CN108872336A - A kind of detection method for pentachlorophenol content in paper wrapper - Google Patents
A kind of detection method for pentachlorophenol content in paper wrapper Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
The present invention provides a kind of detection method for pentachlorophenol content in paper wrapper, includes the following steps：1）Prepare sample solution；2）Preparing standard solution mother liquor；3）Take the standard solution mother liquor of different volumes, it is added separately in phosphate buffer, it is made into the sub- liquid of standard solution of various concentration, it is respectively adopted after the sensor based on function dough nano-carbon material carries out qualitative and quantitative detection and establishes standard curve, sample solution is added in phosphate buffer again, after being detected using the sensor based on function dough nano-carbon material, the content of pentachlorophenol in sample solution is obtained by the standard curve.The present invention further provides a kind of sensors and preparation method thereof based on function dough nano-carbon material.A kind of detection method for pentachlorophenol content in paper wrapper provided by the invention, response is fast, high sensitivity, accuracy are good, strong antijamming capability, is suitable for the quick detection of actual sample.
Description
Technical field
The invention belongs to the detection technique fields of paper wrapper chemical component, are related to a kind of for paper wrapper
The detection method of middle pentachlorophenol content, and in particular to a kind of sensor based on nano-carbon material is for quickly detecting papery packet
The method of pentachlorophenol content in package material.
Background technique
Pentachlorophenol (PCP) is widely used as preservative in timber, textile, paper etc., and physicochemical property is highly stable,
It is not easy to be oxidized under usual conditions, it is also difficult to hydrolyze, can be enriched in animal or even human body through food chain, cause lung, liver, kidney
And the damage of nervous system.Currently, paper wrapper is widely used to food packaging applications, and pentachlorophenol is wrapping
The risk that the residual in paper increases food-safety problem is filled, therefore quick, accurate, convenient qualitative, fixed to pentachlorophenol progress
Amount detection has great significance and practical application value.
The common detection method of pentachlorophenol mainly includes chromatography, spectroscopic methodology, immunization etc..Using gas chromatography or
Person's gas chromatography-mass spectrography is related to derivatization process, increases Check-Out Time, and there are derivatization efficiency to ask for derivative reaction
Topic, causes the rate of recovery to reduce；Though liquid chromatography mass series process has the preferable rate of recovery, lower detection limit and higher spirit
Sensitivity, but instrument itself is expensive, and method use is restricted；Optical means also need derivatization operation, be easy to bring it is secondary
Pollution, sensitivity are low, and exogenous chaff interferent is affected to detection；Immunoassay method be based on antigen-antibody reaction and
A kind of emerging pollutant analysis method established, has the characteristics that operating process is relatively easy, analytical cycle is shorter, but due to exempting from
Antibody preparation commercialization is more difficult in epidemic disease method, therefore the research of pentachlorophenol immunoassay is relatively fewer.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide one kind in paper wrapper
The detection method of pentachlorophenol content, by using the electrochemical method of the sensor based on nano-carbon material to papery packing timber
Pentachlorophenol substance is quickly measured in material, for solve in the prior art expensive equipment, the response time is long, sensitivity is low,
The problems such as anti-interference is poor.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of in paper wrapper
The detection method of pentachlorophenol content, includes the following steps：
1) take the paper wrapper after shredding, stood after methanol ultrasonic extraction is added, pipette solution after extraction carry out from
The heart obtains filtrate after taking supernatant liquid filtering, as sample solution；
2) pentachlorophenol standard items is taken to add methanol dissolution and constant volume, preparing standard solution mother liquor；
3) the standard solution mother liquor in the step 2) of different volumes is taken, is added separately in phosphate buffer, is made into not
With the sub- liquid of standard solution of concentration, after the sensor progress qualitative and quantitative detection based on function dough nano-carbon material is respectively adopted
Standard curve is established, then the sample solution in step 1) is added in phosphate buffer, using based on function dough nanometer
After the sensor of carbon material is detected, the content of pentachlorophenol in sample solution is obtained by the standard curve.
Preferably, in step 1), the paper wrapper is Cigarette paper.
