CN107315042B - Zinc metal organic framework nano material and its application - Google Patents

Zinc metal organic framework nano material and its application Download PDF

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CN107315042B
CN107315042B CN201710432207.XA CN201710432207A CN107315042B CN 107315042 B CN107315042 B CN 107315042B CN 201710432207 A CN201710432207 A CN 201710432207A CN 107315042 B CN107315042 B CN 107315042B
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organic framework
metal organic
nano material
zinc metal
glucose
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CN107315042A (en
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庞欢
郑莎莎
唐燚剑
李清
薛怀国
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Yangzhou University
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Yangzhou University
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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
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • 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
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

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Abstract

The invention discloses a kind of zinc metal organic framework nano materials, its preparation step are as follows: mix the dimethyl formamide solution of the ethylene glycol solution of divalent zinc salt and terephthalic acid (TPA), it is agitated uniformly after, carry out hydro-thermal reaction at 150~200 DEG C, obtain reaction into raw sediment；By sediment to dry after dimethylformamide and ethanol washing to get the zinc metal organic framework nano material.Enzyme-free glucose electrochemical sensor prepared by the present invention is wide to glucose detection range, and for detection range in 0.5 μM of -8.062 mM, detection sensitivity is high, has good interference free performance to uric acid, dopamine, sodium chloride.

