode, degree of modification step (a) unanimously, and as working electrode according to described in step b
Method carry out cyclic voltammetry.The experimental results showed that compared to materials A B C, two-dimentional nickel cobalt bimetallic of the invention
MOFs nanometer sheet has higher sensitivity, the bigger range of linearity and smaller response time.
Claims (3)
1. a kind of two dimension nickel cobalt bimetallic MOFs nanometer sheet, which is characterized in that be prepared by following steps:
(1) 0.8724 g Nickelous nitrate hexahydrate and 0.8731 g cabaltous nitrate hexahydrate are dispersed in the deionized water of 100 mL
In, obtain nickel cobalt metal mixed salt solution；
(2) 0.4348 g amino terephthalic acid (TPA) is dissolved in 20 mL n,N dimethylformamide, obtains organic ligand solution；
(3) solution that the solution for taking 6 mL steps (1) to prepare respectively and 1 mL step (2) are prepared, is transferred to after mixing and is placed with 5
In the 25 mL reaction kettles of mL DMF, and 6 h are reacted at 120 DEG C, obtain purple product；
(4) it after cleaning the purple product that reaction obtains in step (3) with ethyl alcohol, and is dried in vacuo at 60 DEG C, obtains two dimension
Nickel cobalt bimetallic MOFs nanometer sheet.
2. a kind of area load has the preparation method of the nanoporous acupuncture needle of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet, feature exists
In including the following steps:
(1) 0.8724 g Nickelous nitrate hexahydrate and 0.8731 g cabaltous nitrate hexahydrate are dispersed in the deionized water of 100 mL
In, obtain nickel cobalt metal mixed salt solution；
(2) 0.4348 g amino terephthalic acid (TPA) is dissolved in 20 mL n,N dimethylformamide DMF, it is molten obtains organic ligand
Liquid；
(3) it takes mixed solution obtained in 6 mL steps (1) and 1 mL step (2) to be transferred to respectively and is placed with 5 mL DMF and one
In 25 mL reaction kettles of nanoporous acupuncture needle, and 6 h are reacted at 120 DEG C, obtain purple product on nanoporous acupuncture needle；
(4) after the acupuncture needle that reaction in step (3) is obtained load has purple product is cleaned with ethyl alcohol, and vacuum is dry at 60 DEG C
It is dry, obtain the acupuncture needle of two-dimentional nickel cobalt bimetallic MOFs nanometer sheet load.
3. the nanometer that a kind of area load that claim 2 the method is prepared has two-dimentional nickel cobalt bimetallic MOFs nanometer sheet
Application of the porous acupuncture needle in examination of glucose concentration.
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| CN107837820A (en) * | 2017-11-21 | 2018-03-27 | 南京工业大学 | A kind of preparation method of two-dimentional MOFs material loads nano-particle |
| CN109400906B (en) * | 2018-12-12 | 2021-04-30 | 太原理工大学 | Method for directly preparing multi-metal MOFs material by utilizing bimetallic complex |
| CN109776812B (en) * | 2019-02-21 | 2021-11-23 | 河北工业大学 | Preparation method of Cu-based two-dimensional flaky MOFs material |
| CN111044590A (en) * | 2019-11-26 | 2020-04-21 | 云南大学 | CuNi-MOF nano-material modified electrode and application thereof |
| CN111154110A (en) * | 2019-12-30 | 2020-05-15 | 北京交通大学 | Two-dimensional frame structure electrode material and preparation method thereof, electrochemical enzyme-free glucose sensor and preparation method and application thereof |
| CN111537589B (en) * | 2020-05-13 | 2021-09-21 | 山东大学 | Method for detecting glucose based on cobalt-based metal organic framework enzyme-free glucose sensor |
| CN112403440B (en) * | 2020-11-18 | 2022-03-18 | 山西大学 | Magnetic recyclable CoNi-MOFs @ GR adsorbent, preparation method and application to adsorption of organic dye |
| CN112759514B (en) * | 2021-02-04 | 2022-03-25 | 福州大学 | Synthetic method of columnar copper fumarate with double-enzyme activity |
| CN113176315B (en) * | 2021-03-15 | 2023-01-17 | 杭州电子科技大学 | NiO/Au nanotube array flexible electrode with core-shell structure and application thereof |
| CN113933371B (en) * | 2021-10-25 | 2023-12-22 | 扬州大学 | Preparation method of flexible biosensor electrode |
| CN114235920A (en) * | 2021-12-20 | 2022-03-25 | 天津工业大学 | NiCo LDH/NiCoS @ C composite material and preparation method and application thereof |
| CN114539545B (en) * | 2022-01-13 | 2023-06-13 | 中国科学院宁波材料技术与工程研究所 | Bimetal-organic framework material and preparation method and application thereof |
| CN115109262B (en) * | 2022-06-10 | 2023-05-16 | 湖北工业大学 | Metal organic frame nano-sheet, preparation method, working electrode and sensor |
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