CN104655700B - Food preservative electrochemical sensor and preparation method and application - Google Patents
Food preservative electrochemical sensor and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of new Type of Preservatives electrochemical sensor, including computer, the electrochemical workstation being connected with computer, and it is arranged on the detection circuit in the middle of electrochemical workstation and computer；Described computer is connected with the position instrument for the fixed food preservative electrochemical sensor being connected with electrochemical workstation simultaneously；Described food preservative electrochemical sensor includes working electrode, reference electrode, to electrode；Described working electrode is that surface drop coating has electroactive very high Mn2O3The glass-carbon electrode of hollow microsphere-material modified membrane.Mn is based on the invention provides one kind2O3New Type of Preservatives electrochemical sensor of hollow microsphere material and preparation method and application, operating process is simple, it is with low cost, while the detection to preservative in food has the electrochemical sensor of excellent sensitivity and its application in food preservative detection.
Description
Technical field
It is specially that one kind is based on Mn the present invention relates to electrochemical sensor field and Electroanalytical Chemistry field2O3Hollow microsphere
Food preservative electrochemical sensor of material and preparation method and application.
Background technology
Food preservative is to prevent putrid and deteriorated, extension effective period of food quality the additive as caused by microorganism, important
Be that it can suppress most incident putrefaction in varied situations, particularly still have when general sterilization functions are insufficient
The effect of continuation, and after being added in food certain in the period of in effectively, have good stability in food.Preservative
It must use, must not arbitrarily abuse by addition standard, those once occurred cause the large-scale food security of public attention to be asked
Topic, is all because the sanitary standard of food production is not performed effectively, or does not use according to regulations food addition
Agent.Food preservative is detected, is the mechanism of action, species and the concentration and the process of manufacture in food of preservative
In, due to preservative in species, property, use scope, price and toxicity etc. different in the case of, reasonable employment preservative is provided
Important information.
Mn2O3Hollow microsphere material is as a kind of functional material, and synthetic method is simply controllable, raw materials used cheap, product
Can be superior, it is one of focus material of current research circle with many interesting performances.It has higher specific surface area, pole
Have potentiality and be applied to the fields such as catalyst, Molecular Adsorption, ion exchange material, more faraday's reaction active sites can be provided
Point, thus the detection sensitivity of electrochemical sensor can be significantly improved.
At present, the method for detection food preservative mainly has：Thin-layered chromatography, ultraviolet spectrometry, Synchronous fluorimetric method,
AAS, flow injection analysis, the method for high performance liquid chromatography and liquid chromatograph mass spectrography.But these methods
Required expensive equipment, is operated also relatively complicated.It is easy to operate although there is AAS instrument to be easy to get, as a result accurately
The advantages of, but often it is difficult to trace detection.
The features such as electrochemical process has sensitivity height, is easy to on-line checking and good Modern Analytical Instrument compatibility, utilizes electricity
Chemical method has a wide range of applications to carry out at-once monitor and detection food preservative, receives more and more attention.
Accordingly, it is desirable to provide a kind of simple to operate, cost is low, while the detection to food preservative has superior sensitivity
Novel electrochemical sensor has been a urgent problem.
The content of the invention
In order to overcome the detection in the prior art to food preservative to be completed by expensive instrument, and detecting step is multiple
Miscellaneous defect, Mn is based on the invention provides one kind2O3The new Type of Preservatives electrochemical sensor of hollow microsphere material and its
Preparation method and application, operating process are simple, and cost is low, while the detection to preservative in food has the electricity of excellent sensitivity
Chemical sensor and its application in food preservative detection.