Description

Zinc metal organic framework nano material and its application
Technical field
The invention belongs to enzyme-free glucose sensor preparation technical fields, and in particular to a kind of zinc metal organic framework nanometer Material and its application.
Background technique
Glucose is main life process characteristic compounds, its analysis is with detection to the health and disease of the mankind Diagnosis, treatment and control important in inhibiting.Therefore, the research of glucose sensor is chemistry and biosensor always The hot spot of research.Wherein electrochemical glucose sensor is the biosensor developed earliest.By whether there is or not use enzyme to be used to construct Electrochemical glucose sensor can be divided into electrochemical glucose sensor and enzyme-free glucose electricity based on enzyme by biosensor Chemical sensor.Electrochemical glucose sensor based on enzyme using enzyme thus have the characteristics that specificity is high, reaction speed is fast, But there is also many deficiencies, and it to be made to receive certain condition limitation in practical applications.Therefore, enzyme-free glucose electrochemistry The development of sensor becomes another research hotspot of electrochemical glucose sensor.
Currently, there is detection glucose process vulnerable to other chaff interferents in the electrode material without enzyme electrochemical glucose sensor The defect of the influence of matter (such as chloride ion, uric acid), to influence the accuracy of testing result.And existing sensor is to no enzyme Portugal The linearly interval of grape sugar detection is relatively narrow, lesser far below average blood glucose level (empty stomach) range (4.4-6.6 mM) of human body Linearly interval is limited by very large its application in diabetes detection.Therefore, exploitation linearly interval it is wide, not vulnerable to it The new electrode materials that its interfering substance (such as chloride ion, uric acid) influences are extremely urgent.
Summary of the invention
For disadvantages described above, the object of the present invention is to provide a kind of zinc metal organic framework nano material, preparation method and It is applied.
Realizing the technical solution of the object of the invention is:
A kind of zinc metal organic framework nano material, is prepared by the following steps:
(1) dimethylformamide (DMF) solution of the ethylene glycol solution of divalent zinc salt and terephthalic acid (TPA) is mixed, through stirring It after mixing 1~1.5 hour, is carried out hydro-thermal reaction 6 hours at 150~200 DEG C, obtains reaction into raw sediment；
(2) by sediment to dry after DMF and ethanol washing to get the zinc metal organic framework nano material.
Further, divalent zinc salt of the present invention is selected from Zn (NO3)2•6H2O、ZnSO4•H2O or Zn (CH3COO)2• 4H2O any one.The experiment proved that be easier to obtain required product since the acid group of these types of metal salt institute band is easily sloughed, Therefore preferential using these types of metal salt.
Further, in order to obtain product morphology most preferably and best performance, the terephthalic acid (TPA) (C8H6O4) and divalent zinc The molar ratio of salt is 1: 1；The volume ratio that feeds intake of the dimethylformamide (DMF) and ethylene glycol is 8: 5.
Application of the above-mentioned zinc metal organic framework nano material as glucose sensor electrode, under ultrasound condition, institute It states zinc metal organic framework nano material to be dissolved in perfluorosulfonic acid type polymer solution, then modify on glass-carbon electrode, Obtain no enzyme type glucose sensor.
Compared with prior art, the present invention has following marked improvement:
(1) enzyme-free glucose electrochemical sensor prepared by the present invention is wide to glucose detection range, be 0.5 μM- 8.062 mM, detection sensitivity is high, has good interference free performance to uric acid, dopamine, sodium chloride.
(2) zinc metal organic framework nano material prepared by the present invention is prepared by simple hydro-thermal method, the former material of use Expect nontoxic, environmentally friendly, at low cost, simple process, easily operated control is suitable for continuous words large-scale production, preparation process green ring It protects.
(3) zinc metal organic framework nano material prepared by the present invention have outstanding electrochemical response, the range of linearity it is wide, The advantages that high sensitivity, good anti-interference ability and ideal electrochemical stability, it can be used for electrochemical sensing.
Detailed description of the invention
Attached drawing 1 is the big multiplying power scanning electron microscope (SEM) photograph of zinc metal organic framework nano-electrode material prepared by the present invention.
Attached drawing 2 is the small multiplying power scanning electron microscope (SEM) photograph of zinc metal organic framework nano-electrode material prepared by the present invention.
Attached drawing 3 is the circulation volt that zinc metal organic framework nano-electrode material prepared by the present invention is applied to detection glucose Pacify curve graph.
Attached drawing 4 is that zinc metal organic framework nano-electrode material prepared by the present invention detects concentration of glucose current-vs-time Curve.
Attached drawing 5 is the linearly interval fitting that zinc metal organic framework nano-electrode material prepared by the present invention detects glucose Figure.
Attached drawing 6 is when m- electric current of the zinc metal organic framework nano-electrode material prepared by the present invention to disturbance object Response diagram.
Attached drawing 7 is the reproducibility that zinc metal organic framework nano-electrode material prepared by the present invention is applied to detection glucose Time current curve.
Attached drawing 8 is the stability that zinc metal organic framework nano-electrode material prepared by the present invention is applied to detection glucose Time current curve.
Specific embodiment
With example, the invention will be further described with reference to the accompanying drawings and detailed description, but not limited to this.
