CN106115787B - A kind of MnO2/ graphene nanocomposite material and its electrode prepared - Google Patents
A kind of MnO2/ graphene nanocomposite material and its electrode prepared Download PDFInfo
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- CN106115787B CN106115787B CN201610442311.2A CN201610442311A CN106115787B CN 106115787 B CN106115787 B CN 106115787B CN 201610442311 A CN201610442311 A CN 201610442311A CN 106115787 B CN106115787 B CN 106115787B
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
Prepared the present invention relates to material and electrochemical analysis techniques field, specifically disclose a kind of MnO2/ graphene nanocomposite material and its electrode prepared.The preparation method of described material is comprised the following steps：S11. by mesoporous carbon and KMnO4Mixing, adds deionized water and stirs 8 ~ 24h, obtain suspension；S12. the concentrated sulfuric acid is added into suspension, continues to stir 0.5 ~ 3h, obtains mixture；S13. 70 ~ 90 DEG C are heated the mixture to, 0.5 ~ 3h of constant temperature is maintained, obtains reaction solution；S14. reaction solution is diluted 3 ~ 8 times with deionized water, is cooled to room temperature, produce precipitation；S15. the precipitation aperture of generation is collected for 0.20 ~ 0.5mm filter membrane, washs, is drying to obtain described MnO2/ graphene nanocomposite material.The coffee acid content that the electrode prepared using the material can be used in quantitative detection beverage, food or medicine, and have the advantages that detection limit is low, sensitivity is high, stability good and strong interference immunity.
Description
Technical field
Prepared the present invention relates to material and electrochemical analysis techniques field, and in particular to a kind of MnO2/ graphene nano is multiple
Condensation material and its electrode prepared.
Background technology
Nano material has excellent catalytic action, using its preparation modified electrode be widely used in food security,
In the analysis detection in the fields such as bio-pharmaceuticals, clinical medicine and environmental monitoring；Because nanometer material modified electrode is not only clever
Sensitivity is high, test limit is low, but also is simple and convenient to operate with preparation, takes short and low cost and other advantages, can realize fast,
Economic analysis detection.
Caffeic acid also known as Caffeic acid, are a kind of organic acid, phenolic compound.Caffeic acid is widely present in day
In right herbaceous plant, as a kind of important medicine intermediate, its pharmacological action significantly, is mainly shown as with antibacterial, disease-resistant
The functions such as poison, removing toxic substances, blood coagulation, mutagenesis anticancer, are shrinking reinforcement capilary, are improving clotting factor, increasing leukocyte and blood platelet
In terms of can also play its effect.Caffeic acid is except in addition to various, outside the prevention and treatment of internal medicine bleeding, clinically used
It is evident in efficacy in the treatment of the diseases such as gynaecologic hemorrhage, tumor disease chemotherapy, radiotherapy.Relevant report also show many biological
Activity has correlation with caffeic acid, and heavy dose of or long-term use caffeic acid can cause damage to human body, and particularly it has necessarily
It is additive, down in spirits, the from head to foot various withrawal symptoms such as tired weakness occurs once disabling.Therefore, carry out to caffeic acid
Quantitative detection not only contribute to clinical application safety, moreover it is possible to daily prison is carried out to caffeinic content in commercial beverage, food
Control, is conducive to ensureing human physical and mental health.At present, the caffeinic method of domestic report detection is mainly chromatography.Compared to electrification
Detection method is learned, chromatographic instrument and equipment is expensive, it is relative complex to operate, and remains to be further improved.And needed for electrochemical assay
Equipment is simple, speed is fast, sensitivity is high, can be used for Site Detection；Particularly caffeic acid contains easily oxidized unsaturated double-bond
And hydroxyl, it is possible to use the electric signal that its oxidizing process is produced carries out quantitative detection to it.At present, it is related to electrochemical method detection
In caffeinic report, have and carry out electricity using single-walled nanotube Modified graphite electrode and siloxane molecule trace electrode pair caffeic acid
Chemical detection, but these methods are remained to be further improved in terms of detection limit, sensitivity, stability and anti-interference.Than
Such as, the detection of nanogold/Graphene electrodes is limited to 5 × 10 disclosed in existing literature-8mol/L（Zhang Y, Liu Y, He
J, Pang P, Gao Y, Hu Q, Electroanalysis, 193 (2014) 238-246）, siloxane molecule trace electricity
The detection of pole is limited to 1.5 × 10-7mol/L（Leite F R, Santo W J, Kubota L T, Sensors and
Actuators B, 128 (2007) 30-37）.