The object of the present invention is achieved like this：
Food preservative electrochemical sensor, including computer, the electrochemical workstation being connected with computer, and set
Detection circuit in the middle of electrochemical workstation and computer；Described computer is connected with for fixed and electrochemistry work simultaneously
Make the position instrument of the food preservative electrochemical sensor of station connection；Described food preservative electrochemical sensor includes work
Electrode 1, reference electrode 2, to electrode 3；It is characterized in that：Described working electrode 1 is that surface drop coating has electroactive very high
Mn2O3The glass-carbon electrode of hollow microsphere material modified membrane 4；
The preparation method of described new Type of Preservatives electrochemical sensor, comprises the following steps：
①Mn2O3The synthesis of hollow microsphere material：
By 0.169 g MnSO4·H2O is dissolved in 70 mL redistilled waters, is added 7 mL absolute ethyl alcohols and is formed uniform molten
Liquid；Meanwhile, by 0.84 g NaHCO3It is dissolved in 70 mL redistilled waters, then mixes this two parts of solution, after room temperature is stirred evenly
Stand 3 h；The solid that suction filtration is obtained uses absolute ethyl alcohol and redistilled water wash clean respectively, and 55-65 °C of vacuum drying is obtained
MnCO3Solid powder is standby；
Take the above-mentioned MnCO of 0.1 g3Solid powder is scattered in 20 mL redistilled waters, adds the mol/L of 5 mL 0.032
KMnO4Solution is stirred after 1 ~ 2 min, and the HCl solution for adding the mol/L of 5 mL 2.4 continues to stir 1 min；Products therefrom
Absolute ethyl alcohol and redistilled water wash clean are used respectively, in 55-65 °C of vacuum drying；Finally, by product at 450-550 °C
22-26 h are calcined in batch-type furnace, that is, obtain Mn2O3Hollow microsphere material；
②Mn2O3The scattered pretreatment of hollow microsphere material：
Obtained Mn in weighing step 1.2O3Hollow microsphere material solid powder, adds redistilled water, and ultrasonic 2 h is obtained
Mass concentration is 2 mg/mL dispersion liquid, and obtaining dispersion liquid is used for drop coating modified electrode；
3. the pretreatment of glass-carbon electrode：
The step of removal of impurities process can be according to the conventional method progress of this area or in order to simplify removal of impurities process, preferably
Glass-carbon electrode is polished to minute surface by concretely comprising the following steps for removal of impurities process with 0.3 μm and 0.05 μm of aluminum oxide polishing powder respectively, so
Volume ratio is used to be 1 respectively afterwards:1 alcohol-water and redistilled water is cleaned by ultrasonic 1 min；
4. the preparation of electrochemical sensor：
By step 2. in obtained Mn2O3Hollow microsphere material dispersant liquid drop is coated onto step 3. pretreated glass-carbon electrode
New Type of Preservatives electrochemical sensor is obtained after surface, evaporation drying；
The new Type of Preservatives electrochemical sensor can be applied to detect the concentration of 2-phenylphenol in food；
Described food includes orange, apple, hot pickled mustard tube, fermented bean curd；
Described specific testing conditions are：
Determine medium：0.2 mol/L pH 6.5 phosphate buffer solution；
Detect current potential：0.576 V；
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
Described specific detection method is：30 mL 0.01mol/L 2- phenylphenols standard liquid is taken to be determined to 3 mL
In medium, after stirring, collection cyclic voltammetry curve and differentiated pulse volt-ampere curve；Or under 0.2 V current potentials, stirring enrichment
3 min, differentiated pulse volt-ampere curve of the collection 2-phenylphenol of various concentrations on the electrochemical sensor；100 mL are taken respectively
Orange, apple, the extract solution of hot pickled mustard tube and fermented bean curd sample add 3 mL and determined in medium, and different food samples are gathered with the sensor
The differentiated pulse volt-ampere curve of product.
