CN107315043B - 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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- CN107315043B CN107315043B CN201710439278.2A CN201710439278A CN107315043B CN 107315043 B CN107315043 B CN 107315043B CN 201710439278 A CN201710439278 A CN 201710439278A CN 107315043 B CN107315043 B CN 107315043B
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Abstract
The invention discloses nickel metal organic framework nano materials, its preparation step are as follows: mix the dimethyl formamide solution of the ethylene glycol solution of divalent nickel salt and terephthalic acid (TPA), after mixing evenly, hydro-thermal reaction is carried out at 150~200 DEG C, obtains reaction into raw sediment；By sediment with dimethylformamide and ethanol washing after, it is dry to get the nickel metal organic framework nano material.Sensor electrode prepared by the present invention is wide to glucose detection range, can detect the glucose of 0.5 μM of -8.062 mM；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 preparation technical fields of enzyme-free glucose sensor, and in particular to a kind of nickel metal organic framework is received
Rice 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 nickel metal organic framework nano material and its applications.
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) dimethylformamide (DMF) solution of the ethylene glycol solution of divalent nickel salt and terephthalic acid (TPA) is mixed, stirring
It after 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 nickel metal organic framework nano material.
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.The experiment proved that being easier to obtain required production since the acid group of these types of metal salt institute band is easily sloughed
Object, thus it is preferential using these types of metal salt.
Further, in order to obtain, product morphology is best and best performance, terephthalic acid (TPA) of the present invention and divalent
The molar ratio of nickel 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 nickel metal organic framework nano material as glucose sensor electrode, under ultrasound condition, by institute
It states nickel metal organic framework nano material to be dissolved in perfluorosulfonic acid type polymer solution, then modifies on glass-carbon electrode, obtain
To no enzyme type glucose sensor electrode.
Compared with prior art, the present invention has the advantage that
(1) nickel 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.
(2) it has been confirmed by experiments that nickel metal organic framework nano material prepared by the present invention have outstanding electrochemical response,
The advantages that range of linearity is wide, high sensitivity, good anti-interference ability and ideal electrochemical stability can be used for electrochemistry biography
Sense.
(3) sensor electrode prepared by the present invention is wide to glucose detection range, 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.
Detailed description of the invention
Attached drawing 1 is the big multiplying power scanning electron microscope (SEM) photograph of nickel 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 nickel metal organic framework nano-electrode material prepared by the present invention.
Attached drawing 3 is the circulation volt that nickel metal organic framework nano-electrode material prepared by the present invention is applied to detection glucose
Pacify curve graph.
Attached drawing 4 is that nickel 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 nickel metal organic framework nano-electrode material prepared by the present invention detects glucose
Figure.
Attached drawing 6 is when m- electric current of the nickel metal organic framework nano-electrode material prepared by the present invention to disturbance object
Response diagram.
Attached drawing 7 is the reproducibility that nickel 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 nickel 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, nickel metal organic framework nano-electrode material is prepared:
0.05g nickel nitrate is dissolved in 5 mL ethylene glycol, mixed solution I is obtained.
The above nickel nitrate is derived from Ni (NO3)2•6H2O、NiSO4•H2O or Ni (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
Greenish precipitate is dried to arrive nickel metal organic framework nano material after washing 3 times respectively with DMF and ethyl alcohol.
Carry out SEM test to nickel metal organic framework nano material: Fig. 1 is the amplification of nickel metal organic framework nano material
Electron scanning micrograph under 20000 times, Fig. 2 are that the scanning that nickel metal organic framework nano material is amplified under 2000 times is electric
Sub- microscope photo.Test result shows that the nickel metal organic framework nano material of synthesis is laminated structure.
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 nickel 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 nickel 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:
Glucose sensor electrode of the present invention is placed in the sodium hydroxide solution of 0.1 mol/L and is 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 is gradually increased is added, and observes current-responsive result.Under 0.55 V potentiostatic scanning, using this hair
The bright glucose sensor electrode, the continuous glucose that various concentration is 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 0.55 V of current potential 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 reproducibility of electrode repeats glucose (100 μM) to be added 10 times in 0.1 mol/L sodium hydroxide bottom liquid, and observation electric current becomes
Change.The stability for detecting glucose sensor electrode of the present invention, the electro-catalysis 3000 in glucose bottom liquid (100 μM)
After second, curent change is observed.
Fig. 3 shows, glucose sensor electrode of the present invention 0.1 V/s sweep speed under, the oxygen of oxidizing glucose
Change peak to increase with the increase that concentration of glucose is added.
Fig. 4 shows that glucose sensor electrode of the present invention carries out detection electricity to the glucose bottom liquid of various concentration
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 be [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 at 0.55 V of current potential in 0.1 mol/L sodium hydroxide
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, 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, glucose sensor electrode of the present invention have fabulous reproducibility.
Fig. 8 shows that in glucose bottom liquid (100 μM) after electro-catalysis 3000 seconds, response current is kept approximately constant, this
The invention glucose sensor electrode has fabulous stability.
In conclusion the glucose sensor that the present invention uses nickel 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: sensitivity is 1153.3 μ A mM-1cm-2；
3, anti-interference: Ascorbic Acid, uric acid, dopamine, sodium chloride have fine in the detection process of glucose
Interference free performance.
Claims (7)
1. a kind of nickel metal organic framework nano material of laminated structure, which is characterized in that be prepared by the following steps:
(1) by the dimethyl formamide solution of the ethylene glycol solution of divalent nickel 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) dry to get the nickel metal organic framework nanometer material after by sediment with dimethylformamide and ethanol washing
Material.
2. nano material as described in claim 1, which is characterized in that in step (1), divalent nickel salt is selected from Ni (NO3)2•
6H2O、NiSO4•H2O or Ni (CH3COO)2•4H2O any one.
3. 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.
4. nano material as described in claim 1, which is characterized in that in step (1), the throwing of terephthalic acid (TPA) and divalent nickel salt
Expect that molar ratio is 1: 1；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 of the laminated structure as described in claim 1-4 is any.
6. the nickel metal organic framework nano material of the laminated structure as described in claim 1-4 is any is as glucose sensor
The application of 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN112285174B (en) * | 2020-09-24 | 2022-12-16 | 江苏大学 | Enzyme-free glucose sensor and preparation method and application thereof |
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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| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Ni(II)-Based Metal-Organic Framework Anchored on Carbon Nanotubes for Highly Sensitive Non-Enzymatic Hydrogen Peroxide Sensing;Min-Qiang Wang et al.;《Electrochimica Acta》;20161231;第190卷;第2.2.2、2.3节 * |
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