CN107315042A - zinc metal organic framework nano material and its application - Google Patents
zinc metal organic framework nano material and its application Download PDFInfo
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- CN107315042A CN107315042A CN201710432207.XA CN201710432207A CN107315042A CN 107315042 A CN107315042 A CN 107315042A CN 201710432207 A CN201710432207 A CN 201710432207A CN 107315042 A CN107315042 A CN 107315042A
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Abstract
The invention discloses a kind of zinc metal organic framework nano material, its preparation process is：The dimethyl formamide solution of the ethylene glycol solution of divalent zinc salt and terephthalic acid (TPA) is mixed, it is agitated it is uniform after, hydro-thermal reaction is carried out at 150~200 DEG C, raw sediment is reacted into acquirement；By sediment to be dried after dimethylformamide and ethanol washing, described zinc metal organic framework nano material is produced.Enzyme-free glucose electrochemical sensor prepared by the present invention is wide to glucose detection scope, and detection range is in 0.5 μM of 8.062 mM, and detection sensitivity is high, has good interference free performance to uric acid, dopamine, sodium chloride.
Description
Technical field
The invention belongs to enzyme-free glucose sensor preparing technical field, and in particular to a kind of zinc metal organic framework nanometer
Material and its application.
Background technology
Glucose is main life process characteristic compounds, its analysis and health and disease of the detection to the mankind
Diagnosis, treatment and control important in inhibiting.Therefore, the research of glucose sensor is always chemistry and biology sensor
The focus of research.Wherein electrochemical glucose sensor is the biology sensor developed earliest.It is used to build using enzyme by whetheing there is
Electrochemical glucose sensor can be divided into electrochemical glucose sensor and enzyme-free glucose electricity based on enzyme by biology sensor
Chemical sensor.Electrochemical glucose sensor based on enzyme using enzyme thus with selectivity is high, reaction speed is fast the characteristics of,
But, it is received certain condition limitation in actual applications there is also many deficiencies.Therefore, enzyme-free glucose electrochemistry
Another study hotspot of development as electrochemical glucose sensor of sensor.
At present, there is detection glucose process easily by other chaff interferences in the electrode material of no enzyme electrochemical glucose sensor
The defect of the influence of matter (such as chlorion, uric acid), so as to influence the accuracy of testing result.And existing sensor is to without enzyme Portugal
The linearly interval of grape sugar detection is narrower, less far below average blood glucose level (empty stomach) scope (4.4-6.6 mM) of human body
Linearly interval make its diabetes detection in application be limited by very large.Therefore, exploitation linearly interval is wide, be difficult by it
The new electrode materials of its interfering material (such as chlorion, uric acid) influence are extremely urgent.
The content of the invention
For disadvantages described above, it is an object of the invention 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 following steps：
（1）By the ethylene glycol solution of divalent zinc salt and the dimethylformamide of terephthalic acid (TPA)（DMF）Solution is mixed, and agitated 1
After~1.5 hours, hydro-thermal reaction is carried out at 150~200 DEG C 6 hours, raw sediment is reacted into acquirement；
（2）By sediment to be dried after DMF and ethanol washing, described zinc metal organic framework nano material is produced.
Further, divalent zinc salt of the present invention is selected from Zn (NO3)2•6H2O、ZnSO4•H2O or Zn (CH3COO)2•
4H2O any one.It the experiment proved that, by the acid group of this several metal salt institutes band is easily sloughed, be more easy to obtain required product,
Therefore this several metal salt is preferentially used.
Further, in order to obtain, product morphology is optimal and best performance, the terephthalic acid (TPA)（C8H6O4）And divalent zinc
The molar ratio of salt is 1: 1；The dimethylformamide（DMF）The volume ratio that feeds intake with ethylene glycol is 8: 5.
Above-mentioned zinc metal organic framework nano material as glucose sensor electrode application, under ultrasound condition, institute
State 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 scope, is 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 from by simple hydro-thermal method, the former material of use
Expect that nontoxic, environmentally friendly, cost is low, technique is simple, it is easy to operational control, suitable for continuous words large-scale production, preparation process green ring
Protect.
（3）Zinc metal organic framework nano material prepared by the present invention have outstanding electrochemical response, the range of linearity it is wide,
Sensitivity is high, the advantages of good antijamming capability and preferable electrochemical stability, available for electrochemical sensing.