Positive beneficial effect：The invention has the advantages that：（1）Simplicity is prepared, it is with low cost：Synthesized using straightforward procedure
Prepare Mn2O3Hollow microsphere material, yield is higher, and is formd using the method for simple drop coating and evaporation solvent in electrode surface
Uniform film, preparation process only needs 4 min；(2) sensitivity for analysis is high, up to 10-7mol/L；(3) analyze speed is fast, can be straight
Measure is connect, the analysis time of whole sample is about 5 min, the demand of live fast slowdown monitoring can be met；(4) favorable reproducibility, with 20
In the foodstuff samples of individual sensor measure comparable sodium during 2-phenylphenol, relative standard deviation (RSD) is less than 3.5%；(5) grasp
Make simple, be easy to carry, it is practical：By the sensor application in a variety of foodstuff samples, including orange, apple, hot pickled mustard tube and beans
In the measure of fermented bean curd, tested by mark-on, find recovery of standard addition between 97.5%-107%, acquired results are efficient with using
Liquid chromatography eligible result is compared, basically identical, illustrates that sensor degree of accuracy in the measure of actual sample is good, practicality
By force.Present invention also offers the electrochemical sensor according to prepared by above-mentioned preparation method and the electrochemical sensor in inspection
The application surveyed in 2-phenylphenol.
Brief description of the drawings
Fig. 1 is structural representation of the invention；
Fig. 2 is Mn2O3The scanning electron microscope diagram of hollow microsphere material；
Fig. 3 is Mn2O3The transmission electron microscope figure of hollow microsphere material；
Fig. 4 is 2-phenylphenol in bare electrode and Mn2O3Cyclic voltammetry curve on hollow microsphere material modified electrode;
Fig. 5 is 2-phenylphenol in bare electrode and Mn2O3Differentiated pulse volt-ampere on hollow microsphere material modified electrode is bent
Line；
Fig. 6 is differentiated pulse volt-ampere curve of the 2-phenylphenol of various concentrations on the electrochemical sensor, and illustration is inspection
Survey the range of linearity of 2-phenylphenol；
Fig. 7 is the differentiated pulse volt-ampere curve that the sensor detects orange sample；
Fig. 8 is the differentiated pulse volt-ampere curve that the sensor detects apple sample；
Fig. 9 is the differentiated pulse volt-ampere curve that the sensor detects hot pickled mustard tube sample；
Figure 10 is the differentiated pulse volt-ampere curve that the sensor detects fermented bean curd sample；
It is in figure：Working electrode 1, reference electrode 2, to electrode 3, modified membrane 4.
Embodiment
With reference to embodiment, the present invention is described further：
Food preservative electrochemical sensor, including computer, the electrochemical workstation being connected with computer, and set
Detection circuit in the middle of electrochemical workstation and computer；Described computer is connected with for fixed and electrochemistry work simultaneously
Make the position instrument of the food preservative electrochemical sensor of station connection；Described food preservative electrochemical sensor includes work
Electrode 1, reference electrode 2, to electrode 3；Described working electrode 1 is that surface drop coating has electroactive very high Mn2O3Hollow microsphere material
Expect the glass-carbon electrode of modified membrane 4；
The preparation method of described new Type of Preservatives electrochemical sensor, comprises the following steps：
①Mn2O3The synthesis of hollow microsphere material：
By 0.169 g MnSO4·H2O is dissolved in 70 mL redistilled waters, is added 7 mL absolute ethyl alcohols and is formed uniform molten
Liquid；Meanwhile, by 0.84 g NaHCO3It is dissolved in 70 mL redistilled waters, then mixes this two parts of solution, after room temperature is stirred evenly
Stand 3 h；The solid that suction filtration is obtained uses absolute ethyl alcohol and redistilled water wash clean respectively, and 55-65 °C of vacuum drying is obtained
MnCO3Solid powder is standby；