The content of the invention
Primary technical problem to be solved by this invention is, in order to overcome caffeic acid detecting electrode presence inspection in the prior art
There is provided a kind of MnO for being used to prepare caffeic acid detecting electrode for the problem of going out limit for height2/ graphene nanocomposite material.By the material
The electrode prepared has low-down detection limit for caffeinic detection.
Another technical problem to be solved by this invention is to provide a kind of MnO2/ graphene composite film modified electrode and its
Preparation method.
Above-mentioned technical problem to be solved by this invention, is achieved by the following technical programs：
A kind of MnO2The preparation method of/graphene nanocomposite material, it is characterised in that comprise the following steps：
S11. by mesoporous carbon and KMnO4Mixing, adds deionized water and stirs 8 ~ 24h, obtain suspension；
S12. the concentrated sulfuric acid is added into suspension, continues to stir 0.5 ~ 3h, obtains mixture；
S13. 70 ~ 90 DEG C are heated the mixture to, 0.5 ~ 3h of constant temperature is maintained, obtains reaction solution；
S14. reaction solution is diluted 3 ~ 8 times with deionized water, is cooled to room temperature, produce precipitation；
S15. the precipitation aperture of generation is collected for 0.20 ~ 0.5mm filter membrane, wash, be drying to obtain it is described
MnO2/ graphene nanocomposite material；
Mesoporous carbon, KMnO described in step S114Amount ratio with deionized water is 1g：8~12g：400~600mL；
The concentrated sulfuric acid described in step S12 is more than or equal to 70% H for mass fraction2SO4The aqueous solution；The body of the concentrated sulfuric acid
Product consumption is 0.5% ~ 3% of the suspension vol described in step S11.
Preferably, described in step S11 mesoporous carbon, KMnO4Amount ratio with deionized water is 1g：10~12g：400~
500mL；
Most preferably, described in step S11 mesoporous carbon, KMnO4Amount ratio with deionized water is 1g：12g：450mL.
The reaction equation that the step is carried out：4MnO4 − + 3C + H2O = 4 MnO2 + CO3 2− + 2HCO3 −。
Preferably, the mixing time in step S11 is 10 ~ 12h.
Preferably, the concentrated sulfuric acid described in step S12 is the H that mass fraction is more than or equal to 90%2SO4The aqueous solution.
Most preferably, the concentrated sulfuric acid described in step S12 is the H that mass fraction is 96%2SO4The aqueous solution.
Preferably, the volumetric usage of the concentrated sulfuric acid is 0.5% ~ 2% of the suspension vol described in step S11.
It is further preferred that the volumetric usage of the concentrated sulfuric acid be step S11 described in suspension vol 0.5% ~
1%。
Most preferably, the volumetric usage of the concentrated sulfuric acid is 0.8% of the suspension vol described in step S11.
Preferably, the mixing time described in step S12 is 0.5 ~ 1.5h.
Most preferably, the mixing time described in step S12 is 1.2h.
Preferably, 75 ~ 85 DEG C are heated the mixture in step S13,0.5 ~ 1.5h of constant temperature is maintained.
Most preferably, 85 DEG C are heated the mixture in step S13, constant temperature 1.5h is maintained.
Preferably, reaction solution is diluted 3 ~ 5 times with deionized water in step S14.
Most preferably, reaction solution is diluted 5 times with deionized water in step S14.
Preferably, the precipitation aperture of generation is collected for 0.20 ~ 0.25mm filter membrane in step S14.
Most preferably, the filter membrane that the precipitation of generation is 0.25mm with aperture is collected in step S14.
Preferably, the filter membrane described in step S14 is poly tetrafluoroethylene.
Nano composite material can integrate the physicochemical characteristic of monocomponent nanocomposite material to strengthen its concerted catalysis performance.For example
The interaction of graphene film interlayer can be reduced using inorganic nano material functionalization graphene, strengthen the dispersiveness of composite
Can, improve its electricity, optics and catalytic performance.Inorganic, metal oxide/graphene is to modify transition metal oxide material
Or the novel nanocomposite materials that holdfast is prepared on graphene sheet layer, the conductance of material can be effectively improved, makes material
Crystal structure is more stablized, the MnO that the present invention is provided2/ graphene nanocomposite material belongs to this kind of material.
