CN106946688B - The preparation method and applications of sea urchin shape Ni-Zn metal organic framework hollow sphere nano material - Google Patents
The preparation method and applications of sea urchin shape Ni-Zn metal organic framework hollow sphere nano material Download PDFInfo
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Abstract
The preparation method and applications of sea urchin shape Ni-Zn metal organic framework hollow sphere nano material, belong to the preparation technical field of enzyme-free glucose sensor.Hydro-thermal reaction is carried out after the DMF solution of the ethylene glycol mixed solution and terephthalic acid (TPA) of divalent nickel salt and divalent zinc salt is mixed under the conditions of 150~200 DEG C, obtains reaction into raw sediment；Again by sediment with after DMF and ethanol washing dry to get.The present invention is prepared by simple hydro-thermal method, and the raw material of use are nontoxic, environmentally friendly, at low cost, simple process, easily operated control, is suitable for continuous words large-scale production.Under ultrasound condition, bulbus cordis nano material is dissolved in perfluorosulfonic acid type polymer solution, then it modifies on glass-carbon electrode, obtains responding rapid, the good no enzyme type glucose sensor of high sensitivity, stability, have a good application prospect in terms of blood sugar test.
Description
Technical field
The invention belongs to the preparation technical fields of enzyme-free glucose sensor.
Background technique
What glucose was widespread in nature, belong to a kind of monosaccharide, the changes of contents of glucose in human body is to people
The health of class is closely bound up.Diabetes are a kind of worldwide chronic diseases with the characteristics of hyperglycemia.Therefore, blood-sugar content
Detection have become in time diagnosis and strict control diabetes important channel.Check that blood-sugar content height is most in human body at present
It is to extract blood to measure for common method, for this method probably when dealing with improperly, patient can be made
At infection, present some sensors are difficult detection for the glucose of low concentration and obtain, and sensitivity is also very poor.It is right at present
More in the restrictive condition containing enzymatic glucose sensor, the activity of glucose oxidase is by various influences, temperature, air
Humidity, acid-base property all have influence on it, or even the inactivation of enzyme can be caused, make to have the precision of enzyme sensor to reduce and even lose
It goes to act on.Therefore, studying a kind of no enzyme type glucose sensor has very big significance.
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.
Metal-organic framework material (MOFs) is a kind of coordination polymer quickly grown nearly ten years, has three-dimensional hole
Structure, generally using metal ion as tie point, it is except zeolite and carbon nanotube that organic ligand support, which constitutes space 3D and extends,
The important novel porous materials of another class, be all widely used in catalysis, energy storage and separation.Compared to other ligand materials
Material, because of high surface area, high porosity, low-density, controlled architecture, adjustable aperture, MOFs material is considered as the following nanometer neck
One of most promising material in domain.
Summary of the invention
For the above prior art and defect, present invention firstly provides a kind of sea urchin shape Ni-Zn metal organic framework is hollow
The preparation method of ball nano material.
The present invention the following steps are included:
1) divalent nickel salt and divalent zinc salt are dissolved in ethylene glycol solution, the ethylene glycol of divalent nickel salt and divalent zinc salt is made
Mixed solution；
By terephthalic acid (TPA) (C8H6O4) be dissolved in dimethylformamide (DMF) solution, the DMF that terephthalic acid (TPA) is made is molten
Liquid；
2) the ethylene glycol mixed solution of the divalent nickel salt and divalent zinc salt is mixed with the DMF solution of terephthalic acid (TPA),
Hydro-thermal reaction is carried out under the conditions of 150~200 DEG C after stirring at normal temperature 1~1.5 hour, obtains reaction into raw sediment；
3) by sediment to dry after DMF and ethanol washing to get sea urchin shape Ni-Zn metal organic framework hollow sphere material
Material.
Sea urchin shape Ni-Zn metal organic framework hollow sphere electrode material of the invention is prepared by simple hydro-thermal method,
The raw material of use are nontoxic, environmentally friendly, at low cost, simple process, easily operated control, are suitable for continuous words large-scale production, preparation
Process is environmentally protective.
This sea urchin shape Ni-Zn metal organic framework hollow sphere nano material has outstanding electrochemistry it has been confirmed by experiments that
Response, the advantages that range of linearity is wide, high sensitivity, good anti-interference ability and ideal electrochemical stability, can be used for electricity
Chemical sensitisation.
Further, divalent nickel salt of the present invention is Ni (NO3)2•6H2O、NiSO4•H2O or Ni (CH3COO)2•4H2O。
The divalent zinc salt is Zn (NO3)2•6H2O、ZnSO4•H2O or Zn (CH3COO)2•4H2O.The experiment proved that due to these types of gold
The acid group for belonging to salt institute band is easily sloughed, and is easier to obtain required product, therefore preferential using these types of metal salt.