Take the above-mentioned MnCO of 0.1 g3Solid powder is scattered in 20 mL redistilled waters, adds the mol/L of 5 mL 0.032
KMnO4Solution is stirred after 1 ~ 2 min, and the HCl solution for adding the mol/L of 5 mL 2.4 continues to stir 1 min；Products therefrom
Absolute ethyl alcohol and redistilled water wash clean are used respectively, in 55-65 °C of vacuum drying；Finally, by product at 450-550 °C
22-26 h are calcined in batch-type furnace, that is, obtain Mn2O3Hollow microsphere material；
②Mn2O3The scattered pretreatment of hollow microsphere material：
Obtained Mn in weighing step 1.2O3Hollow microsphere material solid powder, adds redistilled water, and ultrasonic 2 h is obtained
Mass concentration is 2 mg/mL dispersion liquid, and obtaining dispersion liquid is used for drop coating modified electrode；
3. the pretreatment of glass-carbon electrode：
The step of removal of impurities process can be according to the conventional method progress of this area or in order to simplify removal of impurities process, preferably
Glass-carbon electrode is polished to minute surface by concretely comprising the following steps for removal of impurities process with 0.3 μm and 0.05 μm of aluminum oxide polishing powder respectively, so
Volume ratio is used to be 1 respectively afterwards:1 alcohol-water and redistilled water is cleaned by ultrasonic 1 min；
4. the preparation of electrochemical sensor：
By step 2. in obtained Mn2O3Hollow microsphere material dispersant liquid drop is coated onto step 3. pretreated glass-carbon electrode
New Type of Preservatives electrochemical sensor is obtained after surface, evaporation drying；
The new Type of Preservatives electrochemical sensor can be applied to detect the concentration of 2-phenylphenol in food；
Described food includes orange, apple, hot pickled mustard tube, fermented bean curd；
Described specific testing conditions are：
Determine medium：0.2 mol/L pH 6.5 phosphate buffer solution；
Detect current potential：0.576 V；
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
Described specific detection method is：30 mL 0.01mol/L 2- phenylphenols standard liquid is taken to be determined to 3 mL
In medium, after stirring, collection cyclic voltammetry curve and differentiated pulse volt-ampere curve；Or under 0.2 V current potentials, stirring enrichment
3 min, differentiated pulse volt-ampere curve of the collection 2-phenylphenol of various concentrations on the electrochemical sensor；100 mL are taken respectively
Orange, apple, the extract solution of hot pickled mustard tube and fermented bean curd sample add 3 mL and determined in medium, and different food samples are gathered with the sensor
The differentiated pulse volt-ampere curve of product.
Embodiment 1
As shown in figure 1, a kind of be based on Mn2O3The new Type of Preservatives electrochemical sensor of hollow microsphere material, including bag
Include working electrode（1）, reference electrode（2）, to electrode（3）, described working electrode（1）Have electroactive very high for surface drop coating
Mn2O3Hollow microsphere material modified membrane（4）Glass-carbon electrode.The preparation method includes following process：
S1、Mn2O3The synthesis of hollow microsphere material：
By 0.169 g MnSO4·H2O is dissolved in 70 mL redistilled waters, is added 7 mL absolute ethyl alcohols and is formed uniform molten
Liquid；Meanwhile, by 0.84 g NaHCO3It is dissolved in 70 mL redistilled waters, then mixes this two parts of solution, after room temperature is stirred evenly
Stand 3 h.The solid that suction filtration is obtained uses absolute ethyl alcohol and redistilled water wash clean respectively, and 55 °C of vacuum drying obtain MnCO3
Solid powder is standby.
Take the above-mentioned MnCO of 0.1 g3Solid powder is scattered in 20 mL redistilled waters, adds the mol/L of 5 mL 0.032
KMnO4Solution is stirred after 1 ~ 2 min, and the HCl solution for adding the mol/L of 5 mL 2.4 continues to stir 1 min.Products therefrom
Respectively with absolute ethyl alcohol and redistilled water wash clean and 55 °C of vacuum drying.Finally, product is forged in 450 °C of batch-type furnaces
22 h are burnt, that is, obtain Mn2O3Hollow microsphere material.