In addition, for the electrode using certain specific chemical composition content of nano composite material formation determination, then needing hair
A person of good sense prepares different nano composite materials according to the property of specific chemical substance to be determined.The electrode pair prepared to be surveyed
The main preparation by nano composite material of quality of detection limit, sensitivity, stability and the anti-interference of fixed material and other effects
Method is determined.The preparation method of nano composite material mainly includes selection, the proportioning of raw material of raw material, and each step
Reaction condition etc..For the nano composite material as electrode, the selection of raw material, proportioning and each step in its preparation method
The difference of rapid reaction condition can all cause the greatest differences of the electrode electrical property subsequently prepared, so as to cause detection limit, spirit
The greatest differences of sensitivity, stability and anti-interference and other effects.
Caffeic acid contains easily oxidized unsaturated double-bond and hydroxyl, it is easy to be electrochemically oxidized；But it is unmodified
Working electrode or one pack system graphene modified electrode on exist that electrochemical response signal is weak, can not detect low concentration coffee
The deficiencies such as the content of coffee acid.
According to caffeinic characteristic, to obtain the caffeic acid detecting electrode with low detection limits, inventor passes through
Technological parameter in substantial amounts of experiment, constantly adjustment raw material composition, proportioning and preparation process, draws above-mentioned MnO2/ graphene
Nano composite material, the MnO prepared with the composite2/ graphene composite film modified electrode has excellent electrochemistry
Response performance, can significantly reduce caffeinic detection limit in sample, and improve the sensitivity of detection, stability with it is anti-interference
Property.
The present invention provides a kind of MnO prepared by above-mentioned preparation method2/ graphene nanocomposite material.
The present invention provides a kind of MnO2The preparation method of/graphene composite film modified electrode, is comprised the following steps：
Pre-process glass-carbon electrode；
By described MnO2/ graphene nanocomposite material solvent dissolves, and fully dispersed dispersion liquid；
Dispersant liquid drop is added in the glassy carbon electrode surface handled well, MnO is produced after drying2/ graphene composite film modification electricity
Pole.
Preferably, the specific method of pretreatment glass-carbon electrode is：Glass-carbon electrode is taken, in Al2O33 ~ 10 are first roughly ground on powder
Min, then the min of fine grinding 3 ~ 10 on polishing powder, clean, stand-by.
Most preferably, the specific method of pretreatment glass-carbon electrode is：Glass-carbon electrode is taken, in Al2O3First roughly ground on powder
5min, then the min of fine grinding 5 on polishing powder, clean, stand-by.
Preferably, MnO2/ graphene nanocomposite material DMF（Dimethylformamide）Dissolving, MnO2/ graphene nano
Composite and DMF amount ratio are 1 ~ 3mg：1mL；Described scattered use ultrasonic disperse.
Most preferably, MnO2/ graphene nanocomposite material DMF dissolves, MnO2/ graphene nanocomposite material and DMF
Amount ratio be 1.8mg：1mL；Described scattered use ultrasonic disperse.
The present invention provides a kind of MnO prepared by above-mentioned preparation method2/ graphene composite film modified electrode.
Above-mentioned MnO2The application of/graphene composite film modified electrode coffee acid content in detection beverage, food and medicine.
Beneficial effect：（1）The present invention solve the instrument and equipment that chromatography exists in caffeic acid continuous mode it is expensive,
Complex operation, there is provided a kind of brand-new MnO for being used to prepare electrode the problems such as time-consuming2/ graphene nanocomposite material；
（2）The caffeic acid that the electrode prepared using the material can be used in quantitative detection beverage, food and medicine, and with inspection
Rising limit is low, sensitivity is high, stability is good and the advantages of strong interference immunity；（3）Embodiment as shown by data, the electrode pair is caffeinic
Detection limit is calculated as 2.71 × 10–10Mol/L, the detection limit for the electrode reported than prior art is greatly lowered；（4）The electrode
In refrigerator preserve one month in reuse, peak current up to first measured value 92%, it was demonstrated that its storage stability is good；（5）Should
Electrode is under the conditions of the exotics such as the ascorbic acid of 10 times of concentration, folic acid, oxalic acid, vanillic aldehyde, glucose and vitamin B1 to coffee
The oxidation peak-to-peak signal of coffee acid is without significantly interfering with, common inorganic ions such as H+、K+、Na+、NH4 +、Ca2+、Mg2+、OH–、Cl–、SO4 2–、
H2PO4 –Deng to caffeinic detection also without significantly interfering with.