Brief description of the drawings
The big multiplying power scanning electron microscope (SEM) photograph for the zinc metal organic framework nano-electrode material that accompanying drawing 1 is prepared for the present invention.
The small multiplying power scanning electron microscope (SEM) photograph for the zinc metal organic framework nano-electrode material that accompanying drawing 2 is prepared for the present invention.
Accompanying drawing 3 is applied to the circulation volt of detection glucose for zinc metal organic framework nano-electrode material prepared by the present invention
Pacify curve map.
The zinc metal organic framework nano-electrode material detection concentration of glucose current-vs-time that accompanying drawing 4 is prepared for the present invention
Curve.
The linearly interval fitting for the zinc metal organic framework nano-electrode material detection glucose that accompanying drawing 5 is prepared for the present invention
Figure.
Accompanying drawing 6 is when m- electric current of the zinc metal organic framework nano-electrode material of the invention prepared to disturbance thing
Response diagram.
Accompanying drawing 7 is applied to the reappearance of detection glucose for zinc metal organic framework nano-electrode material prepared by the present invention
Time current curve.
Accompanying drawing 8 is applied to the stability of detection glucose for zinc metal organic framework nano-electrode material prepared by the present invention
Time current curve.
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 possesses many structure changes and pattern, diversified component and porous new Jie
Porous materials, it has also become the new lover of academia in recent decades.The various physics of metal-organic framework materials and chemical property：Such as
Changeable topological structure, magnetic, catalytic, fluorescence etc., and the performance easily modified, make it be inhaled in small molecule carrier, gas
The fields such as attached and storage, molecular sieve, drug delivery, luminescent material, electrochemical sensing, heterocatalysis possess before huge application
Scape.Compared to other ligand materials because 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 following nm regime.
First, zinc metal organic framework nano-electrode material is prepared：
0.05g zinc nitrates are dissolved in 5 mL ethylene glycol, mixed solution I is obtained.
Above zinc nitrate is derived from Zn (NO3)2•6H2O、ZnSO4•H2O or Zn (CH3COO)2•4H2O。
0.03g terephthalic acid (TPA)s are dissolved in 8mL dimethylformamides（DMF）In, obtain mixed solution I I.
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, are obtained
White precipitate is washed and dried after 3 times respectively with DMF and ethanol, that is, obtains zinc metal organic framework nano material.
SEM tests are carried out to zinc metal organic framework nano material：Fig. 1 amplifies for zinc metal organic framework nano material
Electron scanning micrograph under 5000 times, Fig. 2 is the scanning electron under 500 times of zinc metal organic framework nano material amplification
Microphotograph.Test result shows that the zinc metal organic framework nano material of synthesis wraps up threadiness for circular block shape top
Nano wire.
2nd, the preparation of glucose sensor electrode：
1st, a diameter of 3mm glass-carbon electrode with the sand paper for having adsorbed 1 μm of aluminum oxide suspension and 0 .05 μm of oxygen has been adsorbed into respectively
Change the sand paper sanding and polishing of aluminium suspension.
2nd, the good glass-carbon electrode of sanding and polishing is successively placed on after being cleaned by ultrasonic 3 minutes in absolute ethyl alcohol and deionized water and dried
It is dry, clean glass-carbon electrode is obtained, it is stand-by.
3rd, the zinc metal organic framework nano material for taking 10mg to prepare is dissolved in 1mL concentration for 1% perfluorosulfonic acid type polymer
Ultrasonic mixing in solution, is made mixed solution, then modifies 5 μ L mixed solutions a diameter of 3mm's using the method for coating
Clean glassy carbon electrode surface, produces zinc metal organic framework nano material sensor electrode i.e. of the present invention after drying naturally
Glucose sensor electrode.
4th, electrolyte is prepared：
Using sodium hydroxide as electrolyte, wherein, naoh concentration is 0.1 mol/L.
5th, detecting electrode chemical property：
Zinc metal organic framework nano material sensor electrode is placed in 0.1 mol/L sodium hydroxide solution and surveyed
It is fixed.
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 gradually increases is added, and observes current-responsive result.Under 0.55 V potentiostatic scannings, using zinc gold
Belong to organic backbone nano material sensor electrode, the continuous glucose that various concentrations are 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 under the V of current potential 0.55 0.1
In the liquid of mol/L sodium hydroxides bottom, respectively with concentration be 100 μM of glucose, 5 μM of ascorbic acid, 5 μM of uric acid, 5 μM
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
Expect the reappearance of sensor electrode, in 0.1 mol/L sodium hydroxides bottom liquid, repeat to add glucose (100 μM) 10 times, see
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 lines are 500 μM of glucose solutions, and dotted line is tested for blank control, shown by Fig. 3：Zinc metal is organic
Skeleton nano material sensor electrode material is swept under speed 0.1 V/s's, and 500 μM of glucose solution oxidation peaks substantially compare blank
Group experiment is strong.