Preferably, in step 1), it is broken that the paper wrapper is cut into (0.49-0.51) cm × (0.49-0.51) cm
It is uniformly mixed after piece.It is highly preferred that the paper wrapper is cut into the fragment of (0.50 × 0.50) cm.
Preferably, in step 1), the ratio between the volume (mL) for quality (g) and the methanol addition that the paper wrapper is added
It is 1:20-60.
Preferably, in step 1), the time of the ultrasonic extraction is 20-60min.
Preferably, in step 1), the time of the standing is 1-10min.
Preferably, in step 1), the centrifugation time is 2-10min, and the centrifugation rate is 3000-8000r/min.
Preferably, described to be filtered into membrane filtration in step 1), the filter membrane is 0.22 μm of organic phase filter membrane.
Preferably, in step 2), the concentration of pentachlorophenol is 0.5-2.0g/mL in the standard solution mother liquor.More preferably
Ground, the concentration of pentachlorophenol is 1.0g/mL in the standard solution mother liquor.
Preferably, described that qualitative, quantitative inspection is carried out using the sensor based on function dough nano-carbon material in step 3)
Standard curve is established after survey to refer to：The standard solution mother liquor for taking different volumes, is added separately in phosphate buffer, is made into not
With the sub- liquid of standard solution of concentration, after being detected respectively using the sensor based on function dough nano-carbon material, according to following
The detection voltage of the legal detection pentachlorophenol of ring volt-ampere (CV), so that it is determined that the sensor based on function dough nano-carbon material
It is able to detect pentachlorophenol, quantitative detection is then carried out according to chronoamperometry, with the corresponding electricity of the standard solution of various concentration
Stream response is ordinate, the time is abscissa, draws corresponding standard curve, and the recurrence side of standard curve is calculated
Journey.
Preferably, in step 3), the content for obtaining pentachlorophenol in sample solution by the standard curve refers to：
Sample solution is added in phosphate buffer, is detected using the sensor based on function dough nano-carbon material, it will
The current-responsive value of the sample solution of acquisition, substitutes into the regression equation of standard curve, and pentachlorobenzene in sample solution can be obtained
The content of phenol.
Preferably, described that qualitative detection is carried out using the sensor based on function dough nano-carbon material in step 3)
Condition is：Initial potential (low potential) is -0.4~0.6V, and terminal current potential (high potential) is 0.8~1.2V, and scanning speed is
0.02~0.08V/s.The condition of condition, that is, cyclic voltammetric (CV) method detection of the qualitative detection, by CV method to pentachlorophenol
Carrying out qualitative detection can determine the detection voltage (i.e. the terminal current potential of CV method) of chronoamperometry, quantitative convenient for further progress
Detection.
It is highly preferred that the sensor that uses based on function dough nano-carbon material carry out the condition of qualitative detection for：
Initial potential (low potential) is -0.5V, and terminal current potential (high potential) is 1.0V, scanning speed 0.05V/s.
Preferably, described that quantitative detection is carried out using the sensor based on function dough nano-carbon material in step 3)
Condition is：Initial potential is 0.8~1.2V, and the sampling interval is 0.05~0.2s, and experimental period is 1000~3000s.It is described fixed
The condition of amount detection is the condition of chronoamperometry detection.
It is highly preferred that the sensor that uses based on function dough nano-carbon material carry out the condition of quantitative detection for：
Initial potential is 1.0V, sampling interval 0.1s, experimental period 2000s.
Preferably, in step 3), the concentration of pentachlorophenol is 1.0-10 μ g/L in the sub- liquid of standard solution.
Preferably, in step 3), the concentration of the phosphate buffer (PBS) is 0.04-0.06mol/L (pH=7.4).
It is highly preferred that the concentration of the phosphate buffer (PBS) is 0.05mol/L (pH=7.4).
Preferably, in step 3), the sensor based on function dough nano-carbon material is in electrode surface dropwise addition official
It is dry after energy dough nano-carbon material solution, then the drying after perfluorinated sulfonic acid (Nafion) solution is added dropwise in electrode surface, it is made.
It is highly preferred that the electrode is selected from glass-carbon electrode, gold electrode, graphite electrode, gold disc electrode, ito glass electrode, silk
One of wire mark brush carbon electrode (SPCE) or silk-screen printing gold film electrode.