Brief description of the drawings
Fig. 1 is graphene（A）And MnO2/ graphene nanocomposite material（B）Scanning electron microscope (SEM) photograph, and MnO2/ graphene
The infrared spectrogram of nano composite material（C）.
Fig. 2 is glass-carbon electrode（a）, graphene/glass-carbon electrode（b）And MnO2/ graphene composite film modified electrode（c）
0.01 mol/L K3[Fe(CN)6] and 0.20 mol/L KCl bottoms liquid in cyclic voltammogram（A）With AC impedance figure（B）.
Fig. 3 is glass-carbon electrode（a）, graphene/glass-carbon electrode（b）And MnO2/ graphene composite film modified electrode（c）
1.0×10-3Square wave voltammogram in mol/L coffee acid solutions.
Fig. 4 is 1.0 × 10-3Mol/L caffeic acids are in MnO2In under different pH condition on/graphene composite film modified electrode
Square wave volt-ampere curve figure（Curve a ~ g pH value is 2.0 ~ 8.0）.
Fig. 5 is MnO2The square wave volt-ampere curve figure of/graphene composite film modified electrode in various concentrations caffeic acid（A）With
And coffee acid concentration and the linear relationship chart of its oxidation peak current（B）.
Embodiment
The present invention is explained further below in conjunction with specific embodiment, but embodiment does not do any type of limit to the present invention
It is fixed.
The MnO of embodiment 12The preparation of/graphene nanocomposite material
A kind of MnO2The preparation method of/graphene nanocomposite material, is comprised the following steps：
S11. by mesoporous carbon and KMnO4Mixing, adds deionized water stirring 12h, obtains suspension；
S12. the concentrated sulfuric acid is added into suspension, continues to stir 1.2h, obtains mixture；
S13. 85 DEG C are heated the mixture to, constant temperature 1.5h is maintained, obtains reaction solution；
S14. reaction solution is diluted 5 times with deionized water, is cooled to room temperature, produce precipitation；
S15. the filter membrane that the precipitation of generation is 0.25mm with aperture is collected, washs, is drying to obtain described MnO2/ stone
Black alkene nano composite material；
Mesoporous carbon, KMnO described in step S114The amount ratio of mixing and deionized water is 1g：12g：450mL；
The concentrated sulfuric acid described in step S12 is the H that mass fraction is 96%2SO4The aqueous solution；The volumetric usage of the concentrated sulfuric acid
For 0.8% of the suspension vol described in step S11；
Filter membrane described in step S14 is poly tetrafluoroethylene.
MnO manufactured in the present embodiment2The pattern and optical signature of/graphene nanocomposite material are as follows：Figure 1A and
Figure 1B is the graphene and MnO of ultrasonic disperse2The scanning electron microscope (SEM) photograph of/graphene nanocomposite material, stone is can be observed from Figure 1A
Black alkene has typical fold, laminar structured.Figure 1B can be clearly observed a large amount of spherical MnO2Particle is attached to bending
On the flake graphite alkene lamella of fold, most of MnO2The particle diameter of particle is about 450nm or so, shows MnO2/ graphene nano is multiple
Condensation material is successfully prepared.It is visible in 530cm from Fig. 1 C infrared spectrogram-1Nearby there is an obvious MnO2Spy
Peak is levied, MnO is further illustrated2Successfully it is supported on graphene.
The MnO of embodiment 22The preparation of/graphene nanocomposite material
A kind of MnO2The preparation method of/graphene nanocomposite material, is comprised the following steps：
S11. by mesoporous carbon and KMnO4Mixing, adds deionized water stirring 8h, obtains suspension；
S12. the concentrated sulfuric acid is added into suspension, continues to stir 2h, obtains mixture；
S13. 90 DEG C are heated the mixture to, constant temperature 2h is maintained, obtains reaction solution；
S14. reaction solution is diluted 6 times with deionized water, is cooled to room temperature, produce precipitation；
S15. the filter membrane that the precipitation of generation is 0.20mm with aperture is collected, washs, is drying to obtain described MnO2/ stone
Black alkene nano composite material；
Mesoporous carbon, KMnO described in step S114Amount ratio with deionized water is 1g：10g：600mL；
The concentrated sulfuric acid described in step S12 is the H that mass fraction is 90%2SO4The aqueous solution；The volumetric usage of the concentrated sulfuric acid
For 2% of the suspension vol described in step S11；
Filter membrane described in step S14 is poly tetrafluoroethylene.