In order to obtain product morphology most preferably and best performance, the terephthalic acid (TPA) (C8H6O4) and divalent nickel salt, divalent zinc
The molar ratio of salt is 1: 1: 1.
Another object of the present invention also proposes to exist using sea urchin shape Ni-Zn MOF hollow sphere nano material made of above method
Application in sensor.
Under ultrasound condition, the sea urchin shape Ni-Zn metal organic framework hollow sphere nano material is dissolved in perfluorinated sulfonic acid
It in type polymer solution, then modifies on glass-carbon electrode, obtains no enzyme type glucose sensor.
Sensor electrode prepared by the present invention is able to respond rapidly glucose, and the range of linearity is wide, high sensitivity, surely
Qualitative good, detection lower limit is low, also has strong interference immunity, advantage at low cost, has good answer in terms of blood sugar test
Use prospect.
Present invention has an advantage that
1, linearity test interval range: 0.5 μM of -8 mM glucose；
2, detection sensitivity: sensitivity is 46.14 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；
4, compared with prior art, enzyme-free glucose electrochemical sensor of the invention is wide to glucose detection range, is
0.5 μM-8 mM.Detection 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 scanning electron microscope (SEM) photograph of sea urchin shape Ni-Zn MOF hollow sphere electrode material prepared by the present invention.
Attached drawing 2 is the transmission electron microscope picture of sea urchin shape Ni-Zn MOF hollow sphere electrode material prepared by the present invention.
Attached drawing 3 is that sea urchin shape Ni-Zn MOF hollow sphere electrode material prepared by the present invention is applied to following for detection glucose
Ring volt-ampere curve figure.
Attached drawing 4 be sea urchin shape Ni-Zn MOF hollow sphere electrode material prepared by the present invention detect concentration of glucose electric current-when
Half interval contour.
Attached drawing 5 is the linearly interval that sea urchin shape Ni-Zn MOF hollow sphere electrode material prepared by the present invention detects glucose
Fitted figure.
Attached drawing 6 is when m- electricity of the sea urchin shape Ni-Zn MOF hollow sphere electrode material prepared by the present invention to disturbance object
Flow response diagram.
Attached drawing 7 is the weight that sea urchin shape Ni-Zn MOF hollow sphere electrode material prepared by the present invention is applied to detection glucose
Existing property time current curve.
Attached drawing 8 is that sea urchin shape Ni-Zn MOF hollow sphere electrode material prepared by the present invention is applied to the steady of detection glucose
Characteristic 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.
One, sea urchin shape Ni-Zn MOF hollow sphere nano material is prepared:
0.05g nickel nitrate and 0.05g zinc nitrate are 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。
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 1~1.5 hour, then hydro-thermal reaction 12 was small under the conditions of 150~200 DEG C
When, drying is received after obtained greenish precipitate washs 3 times with DMF and ethyl alcohol respectively to get to sea urchin shape Ni-Zn MOF hollow sphere
Rice material, i.e. sea urchin shape Ni-Zn metal organic framework hollow sphere nano material.
Carry out SEM test to sea urchin shape Ni-Zn MOF hollow sphere nano material: Fig. 1 is that Ni-Zn MOF amplifies 10000 times
Under electron scanning micrograph, test result shows that the Ni-Zn MOF microsphere nano material size shape of synthesis is substantially equal
Even consistent, average diameter is about 2.5 μm.
Carry out TEM test to sea urchin shape Ni-Zn MOF hollow sphere nano material: Fig. 2 is the transmission electron microscope of Ni-Zn MOF
Figure further confirms that Ni-Zn MOF material is hollow 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% perfluor that the sea urchin shape Ni-Zn MOF hollow sphere nano material for taking 10mg step to prepare, which is dissolved in 1mL concentration,
Mixed solution is made in ultrasonic mixing in sulfonic acid polymer solution, and then 5 μ L mixed solutions are existed using the method modification of coating
The clean glassy carbon electrode surface that diameter is 3mm, after natural drying up to Ni-Zn MOF hollow sphere sensor electrode.
4, electrolyte is configured:
Using sodium hydroxide as electrolyte, wherein naoh concentration is 0.1 mol/L.