S2、Mn2O3The scattered pretreatment of hollow microsphere material：
Weigh the Mn of certain mass2O3Hollow microsphere material solid powder, adds the redistilled water of certain volume, ultrasound 2
H obtains the dispersion liquid that mass concentration is 2 mg/mL.Obtained dispersion liquid is used for drop coating modified electrode.
S3, glass-carbon electrode pretreatment：
In the present invention, the removal of impurities process can be carried out according to the conventional method of this area, in order to simplify removal of impurities process
The step of, preferably concretely comprising the following steps for removal of impurities process is respectively polished glass-carbon electrode with 0.3 and 0.05 mm aluminum oxide polishing powder
To minute surface, then volume ratio is used to be 1 respectively:1 alcohol-water and redistilled water is cleaned by ultrasonic 1 min；
S4, the electrochemical sensor preparation：
The Mn that will be obtained in step S22O3Hollow microsphere material dispersant liquid drop is coated onto the pretreated glass-carbon electrodes of step S3
New Type of Preservatives electrochemical sensor is obtained after surface, evaporation drying；
It is described to be based on Mn2O3The new Type of Preservatives electrochemical sensor of hollow microsphere material can be used in detection food
The concentration of 2-phenylphenol.
Described specific test condition is：
Determine medium：0.2 mol/L pH 6.5 phosphate buffer solution；
Detect current potential：0.576 V；
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
30 mL 0.01mol/L 2-phenylphenol standard liquid is taken to be determined to 3 mL in medium, after stirring, collection
Cyclic voltammetry curve and differentiated pulse volt-ampere curve；Or under 0.2 V current potentials, stirring 3 min of enrichment gather 2-benzene of various concentrations
Differentiated pulse volt-ampere curve of the base phenol on the electrochemical sensor；100 mL oranges, apple, hot pickled mustard tube, fermented bean curd are taken respectively
The extract solution of sample adds 3 mL and determined in medium, and the differentiated pulse volt-ampere curve of different foodstuff samples is gathered with the sensor.
Embodiment 2
As shown in figure 1, a kind of be based on hollow microsphere Mn2O3The new Type of Preservatives electrochemical sensor of material, including bag
Include working electrode 1, reference electrode 2, be that surface drop coating has electroactive very high Mn to electrode 3, described working electrode 12O3It is hollow
The glass-carbon electrode of micro-sphere material modified membrane 4.The preparation method includes following process：
S1、Mn2O3The synthesis of hollow microsphere material：
By 0.169 g MnSO4·H2O is dissolved in 70 mL redistilled waters, is added 7 mL absolute ethyl alcohols and is formed uniform molten
Liquid；Meanwhile, by 0.84 g NaHCO3It is dissolved in 70 mL redistilled waters, then mixes this two parts of solution, after room temperature is stirred evenly
Stand 3 h.The solid that suction filtration is obtained uses absolute ethyl alcohol and redistilled water wash clean respectively, and 60 °C of vacuum drying obtain MnCO3
Solid powder is standby.
Take the above-mentioned MnCO of 0.1 g3Solid powder is scattered in 20 mL redistilled waters, adds the mol/L of 5 mL 0.032
KMnO4Solution is stirred after 1 ~ 2 min, and the HCl solution for adding the mol/L of 5 mL 2.4 continues to stir 1 min.Products therefrom
Respectively with absolute ethyl alcohol and redistilled water wash clean and 60 °C of vacuum drying.Finally, product is forged in 500 °C of batch-type furnaces
24 h are burnt, that is, obtain Mn2O3Hollow microsphere material.The transmission electron microscope and SEM of the material are respectively as schemed
2nd, shown in Fig. 3.
S2、Mn2O3The scattered pretreatment of hollow microsphere material：
Weigh the Mn of certain mass2O3Hollow microsphere material solid powder, adds the redistilled water of certain volume, ultrasound 2
H obtains the dispersion liquid that mass concentration is 2 mg/mL.Obtained dispersion liquid is used for drop coating modified electrode.