The MnO of embodiment 32The preparation of/graphene nanocomposite material
A kind of MnO2The preparation method of/graphene nanocomposite material, is comprised the following steps：
S11. by mesoporous carbon and KMnO4Mixing, adds deionized water stirring 24h, obtains suspension；
S12. the concentrated sulfuric acid is added into suspension, continues to stir 0.5h, obtains mixture；
S13. 75 DEG C are heated the mixture to, constant temperature 0.5h is maintained, obtains reaction solution；
S14. reaction solution is diluted 3 times with deionized water, is cooled to room temperature, produce precipitation；
S15. the filter membrane that the precipitation of generation is 0.30mm with aperture is collected, washs, is drying to obtain described MnO2/ stone
Black alkene nano composite material；
Mesoporous carbon, KMnO described in step S114The amount ratio of mixing and deionized water is 1g：8g：400mL；
The concentrated sulfuric acid described in step S12 is the H that mass fraction is 70%2SO4The aqueous solution；The volumetric usage of the concentrated sulfuric acid
For 3% of the suspension vol described in step S11；
Filter membrane described in step S14 is poly tetrafluoroethylene.
The MnO of embodiment 42/ graphene composite film modified electrode
MnO2The preparation method of/graphene composite film modified electrode is as follows：
Pre-process glass-carbon electrode；Pretreatment glass-carbon electrode specific method be：Glass-carbon electrode is taken, first in Al2O3It is thick on powder
5min is ground, then the min of fine grinding 5 on polishing powder, it is clean, stand-by.
The MnO that embodiment 1 is prepared2/ graphene nanocomposite material DMF dissolves, ultrasonic disperse 10min, makes
Its fully dispersed dispersion liquid；MnO2/ graphene nanocomposite material and DMF amount ratio are 1.8mg：1mL；Again by dispersion liquid
It is added dropwise in the glassy carbon electrode surface handled well, is uniformly distributed it, the drying MnO under infrared lamp2/ graphene composite film is repaiied
Adorn electrode.
The MnO of embodiment 52/ graphene composite film modified electrode performance detection
The MnO that the present embodiment is prepared with embodiment 42/ graphene composite film modified electrode is as experimental subjects, by it
Three-electrode system is constituted with platinized platinum auxiliary electrode, SCE reference electrodes, CHI660 electrochemical workstations are connected（Shanghai morning China's instrument
Co., Ltd）Carry out chemical property detection.
（1）The Electrochemical Characterization of Different electrodes
With K3[Fe(CN)6] it is the electrochemistry that probe has investigated different modifying electrode using cyclic voltammetric and AC impedence method
Performance.Fig. 2 represents probe ion in glass-carbon electrode（a）, graphene/glass-carbon electrode（b）And MnO2/ graphene composite film modification electricity
Pole（c）On volt-ampere and impedance behavior.From Fig. 2A and 2B, probe ion is in MnO2On/graphene composite film modified electrode
Oxidation peak current it is maximum（25.2µA）, electrochemical impedance it is minimum（1.2kΩ）；Illustrate the MnO that the present invention is prepared2/ graphite
The complex film modified electrode of alkene has more preferable electrocatalysis characteristic.This is due to MnO2Graphenic surface is supported on, is effectively increased
Composite specific surface area, so as to optimize the comprehensive electrochemical of composite modified electrode.
（2）Different electrodes are contrasted to caffeinic electrocatalysis characteristic
More intuitively to embody MnO2/ graphene composite film modified electrode is to caffeinic electrocatalysis characteristic, by glass
Carbon electrode（a）, graphene/glass-carbon electrode（b）And MnO2/ graphene composite film modified electrode（c）Three kinds of Different electrodes are put respectively
In 1.0 × 10-3In mol/L coffee acid solution, its square wave voltammogram is measured.As shown in figure 3, in the coffee acid solution of isoconcentration
In, the MnO that the present invention is prepared2/ graphene composite film modified electrode shows optimal electrochemical response signal, and it is aoxidized
Peak current is maximum（7.5µA）, peak type preferably, illustrate the MnO for preparing of the present invention2/ graphene composite film modified electrode energy
Effectively improve the detection sensitivity of sensor.