5, detecting electrode chemical property:
Ni-Zn MOF hollow sphere sensor electrode is placed in the sodium hydroxide solution of 0.1 mol/L 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 is gradually increased is added, and observes current-responsive result；Under 0.55 V potentiostatic scanning, sample Ni-
The electrode of Zn MOF hollow sphere modification is continuously added dropwise the glucose of various concentration in the liquid of sodium hydroxide bottom and is stirred continuously progress
Detect current versus time curve；The electrode of sample Ni-Zn MOF hollow sphere modification is in 0.55 V of current potential in 0.1 mol/L hydroxide
It with concentration is respectively 100 μM of glucose, 5 μM of ascorbic acid, 5 μM of uric acid, 5 μM of dopamines, 5 μ in the liquid of sodium bottom
The standard liquid of M sodium chloride and 100 μM of glucose carries out dropwise addition test；The reproducibility for testing electrode material, in 0.1 mol/L hydrogen
It in the liquid of sodium oxide molybdena bottom, repeats glucose (100 μM) to be added 10 times, observes curent change；The stability of detecting electrode material, In
In glucose bottom liquid (100 μM) after electro-catalysis 3000 seconds, curent change is observed.
Fig. 3 shows, Ni-Zn MOF hollow sphere sensor electrode material 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 Ni-Zn MOF hollow sphere sensor electrode carries out detection electric current-to the glucose bottom liquid of various concentration
Time graph, it can be seen that sample Ni-Zn MOF hollow sphere quick, sensitive catalytic response ability occurs to glucose.
Fig. 5 shows that the concentration range of linearity of acquisition is 0.5 μM of -8 mM, and linear equation is [R=0.98989, Current
I (μ A)=0.44995+ 0.00326C (μM)], sensitivity is 46.14 μ A mM-1cm-2。
Fig. 6 shows that the electrode of sample Ni-Zn MOF hollow sphere modification is in 0.55 V of current potential in 0.1 mol/L sodium hydroxide
It with concentration is respectively 100 μM of glucose, 5 μM of ascorbic acid, 5 μM of uric acid, 5 μM of dopamines, 5 μM of chlorinations in the liquid of bottom
The standard liquid of 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, electrode material have fabulous reproducibility.
Fig. 8 shows that in glucose bottom liquid (100 μM) after electro-catalysis 3000 seconds, response current is kept approximately constant, electricity
Pole material has fabulous stability.
Claims (5)
1. the preparation method of sea urchin shape Ni-Zn metal organic framework hollow sphere nano material, it is characterised in that the following steps are included:
1) divalent nickel salt and divalent zinc salt are dissolved in ethylene glycol solution, the ethylene glycol mixing of divalent nickel salt and divalent zinc salt is made
Solution；
Terephthalic acid (TPA) is dissolved in dimethyl formamide solution, the dimethyl formamide solution of terephthalic acid (TPA) is made；
2) by the dimethyl formamide solution of the ethylene glycol mixed solution and terephthalic acid (TPA) of the divalent nickel salt and divalent zinc salt
Mixing carries out hydro-thermal reaction after stirring at normal temperature 1~1.5 hour under the conditions of 150~200 DEG C, obtains reaction into raw precipitating
Object；
3) sediment is hollow to get sea urchin shape Ni-Zn metal organic framework with drying after dimethylformamide and ethanol washing
Ball material.
2. preparation method according to claim 1, it is characterised in that the divalent nickel salt is Ni (NO3)2•6H2O、NiSO4•
H2O or Ni (CH3COO)2•4H2O。
3. preparation method according to claim 1, it is characterised in that the divalent zinc salt is Zn (NO3)2•6H2O、ZnSO4•
H2O or Zn (CH3COO)2•4H2O。
4. preparation method according to claim 1, it is characterised in that the terephthalic acid (TPA) and divalent nickel salt, divalent zinc salt
Molar ratio be 1: 1: 1.
5. the sea urchin shape Ni-Zn metal organic framework hollow sphere nano material that preparation method as described in claim 1 obtains is passing
Application in sensor, it is characterised in that: under ultrasound condition, the sea urchin shape Ni-Zn metal organic framework hollow sphere nanometer material
Material is dissolved in perfluorosulfonic acid type polymer solution, is then modified on glass-carbon electrode, is obtained no enzyme type glucose sensor.
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| CN107473189B (en) * | 2017-09-30 | 2019-11-26 | 合肥师范学院 | The preparation method of sea urchin shape nanometer lead telluride and the sea urchin shape nanometer lead telluride being prepared |
| CN108559094B (en) * | 2018-03-27 | 2020-11-20 | 北京化工大学 | Preparation method of thorn-ball-shaped Yolk-shell structure bimetal organic framework material |
| 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 |
| CN110787790B (en) * | 2019-11-13 | 2022-04-29 | 武汉纺织大学 | Sea urchin-shaped metal oxide porous photocatalytic material and preparation method 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 |
| CN113267547A (en) * | 2021-05-20 | 2021-08-17 | 河南工业大学 | Preparation method of nickel-zinc-based metal organic framework material with biomass charcoal as carbon source |
| CN114976484B (en) * | 2022-07-11 | 2023-04-11 | 大连理工大学 | Loaded with Ni 2 P-Co Schottky junction active site echinoid carbon material electrocatalyst, preparation method and application thereof |
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