S3, glass-carbon electrode pretreatment：
In the present invention, the removal of impurities process can be carried out according to the conventional method of this area, in order to simplify removal of impurities process
The step of, preferably concretely comprising the following steps for removal of impurities process is respectively polished glass-carbon electrode with 0.3 and 0.05 mm aluminum oxide polishing powder
To minute surface, then volume ratio is used to be 1 respectively:1 alcohol-water and redistilled water is cleaned by ultrasonic 1 min；
S4, the electrochemical sensor preparation：
The Mn that will be obtained in step S22O3Hollow microsphere material dispersant liquid drop is coated onto the pretreated glass-carbon electrodes of step S3
New Type of Preservatives electrochemical sensor is obtained after surface, evaporation drying；
It is described to be based on Mn2O3The new Type of Preservatives electrochemical sensor of hollow microsphere material can be used in detection food
The concentration of 2-phenylphenol.
Described specific test condition is：
Determine medium：0.2 mol/L pH 6.5 phosphate buffer solution；
Detect current potential：0.576 V；
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
30 mL 0.01mol/L 2-phenylphenol standard liquid is taken to be determined to 3 mL in medium, after stirring, collection
Cyclic voltammetry curve and differentiated pulse volt-ampere curve, as shown in Figure 4, Figure 5；Or under 0.2 V current potentials, stirring 3 min of enrichment are adopted
Collect differentiated pulse volt-ampere curve of the 2-phenylphenol of various concentrations on the electrochemical sensor, as a result as shown in Figure 6；Take respectively
100mL oranges, apple, hot pickled mustard tube, the extract solution of fermented bean curd sample add 3 mL and determined in medium, and different foods are gathered with the sensor
The differentiated pulse volt-ampere curve of thing sample, as shown in Fig. 7, Fig. 8, Fig. 9, Figure 10.
Embodiment 3
As shown in figure 1, a kind of be based on Mn2O3The new Type of Preservatives electrochemical sensor of hollow microsphere material, including work
Make electrode 1, reference electrode 2, be that surface drop coating has electroactive very high Mn to electrode 3, described working electrode 12O3Hollow microsphere
The glass-carbon electrode of material modified membrane 4.The preparation method includes following process：
S1、Mn2O3The synthesis of hollow microsphere material：
By 0.169 g MnSO4·H2O is dissolved in 70 mL redistilled waters, is added 7 mL absolute ethyl alcohols and is formed uniform molten
Liquid；Meanwhile, by 0.84 g NaHCO3It is dissolved in 70 mL redistilled waters, then mixes this two parts of solution, after room temperature is stirred evenly
Stand 3 h.The solid that suction filtration is obtained uses absolute ethyl alcohol and redistilled water wash clean respectively, and 65 °C of vacuum drying obtain MnCO3
Solid powder is standby.
Take the above-mentioned MnCO of 0.1 g3Solid powder is scattered in 20 mL redistilled waters, adds the mol/L of 5 mL 0.032
KMnO4Solution is stirred after 1 ~ 2 min, and the HCl solution for adding the mol/L of 5 mL 2.4 continues to stir 1 min.Products therefrom
Respectively with absolute ethyl alcohol and redistilled water wash clean and 65 °C of vacuum drying.Finally, product is forged in 550 °C of batch-type furnaces
26 h are burnt, that is, obtain Mn2O3Hollow microsphere material.
S2、Mn2O3The scattered pretreatment of hollow microsphere material：
Weigh the Mn of certain mass2O3Hollow microsphere material solid powder, adds the redistilled water of certain volume, ultrasound 2
H obtains the dispersion liquid that mass concentration is 2 mg/mL.Obtained dispersion liquid is used for drop coating modified electrode.