（3）The MnO that the present invention is prepared2/ graphene composite film modified electrode is under different pH condition to caffeic acid
Electrochemical response performance
The MnO prepared with the present embodiment 42/ graphene composite film modified electrode is the three-electrode system of working electrode
In oxidation peak current situation of change of the caffeic acid in different pH value supporting electrolytes has been investigated with square wave voltammetry, as a result show
（Fig. 4）It is to occur obvious peak in the range of 2.0 ~ 8.0 in pH value, peak current first becomes larger with pH reduction, until
During pH=5.0, peak current reaches its maximum；Then when pH value continues to reduce, there is reduction trend in peak current, illustrates this hair
The electrode of bright preparation has best electro-chemical test performance to caffeic acid under conditions of pH value is 5.0.
（4）The MnO that the present invention is prepared2/ graphene composite film modified electrode is to caffeinic Electrochemical Detection performance
The MnO prepared with the present embodiment 42/ graphene composite film modified electrode is the three-electrode system of working electrode
In, take 5.0 Potassium Hydrogen Phthalate as bottom liquid of pH, enrichment time is 120s, a series of coffee acid solution of concentration is entered
Row square wave voltammetric scan, as a result shows（See Fig. 5）Caffeinic oxidation peak current increases and increased with its concentration, in two sections of concentration
In the range of there is good linear relationship, linear equation is respectively：i p =1.24×10-2 c+4.0×10-7(R 2=0.973) andi p=
4.46×10-3 c+2.0×10-6 (R 2=0.980)；Detection limit is calculated as 2.71 × 10-10 mol/L.Illustrate prepared electrode tool
There are good linear relationship, high sensitivity and low detection limit.
（5）The MnO that the present invention is prepared2The antijamming capability and stability of/graphene composite film modified electrode.
The MnO prepared with the present embodiment 42/ graphene composite film modified electrode is the three-electrode system of working electrode
In, take 5.0 Potassium Hydrogen Phthalate as bottom liquid of pH, enrichment time is 120s, simulation interference is investigated using square wave voltammetry
Material is to 1.0 × 10-3Mol/L caffeinic oxidation peak current influence.As a result the MnO prepared with the present invention is shown2/ stone
The black complex film modified electrode of alkene is in the ascorbic acid of 10 times of concentration, folic acid, oxalic acid, vanillic aldehyde, glucose and vitamin B1Deng outer
Come under material interference to have no significant effect caffeinic oxidation peak current；Common inorganic ions such as H+、K+、Na+、NH4 +、Ca2+、
Mg2+、OH–、Cl–、SO4 2–、H2PO4 –Deng being detected also to caffeinic without significantly interfering with, so as to confirm electrode tool prepared by the present invention
There is excellent selectivity, caffeinic detection in actual sample can be used for.
MnO is investigated with square wave voltammetry2The stability of/graphene composite film modified electrode.First by prepared electrode with
The three-electrode system connection electrochemical workstation that platinum plate electrode, SCE electrodes are constituted, at the Potassium Hydrogen Phthalate bottom that pH is 5.0
In liquid, 1.0 × 10 are measured with 120s enrichment times-3The caffeinic oxidation peak current initial values of mol/L.By the electrode in refrigerator
Preserve the caffeic acid in one month again with similarity condition for same concentration to be measured, as a result find its peak point current up to just
The 92% of measured value, it was confirmed that electrode prepared by the present invention has good storage stability.
The actual sample of embodiment 6 is detected
Certain brand instant coffee is configured to 0.05g/mL solution to be measured, filtered out after insoluble matter with the adjacent benzene two that pH is 5.0
Formic acid hydrogen potassium solution is settled to 1L as actual measurement sample 1；500mg carrots are crushed in juice extractor, filtrate is used into pH after filtering
1L is settled to as actual measurement sample 2 for 5.0 Potassium Hydrogen Phthalate solution；Certain tablet is taken into 500mg, pulverized in grinding
Afterwards, it will be filtered after ultrasound in its 10mL ethanol, filtrate be settled to 1L as reality with pH for 5.0 Potassium Hydrogen Phthalate solution
Test sample product 3；The MnO prepared using embodiment 42/ graphene composite film modified electrode to handling well after three kinds of actual samples
Coffee acid content in product carries out mark-on reclaims measure, and its rate of recovery is between 98.9 ~ 102.3%, and relative standard deviation is 2.1
Between ~ 3.6%；Illustrate MnO prepared by the present invention2/ graphene composite film modified electrode is used for caffeinic inspection in actual sample
Measuring tool has the higher degree of accuracy and feasibility.
