CN107315043A - nickel metal organic framework nano material and its application - Google Patents
nickel metal organic framework nano material and its application Download PDFInfo
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- CN107315043A CN107315043A CN201710439278.2A CN201710439278A CN107315043A CN 107315043 A CN107315043 A CN 107315043A CN 201710439278 A CN201710439278 A CN 201710439278A CN 107315043 A CN107315043 A CN 107315043A
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- nano material
- organic framework
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- nickel metal
- glucose
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- G—PHYSICS
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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
- G01N27/28—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
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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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses nickel metal organic framework nano material, its preparation process is：The dimethyl formamide solution of the ethylene glycol solution of divalent nickel salt and terephthalic acid (TPA) is mixed, after stirring, hydro-thermal reaction is carried out at 150~200 DEG C, raw sediment is reacted into acquirement；After sediment is washed with dimethylformamide and ethanol, dry, produce the nickel metal organic framework nano material.Sensor electrode prepared by the present invention is wide to glucose detection scope, can detect 0.5 μM of 8.062mM glucose；Detection sensitivity is high, and Ascorbic Acid, uric acid, dopamine, sodium chloride have good interference free performance.
Description
Technical field
The invention belongs to the preparing technical field of enzyme-free glucose sensor, and in particular to a kind of nickel metal organic framework is received
Rice 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 nickel metal organic framework nano material and its application.
Realizing the technical solution of the object of the invention is：
A kind of nickel metal organic framework nano material, is prepared by following steps：
（1）By the ethylene glycol solution of divalent nickel salt and the dimethylformamide of terephthalic acid (TPA)（DMF）Solution is mixed, and stirring 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, the nickel metal organic framework nano material is produced.
Further, divalent nickel salt of the present invention is selected from Ni (NO3)2•6H2O、NiSO4•H2O or Ni (CH3COO)2•
4H2Any one in O.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 production
Thing, therefore preferentially use this several metal salt.
Further, in order to obtain, product morphology is optimal and best performance, terephthalic acid (TPA) of the present invention and divalence
The molar ratio of nickel salt is 1: 1；Described dimethylformamide（DMF）The volume ratio that feeds intake with ethylene glycol is 8: 5.
Above-mentioned nickel metal organic framework nano material as glucose sensor electrode application, under ultrasound condition, by institute
State nickel metal organic framework nano material to be dissolved in perfluorosulfonic acid type polymer solution, then modify on glass-carbon electrode, obtain
To without enzyme type glucose sensor electrode.
Compared with prior art, the invention has the advantages that：
（1）Nickel metal organic framework nano material prepared by the present invention is prepared from by simple hydro-thermal method, the raw material of use without
Poison, environmental protection, cost are low, and technique is simple, it is easy to operational control, suitable for continuous words large-scale production, preparation process environmental protection.
（2）Be experimentally verified that, the nickel metal organic framework nano material for preparing of the present invention have outstanding electrochemical response,
The range of linearity is wide, sensitivity is high, the advantages of good antijamming capability and preferable electrochemical stability, is passed available for electrochemistry
Sense.
（3）Sensor electrode prepared by the present invention is wide to glucose detection scope, is 0.5 μM of -8.062 mM.Detection spirit
Sensitivity is high, and Ascorbic Acid, uric acid, dopamine, sodium chloride have good interference free performance.
Brief description of the drawings
The big multiplying power scanning electron microscope (SEM) photograph for the nickel 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 nickel 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 nickel metal organic framework nano-electrode material prepared by the present invention
Pacify curve map.
The nickel 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 nickel 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 nickel 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 nickel 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 nickel 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, nickel metal organic framework nano-electrode material is prepared：
0.05g nickel nitrates are dissolved in 5 mL ethylene glycol, mixed solution I is obtained.
Above nickel nitrate is derived from Ni (NO3)2•6H2O、NiSO4•H2O or Ni (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
Greenish precipitate is washed and dried after 3 times respectively with DMF and ethanol, that is, obtains nickel metal organic framework nano material.
SEM tests are carried out to nickel metal organic framework nano material：Fig. 1 amplifies for nickel metal organic framework nano material
Electron scanning micrograph under 20000 times, Fig. 2 is that the scanning that nickel metal organic framework nano material is amplified under 2000 times is electric
Sub- microphotograph.Test result shows that the nickel metal organic framework nano material of synthesis is laminated structure.
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 nickel 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 nickel 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：
Glucose sensor electrode of the present invention is placed in 0.1 mol/L sodium hydroxide solution and is measured.
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 this hair
Bright described glucose sensor electrode, the continuous glucose that various concentrations are added dropwise, be stirred continuously in the liquid of sodium hydroxide bottom into
Row detection current versus time curve.Using glucose sensor electrode of the present invention, in the V of current potential 0.55 in 0.1 mol/L
It is respectively 100 μM of glucose, 5 μM of ascorbic acid, 5 μM of uric acid, 5 μM of DOPA with concentration in the liquid of sodium hydroxide bottom
The standard liquid of amine, 5 μM of sodium chloride and 100 μM of glucose carries out dropwise addition test.Test glucose sensor of the present invention
The reappearance of electrode, in 0.1 mol/L sodium hydroxides bottom liquid, repeats to add glucose (100 μM) 10 times, and observation electric current becomes
Change.The stability of glucose sensor electrode of the present invention is detected, the electro-catalysis 3000 in glucose bottom liquid (100 μM)
After second, curent change is observed.