S3, glass-carbon electrode pretreatment：
In the present invention, the removal of impurities process can be carried out according to the conventional method of this area, in order to simplify removal of impurities process
The step of, preferably concretely comprising the following steps for removal of impurities process is respectively polished glass-carbon electrode with 0.3 and 0.05 mm aluminum oxide polishing powder
To minute surface, then volume ratio is used to be 1 respectively:1 alcohol-water and redistilled water is cleaned by ultrasonic 1 min；
S4, the electrochemical sensor preparation：
The Mn that will be obtained in step S22O3Hollow microsphere material dispersant liquid drop is coated onto the pretreated glass-carbon electrodes of step S3
New Type of Preservatives electrochemical sensor is obtained after surface, evaporation drying；
It is described to be based on Mn2O3The new Type of Preservatives electrochemical sensor of hollow microsphere material can be used in detection food
The concentration of 2-phenylphenol.
Described specific test condition is：
Determine medium：0.2 mol/L pH 6.5 phosphate buffer solution；
Detect current potential：0.576 V；
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
30 mL 0.01mol/L 2-phenylphenol standard liquid is taken to be determined to 3 mL in medium, after stirring, collection
Cyclic voltammetry curve and differentiated pulse volt-ampere curve；Or under 0.2 V current potentials, stirring 3 min of enrichment gather 2-benzene of various concentrations
Differentiated pulse volt-ampere curve of the base phenol on the electrochemical sensor；100 mL oranges, apple, hot pickled mustard tube, fermented bean curd are taken respectively
The extract solution of sample adds 3 mL and determined in medium, and the differentiated pulse volt-ampere curve of different foodstuff samples is gathered with the sensor.
Practical application：The electrochemical sensor of the present invention is used for institute in the detection of actual foodstuff samples, actual sample
Concentration containing 2-phenylphenol is tested by differentiated pulse volt-ampere and combines standard samples recovery calculating and obtained.Each sample is parallel to be surveyed
Fixed 10 times, RSD is less than 4.5%, illustrates the sensor favorable reproducibility.Same sample is determined with high performance liquid chromatography (HPLC)
Product are compareed, and the results are shown in Table 1.HPLC measures result and the sensor acquired results and coincide very much that (relative deviation is less than
3.5%), illustrate that the sensor can be used in the measure of actual sample.
The measure of 2-phenylphenol in the actual foodstuff samples of table 1
The invention has the advantages that：(1) simplicity is prepared, it is with low cost：Mn is prepared using simple method for synthesizing2O3It is hollow
Micro-sphere material, yield is higher, and in electrode surface forms uniform film using the method for simple drop coating and evaporation solvent, makes
Standby process only needs 4 min；(2) sensitivity for analysis is high, up to 10-7mol/L；(3) can directly it determine, analyze speed is fast, whole sample
Min of analysis time 5 of product or so, can meet the requirement of live fast slowdown monitoring；(4) favorable reproducibility, determines same with 20 sensors
In the foodstuff samples of isoconcentration during 2-phenylphenol, relative standard deviation (RSD) is less than 3.5%；(5) it is simple to operate, it is easy to take
Band, it is practical, by the sensor application in a variety of foodstuff samples, including in orange, apple, the measure of hot pickled mustard tube and fermented bean curd,
Sensor has the good degree of accuracy in actual sample measure, practical.
Above example only describes the preferred embodiment of the present invention, but is not limited to several in above-mentioned embodiment
Details, within the spirit and principles in the present invention, can be combined, in order to avoid unnecessary weight by any suitable means
It is multiple, no longer separately illustrate.In addition, the combination between a variety of embodiments of the present invention, as long as it is without prejudice to the present invention
Thought, be equally considered as content disclosed in this invention.