Claims (10)
1. a kind of MnO2/ graphene composite film modified electrodes for being used to detect coffee acid content in beverage, food or medicine, it is special
Levy and be, prepared by the method comprised the following steps：
Pre-process glass-carbon electrode；
MnO2/ graphene nanocomposite material solvents are dissolved, and fully dispersed dispersion liquid；
Dispersant liquid drop is added in the glassy carbon electrode surface handled well, MnO2/ graphene composite film modified electrodes are produced after drying；
Described MnO2/ graphene nanocomposite materials, are prepared by the method comprised the following steps：
S11. mesoporous carbon is mixed with KMnO4, adds deionized water and stir 8 ~ 24h, obtain suspension；
S12. the concentrated sulfuric acid is added into suspension, continues to stir 0.5 ~ 3h, obtains mixture；
S13. 70 ~ 90 DEG C are heated the mixture to, 0.5 ~ 3h of constant temperature is maintained, obtains reaction solution；
S14. reaction solution is diluted 3 ~ 8 times with deionized water, is cooled to room temperature, produce precipitation；
S15. the filter membrane that the precipitation aperture of generation is the .5mm of 0 .20 ~ 0 is collected, washs, is drying to obtain described MnO2/
Graphene nanocomposite material；
The amount ratio of mesoporous carbon, KMnO4 and deionized water described in step S11 is 1g：8~12g：400~600mL；
The concentrated sulfuric acid described in step S12 is more than or equal to the 70% H2SO4 aqueous solution for mass fraction；The volume of the concentrated sulfuric acid
Consumption is 0.5% ~ 3% of the suspension vol described in step S11.
2. MnO2/ graphene composite films modified electrode according to claim 1, it is characterised in that described in step S11
The amount ratio of mesoporous carbon, KMnO4 and deionized water is 1g：10~12g：400~500mL.
3. MnO2/ graphene composite films modified electrode according to claim 2, it is characterised in that described in step S11
The amount ratio of mesoporous carbon, KMnO4 and deionized water is 1g：12g：450mL.
4. MnO2/ graphene composite films modified electrode according to claim 1, it is characterised in that described in step S12
The concentrated sulfuric acid is the H2SO4 aqueous solution that mass fraction is more than or equal to 90%；The volumetric usage of the concentrated sulfuric acid is described in step S11
Suspension vol 0.5% ~ 2%.
5. MnO2/ graphene composite films modified electrode according to claim 4, it is characterised in that the body of the concentrated sulfuric acid
Product consumption is 0.5% ~ 1% of the suspension vol described in step S11.
6. MnO2/ graphene composite films modified electrode according to claim 1, it is characterised in that the stirring in step S11
Time is 10 ~ 12h；Mixing time described in step S12 is 0.5 ~ 1.5h；75 ~ 85 are heated the mixture in step S13
DEG C, maintain 0.5 ~ 1.5h of constant temperature.
7. MnO2/ graphene composite films modified electrode according to claim 1, it is characterised in that will reaction in step S14
Liquid dilutes 3 ~ 5 times with deionized water.
8. MnO2/ graphene composite films modified electrode according to claim 1, it is characterised in that will be produced in step S14
Precipitation aperture for 0.20 ~ 0.25mm filter membrane collect.
9. MnO2/ graphene composite films modified electrode according to claim 1, it is characterised in that described in step S14
Filter membrane is poly tetrafluoroethylene.
10. MnO2/ graphene composite films modified electrode according to claim 1, it is characterised in that pretreatment glass-carbon electrode
Specific method be：Glass-carbon electrode is taken, 3 ~ 10min is first roughly ground on Al2O3 powder, then 3 ~ 10min of fine grinding on polishing powder,
It is clean, stand-by；Described MnO2/ graphene nanocomposite materials are scattered with DMF, MnO2/ graphene nanocomposite materials and DMF
Amount ratio be 1 ~ 3mg：1mL；Described scattered use ultrasonic disperse.
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| CN110668501B (en) * | 2019-09-20 | 2022-06-03 | 苏州科技大学 | Biomass-based three-dimensional porous carbon/manganese oxyhydroxide bionic enzyme material and preparation method and application thereof |
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