Fig. 3 shows that glucose sensor electrode of the present invention is swept under speed 0.1 V/s's, the oxygen of oxidizing glucose
Change peak with the increase for adding concentration of glucose to increase.
Fig. 4 shows that glucose sensor electrode of the present invention carries out detection electricity to the glucose bottom liquid of various concentrations
Stream-time graph, it can be seen that glucose sensor electrode of the present invention quick, sensitive catalytic response occurs to glucose
Ability.
Fig. 5 shows, the concentration range of linearity of acquisition is 0.5 μM of -8.062 mM, linear equation for [R=0.99285,
Current I (μ A)=36.17363+ 0.08148C (μM)], sensitivity is 1153.3 μ A mM-1cm-2。
Fig. 6 shows that glucose sensor electrode of the present invention is under the V of current potential 0.55 in 0.1 mol/L sodium hydroxides
It is respectively 100 μM of glucose, 5 μM of ascorbic acid, 5 μM of uric acid, 5 μM of dopamines, 5 μM of chlorine with concentration in the liquid of bottom
The standard liquid for changing sodium and 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, glucose sensor electrode of the present invention has fabulous reappearance.
Fig. 8 shown, in glucose bottom liquid (100 μM) after electro-catalysis 3000 seconds, response current is kept approximately constant, this
The described glucose sensor electrode of invention has fabulous stability.
In summary, the glucose sensor that the present invention is prepared using nickel 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：Sensitivity is 1153.3 μ A mM-1cm-2；
3rd, anti-interference：Ascorbic Acid, uric acid, dopamine, sodium chloride have anti-well in the detection process of glucose
Jamming performance.
Claims (7)
1. a kind of nickel metal organic framework nano material, it is characterised in that prepared by following steps：
（1）The dimethyl formamide solution of the ethylene glycol solution of divalent nickel salt and terephthalic acid (TPA) is mixed, after stirring,
Hydro-thermal reaction is carried out at 150~200 DEG C, raw sediment is reacted into acquirement；
（2）After sediment is washed with dimethylformamide and ethanol, dry, produce the nickel metal organic framework nanometer material
Material.
2. nano material as claimed in claim 1, it is characterised in that step（1）In, divalent nickel salt is selected from Ni (NO3)2•
6H2O、NiSO4•H2O or Ni (CH3COO)2•4H2Any one in O.
3. nano material as claimed in claim 1, it is characterised in that step（1）In, mixing time is 1~1.5 hour；Water
The thermal response time is 6 hours.
4. nano material as claimed in claim 1, it is characterised in that step（1）In, the throwing of terephthalic acid (TPA) and divalent nickel salt
It is 1: 1 to expect mol ratio；The volume ratio that feeds intake of dimethylformamide and ethylene glycol is 8: 5.
5. the preparation method of the nickel metal organic framework nano material as described in claim 1-4 is any.
6. nickel 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301217A (en) * | 2018-09-30 | 2019-02-01 | 西北有色金属研究院 | A kind of preparation method and applications of layered laminate NiO micro Nano material |
| CN109557161A (en) * | 2019-01-03 | 2019-04-02 | 河北工业大学 | A kind of preparation method and applications of cobalt acid nickel carbon titanium composite material |
| WO2022062409A1 (en) * | 2020-09-24 | 2022-03-31 | 江苏大学 | Enzyme-free glucose sensor, manufacturing method for same, and uses thereof |
| US11733199B2 (en) | 2020-09-24 | 2023-08-22 | Jiangsu University | Fabrication method of enzyme-free glucose sensor and use of enzyme-free glucose sensor fabricated by the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105203612A (en) * | 2014-06-10 | 2015-12-30 | 中国科学院大连化学物理研究所 | Biosensor based on metal organic skeleton material and application thereof |
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2017
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105203612A (en) * | 2014-06-10 | 2015-12-30 | 中国科学院大连化学物理研究所 | Biosensor based on metal organic skeleton material and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| MIN-QIANG WANG ET AL.: "Ni(II)-Based Metal-Organic Framework Anchored on Carbon Nanotubes for Highly Sensitive Non-Enzymatic Hydrogen Peroxide Sensing", 《ELECTROCHIMICA ACTA》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301217A (en) * | 2018-09-30 | 2019-02-01 | 西北有色金属研究院 | A kind of preparation method and applications of layered laminate NiO micro Nano material |
| CN109557161A (en) * | 2019-01-03 | 2019-04-02 | 河北工业大学 | A kind of preparation method and applications of cobalt acid nickel carbon titanium composite material |
| WO2022062409A1 (en) * | 2020-09-24 | 2022-03-31 | 江苏大学 | Enzyme-free glucose sensor, manufacturing method for same, and uses thereof |
| US11733199B2 (en) | 2020-09-24 | 2023-08-22 | Jiangsu University | Fabrication method of enzyme-free glucose sensor and use of enzyme-free glucose sensor fabricated by the same |
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| CN107315043B (en) | 2019-11-15 |
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