Fig. 4 shows, zinc metal organic framework sensor electrode the glucose bottom liquid of various concentrations is carried 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 for [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 the V of current potential 0.55 in 0.1 mol/L sodium hydroxides 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, as a result shows, electrode material has fabulous antijamming capability.
Fig. 7 is shown, in 0.1 mol/L sodium hydroxides bottom liquid, repeats to add glucose (100 μM) 10 times, with almost
Identical current-responsive, electrode material has fabulous reappearance.
Fig. 8 shown, in glucose bottom liquid (100 μM) after electro-catalysis 3500 seconds, response current is kept approximately constant, electricity
Pole material has fabulous stability.
In summary, the glucose sensor that the present invention is prepared using zinc metal organic framework as sensor electrode material
The advantage of electrode is：
1st, linearity test interval range：0.5 μM of -8.062 mM glucose；
2nd, detection sensitivity：The mA mM of sensitivity 310.686-1cm-2；
3rd, anti-interference：There is good interference free performance to uric acid, dopamine, sodium chloride in the detection process of glucose.
Claims (7)
1. a kind of zinc metal organic framework nano material, it is characterised in that prepared by following steps：
(1) dimethyl formamide solution of the ethylene glycol solution of divalent zinc salt and terephthalic acid (TPA) is mixed, it is agitated it is uniform after,
Hydro-thermal reaction is carried out at 150~200 DEG C, raw sediment is reacted into acquirement；
(2) sediment is produced into described zinc metal organic framework nanometer material to be dried after dimethylformamide and ethanol washing
Material.
2. nano material as claimed in claim 1, it is characterised 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 claimed in claim 1, it is characterised in that in step (1), the throwing of terephthalic acid (TPA) and divalent zinc salt
It is 1: 1 to expect mol ratio；The volume ratio that feeds intake of dimethylformamide and ethylene glycol is 8: 5.
4. nano material as claimed in claim 1, it is characterised in that in step (1), mixing time is 1~1.5 hour；Water
The thermal response time is 6 hours.
5. the preparation method of the zinc metal organic framework nano material as described in claim 1-4 is any.
6. zinc metal organic framework nano material the answering as glucose sensor electrode as described in claim 1-4 is any
With.
7. application as claimed in claim 6, it is characterised in that under ultrasound condition, described nano material is dissolved in perfluor
In sulfonic acid polymer solution, then modify on glass-carbon electrode, obtain described glucose sensor electrode.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107478696A (en) * | 2017-07-14 | 2017-12-15 | 长江大学 | Preparation method for the carbon material modified glassy carbon electrode of 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 |
| CN109402755A (en) * | 2018-10-30 | 2019-03-01 | 武汉纺织大学 | The preparation method of composite fibre of the surface embedded with metal organic framework nanofiber |
| CN109467493A (en) * | 2018-11-16 | 2019-03-15 | 西北工业大学 | The preparation method of metal-organic framework material modified Nano metallic 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 |
| CN112934271A (en) * | 2021-01-29 | 2021-06-11 | 广东工业大学 | Porous nanowire with metal-organic framework and preparation method and application thereof |
| CN113912863A (en) * | 2021-11-26 | 2022-01-11 | 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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Cited By (13)
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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 |
| CN107478696A (en) * | 2017-07-14 | 2017-12-15 | 长江大学 | Preparation method for the carbon material modified glassy carbon electrode of 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 |
| CN109402755A (en) * | 2018-10-30 | 2019-03-01 | 武汉纺织大学 | The preparation method of composite fibre of the surface embedded with metal organic framework nanofiber |
| CN109467493A (en) * | 2018-11-16 | 2019-03-15 | 西北工业大学 | The preparation method of metal-organic framework material modified Nano metallic particles |
| 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 |
| CN112934271A (en) * | 2021-01-29 | 2021-06-11 | 广东工业大学 | Porous nanowire with metal-organic framework and preparation method and application thereof |
| 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 |
| CN113912863A (en) * | 2021-11-26 | 2022-01-11 | 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 |
| 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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