Claims (3)
1. food preservative electrochemical sensor, including computer, the electrochemical workstation being connected with computer, and be arranged on
Detection circuit in the middle of electrochemical workstation and computer；Described computer is connected with for fixed and electrochemical operation simultaneously
Stand connection food preservative electrochemical sensor position instrument；Described food preservative electrochemical sensor includes work electricity
Pole（1）, reference electrode（2）, to electrode（3）；It is characterized in that：Described working electrode（1）There is electroactive height for surface drop coating
Mn2O3Hollow microsphere material modified membrane（4）Glass-carbon electrode；
The preparation method of described food preservative electrochemical sensor, it is characterised in that comprise the following steps：
①Mn2O3The synthesis of hollow microsphere material：
By 0.169 g MnSO4·H2O is dissolved in 70 mL redistilled waters, adds 7 mL absolute ethyl alcohols formation homogeneous solution；Together
When, by 0.84 g NaHCO3It is dissolved in 70 mL redistilled waters, then mixes this two parts of solution, room temperature stands 3 after stirring evenly
h；The solid that suction filtration is obtained uses absolute ethyl alcohol and redistilled water wash clean respectively, and 55-65 °C of vacuum drying obtains MnCO3Gu
Body powder is standby；
Take the above-mentioned MnCO of 0.1 g3Solid powder is scattered in 20 mL redistilled waters, adds the mol/L's of 5 mL 0.032
KMnO4Solution is stirred after 1 ~ 2 min, and the HCl solution for adding the mol/L of 5 mL 2.4 continues to stir 1 min；Products therefrom point
Not Yong absolute ethyl alcohol and redistilled water wash clean, 55-65 °C vacuum drying；Finally, by product in 450-550 °C of case
22-26 h are calcined in formula stove, that is, obtain Mn2O3Hollow microsphere material；
②Mn2O3The scattered pretreatment of hollow microsphere material：
Obtained Mn in weighing step 1.2O3Hollow microsphere material solid powder, adds redistilled water, and ultrasonic 2 h obtains quality
Concentration is 2 mg/mL dispersion liquid, and obtaining dispersion liquid is used for drop coating modified electrode；
3. the pretreatment of glass-carbon electrode：
The step of removal of impurities process is according to the conventional method progress of this area or in order to simplify removal of impurities process, the specific step of removal of impurities process
Rapid is that glass-carbon electrode is polished into minute surface with 0.3 μm and 0.05 μm of aluminum oxide polishing powder respectively, is then with volume ratio respectively
1:1 alcohol-water and redistilled water is cleaned by ultrasonic 1 min；
4. the preparation of electrochemical sensor：
By step 2. in obtained Mn2O3Hollow microsphere material dispersant liquid drop is coated onto step 3. pretreated glassy carbon electrode surface,
Food preservative electrochemical sensor is obtained after evaporation drying.
2. the application of food preservative electrochemical sensor as claimed in claim 1, it is characterised in that：For detecting 2 in food-
The concentration of phenylphenol；Described food includes orange, apple, hot pickled mustard tube and fermented bean curd.
3. the application of food preservative electrochemical sensor as claimed in claim 2, it is characterised in that specific testing conditions
For：
Determine medium：0.2 mol/L pH 6.5 phosphate buffer solution；
Detect current potential：0.576 V；
Differentiated pulse condition：Amplitude is 0.05 V, and the pulse period is 0.5 s, and pulse width is 0.05 s；
Described specific detection method is：30 mL 0.01mol/L 2- phenylphenols standard liquid is taken to determine medium to 3 mL
In, after stirring, collection cyclic voltammetry curve and differentiated pulse volt-ampere curve；Or under 0.2 V current potentials, stirring enrichment 3
Min, differentiated pulse volt-ampere curve of the collection 2-phenylphenol of various concentrations on the electrochemical sensor；100 mL tangerines are taken respectively
Son, apple, the extract solution of hot pickled mustard tube and fermented bean curd sample add 3 mL and determined in medium, and different foodstuff samples are gathered with the sensor
Differentiated pulse volt-ampere curve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510113829.7A CN104655700B (en) | 2015-03-17 | 2015-03-17 | Food preservative electrochemical sensor and preparation method and application |
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