Metal-organic framework materials, one kind possessing changeable structure and pattern, diversified component and porous novel Jie Porous materials, it has also become the new lover of academia in recent decades.The physics and chemical property of metal-organic framework materials multiplicity: such as Changeable topological structure, magnetism, catalytic, fluorescence etc., and the performance easily modified inhale it in small molecule carrier, gas Before the fields such as attached and storage, molecular sieve, drug delivery, luminescent material, electrochemical sensing, heterocatalysis possess huge application Scape.Compared to other ligand materials, because of high surface area, high porosity, low-density, controlled architecture, adjustable aperture, metal is organic Framework material is considered as one of most promising material in the following nm regime.
One, zinc metal organic framework nano-electrode material is prepared:
0.05g zinc nitrate is dissolved in 5 mL ethylene glycol, mixed solution I is obtained.
The above zinc nitrate is derived from Zn (NO3)2•6H2O、ZnSO4•H2O or Zn (CH3COO)2•4H2O。
0.03g terephthalic acid (TPA) is dissolved in 8mL dimethylformamide (DMF), mixed solution I I is obtained.
Solution I and II are mixed, stirring at normal temperature 1 hour, then hydro-thermal reaction 12 hours under the conditions of 150 DEG C, obtained White precipitate is dried to arrive zinc metal organic framework nano material after washing 3 times respectively with DMF and ethyl alcohol.
Carry out SEM test to zinc metal organic framework nano material: Fig. 1 is the amplification of zinc metal organic framework nano material Electron scanning micrograph under 5000 times, Fig. 2 are the scanning electron under 500 times of zinc metal organic framework nano material amplification Microscope photo.Test result shows that the zinc metal organic framework nano material of synthesis is circular block shape top package threadiness Nano wire.
Two, the preparation of glucose sensor electrode:
1, the glass-carbon electrode that diameter is 3mm with the sand paper for having adsorbed 1 μm of aluminum oxide suspension and 0 .05 has been adsorbed into respectively The sand paper sanding and polishing of μm aluminum oxide suspension.
2, the good glass-carbon electrode of sanding and polishing is successively placed on after being cleaned by ultrasonic 3 minutes in dehydrated alcohol and deionized water and is dried It is dry, clean glass-carbon electrode is obtained, for use.
3, it is 1% perfluorosulfonic acid type polymer that the zinc metal organic framework nano material for taking 10mg to prepare, which is dissolved in 1mL concentration, Mixed solution is made in ultrasonic mixing in solution, then modifies the method that 5 μ L mixed solutions use coating in diameter as 3mm's Clean glassy carbon electrode surface, after natural drying up to zinc metal organic framework nano material sensor electrode, that is, of the present invention Glucose sensor electrode.
4, electrolyte is prepared:
Using sodium hydroxide as electrolyte, wherein naoh concentration is 0.1 mol/L.
5, detecting electrode chemical property:
Zinc metal organic framework nano material sensor electrode is placed in the sodium hydroxide solution of 0.1 mol/L and is carried out Measurement.
Under current potential between -0.1~0.8 V, sweep speed control is 0.1 V/s, carries out cyclic voltammetry scan, successively The glucose solution that concentration is gradually increased is added, and observes current-responsive result.Under 0.55 V potentiostatic scanning, using zinc gold Belong to organic backbone nano material sensor electrode, the continuous glucose that various concentration is added dropwise is stirred continuously in the liquid of sodium hydroxide bottom Carry out detection current versus time curve.Using zinc metal organic framework nano material sensor electrode 0.1 at 0.55 V of current potential It is respectively 100 μM of glucose, 5 μM of ascorbic acid, 5 μM of uric acid, 5 μM with concentration in the liquid of mol/L sodium hydroxide bottom The standard liquid of dopamine, 5 μM of sodium chloride and 100 μM of glucose carries out dropwise addition test.Test zinc metal organic framework nanometer material The reproducibility for expecting sensor electrode repeats glucose (100 μM) to be added 10 times in 0.1 mol/L sodium hydroxide bottom liquid, sees Examine curent change.Detect the stability of zinc metal organic framework nano material sensor electrode, liquid (100 μM) at glucose bottom After middle electro-catalysis 3500 seconds, curent change is observed.
Fig. 3 solid line is 500 μM of glucose solutions, and dotted line is blank control experiment, and shown by Fig. 3: zinc metal is organic Skeleton nano material sensor electrode material 0.1 V/s sweep speed under, 500 μM of glucose solution oxidation peaks obviously compare blank Group test is strong.
Fig. 4 shows, zinc metal organic framework sensor electrode to the glucose bottom liquid of various concentration carry out detection electric current-when Half interval contour, it can be seen that zinc metal organic framework nano material quick, sensitive catalytic response ability occurs to glucose.
Fig. 5 shows, the concentration range of linearity of acquisition is 0.5 μM of -8.062 mM, linear equation be [R=0.98939, Current I (μ A)=0.20726+ 2.195*10^-5C (μM)], sensitivity is 310.686 mA mM-1cm-2。
Fig. 6 shows that zinc metal organic framework sensor electrode is in 0.55 V of current potential in 0.1 mol/L sodium hydroxide bottom liquid With concentration be respectively 100 μM of glucose, 5 μM of ascorbic acid, 5 μM of uric acid, 5 μM of dopamines, 5 μM of sodium chloride and The standard liquid of 100 μM of glucose carries out dropwise addition test, the results showed that, electrode material has fabulous anti-interference ability.
Fig. 7 is shown, in 0.1 mol/L sodium hydroxide bottom liquid, repeats glucose (100 μM) to be added 10 times, have almost Identical current-responsive, electrode material have fabulous reproducibility.
Fig. 8 shows that in glucose bottom liquid (100 μM) after electro-catalysis 3500 seconds, response current is kept approximately constant, electricity Pole material has fabulous stability.
In conclusion the glucose sensor that the present invention uses zinc metal organic framework to prepare as sensor electrode material The advantage of electrode is:
1, linearity test interval range: 0.5 μM of -8.062 mM glucose；
2, detection sensitivity: 310.686 mA mM of sensitivity-1cm-2；
3, anti-interference: there is good anti-interference to uric acid, dopamine, sodium chloride in the detection process of glucose Energy.

Claims (7)

1. a kind of blocky zinc metal organic framework nano material of fibrous nano line cladding, which is characterized in that by following steps Preparation:
(1) by the dimethyl formamide solution of the ethylene glycol solution of divalent zinc salt and terephthalic acid (TPA) mix, it is agitated uniformly after, Hydro-thermal reaction is carried out at 150~200 DEG C, obtains reaction into raw sediment；
(2) by sediment to dry after dimethylformamide and ethanol washing to get the zinc metal organic framework nanometer material Material.
2. nano material as described in claim 1, which is characterized in that in step (1), divalent zinc salt is selected from Zn (NO3)2• 6H2O、ZnSO4•H2O or Zn (CH3COO)2•4H2O any one.
3. nano material as described in claim 1, which is characterized in that in step (1), the throwing of terephthalic acid (TPA) and divalent zinc salt Expect that molar ratio is 1: 1；The volume ratio that feeds intake of dimethylformamide and ethylene glycol is 8: 5.
4. nano material as described in claim 1, which is characterized in that in step (1), mixing time is 1~1.5 hour；Water The thermal response time is 6 hours.
5. the system for the blocky zinc metal organic framework nano material that the fibrous nano line as described in claim 1-4 is any coats Preparation Method.
6. the blocky zinc metal organic framework nano material conduct that the fibrous nano line as described in claim 1-4 is any coats The application of glucose sensor electrode.
7. application as claimed in claim 6, which is characterized in that under ultrasound condition, the nano material is dissolved in perfluor It in sulfonic acid polymer solution, then modifies on glass-carbon electrode, which, which first uses, has adsorbed 1 μm of aluminum oxide suspension Sand paper polished after again obtained by the sand paper sanding and polishing for having adsorbed 0.05 μm of aluminum oxide suspension, finally obtain described Glucose sensor electrode.
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CN107478696B (en) * 2017-07-14 2019-06-18 长江大学 The preparation method of carbon material modified glassy carbon electrode for cadmium ion detection
CN107727720A (en) * 2017-11-29 2018-02-23 河南科技学院 HKUST‑1（Cu‑MOFs）Application in glucose sensor electrode is prepared
CN108063266A (en) * 2017-12-14 2018-05-22 扬州大学 A kind of preparation method of the Prussian blue similar object modified electrode of high-performance
CN109402755B (en) * 2018-10-30 2021-07-20 武汉纺织大学 Preparation method of composite fiber with surface embedded with metal organic framework nanofiber
CN109467493B (en) * 2018-11-16 2020-10-27 西北工业大学 Preparation method of metal organic framework material modified nano metal particles
CN110320257A (en) * 2019-07-02 2019-10-11 吉林省裕林药业有限公司 A kind of blood glucose sensor and preparation method thereof based on metallic zinc organic transistor
CN112934271B (en) * 2021-01-29 2022-10-28 广东工业大学 Porous nanowire with metal-organic framework and preparation method and application thereof
CN113912863B (en) * 2021-11-26 2023-02-24 江西理工大学 Zinc-based metal-organic framework with fluorescent recognition performance on tetracycline, benzaldehyde and uric acid and preparation method thereof

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