It is highly preferred that the concentration that function dough nano-carbon material solution is added dropwise in the electrode surface is 1-3mg/mL, function
The volume of dough nano-carbon material solution is 2-10 μ L.It is further preferred that function dough nano-sized carbon is added dropwise in the electrode surface
The concentration of material solution is 2mg/mL.The function dough nano-carbon material solution is the water-soluble of function dough nano-carbon material
Liquid.
It is highly preferred that the function dough nano-carbon material solution needs ultrasonic disperse 1-3h.It is further preferred that described
Function dough nano-carbon material solution needs ultrasonic disperse 2h.
It is highly preferred that the concentration that perfluorinated sulfonic acid (Nafion) solution is added dropwise in the electrode surface is 0.04-0.06wt%, entirely
The volume of fluosulfonic acid (Nafion) solution is 1-3 μ L.It is further preferred that perfluorinated sulfonic acid (Nafion) is added dropwise in the electrode surface
The concentration of solution is 0.05wt%, and the volume of perfluorinated sulfonic acid (Nafion) solution is 2 μ L.Perfluorinated sulfonic acid (Nafion) solution
For the aqueous solution of perfluorinated sulfonic acid (Nafion).
It is highly preferred that the drying is to be placed on natural drying at room temperature in drier.
It is highly preferred that the sensor based on function dough nano-carbon material be stored in phosphate buffer (PBS) or
In dry environment.
It is further preferred that the concentration of the phosphate buffer (PBS) is 0.04-0.06mol/L (pH=7.4).Most
Preferably, the concentration of the phosphate buffer (PBS) is 0.05mol/L (pH=7.4).
It is highly preferred that the preparation of the function dough nano-carbon material, includes the following steps：
A) H is added in nano-carbon material2O2It after carrying out ultrasound for the first time, is filtered, washed, dries, obtain intermediate product；
B) it after intermediate product addition mixed acid being carried out second of ultrasound, flows back, wash, drying is received to get function dough
Rice carbon material.
It is further preferred that the nano-carbon material is selected from mono-layer graphite piece, Multi-layer graphite piece, single wall carbon in step a)
Nanotube, multi-walled carbon nanotube (MWCNTs), single-layer graphene, multi-layer graphene, hollow Nano carbon ball, active carbon nanoparticles and its
One of nitrating compound or multiple combinations.The nitrating compound is mono-layer graphite piece, Multi-layer graphite piece, single
The nitrating of pipe, multi-walled carbon nanotube (MWCNTs), single-layer graphene, multi-layer graphene, hollow Nano carbon ball or active carbon nanoparticles
Compound.
It is further preferred that in step a), quality (g) and H that the nano-carbon material is added2O2The volume (mL) of addition
The ratio between be 1:45-1:55.Most preferably, the quality (g) and H that the nano-carbon material is added2O2The ratio between volume (mL) of addition is
1:50。
It is further preferred that in step a), the H2O2For the aqueous solution for the hydrogen peroxide that percent by volume is 25-35%.
It is further preferred that the time of the first time ultrasound is 2-6h in step a).Keep nano-carbon material evenly dispersed
In H2O2In solution.
It is further preferred that described to be filtered into membrane filtration, the filter membrane is 0.45 μm of filter membrane in step a).
It is further preferred that the washing is using washing 3-5 times in step a).Most preferably, the washing is use
Washing 3 times.
It is further preferred that in step a), the drying condition is：Drying device is vacuum oven, and drying temperature is
40-50 DEG C, drying time 11-13h.Most preferably, the drying condition is：Drying temperature is 45 DEG C, and drying time is
12h。
It is further preferred that the mixed acid is the mixed acid of nitric acid and sulfuric acid in step b).
Most preferably, in the mixed acid, the volume ratio of the nitric acid and sulfuric acid is 1:3.
It is further preferred that in step b), the volume (mL) for quality (g) and the mixed acid addition that the intermediate product is added
The ratio between be 1:10-1:30.Most preferably, the quality (g) and H that the nano-carbon material is added2O2The ratio between volume (mL) of addition is
1:20。
It is further preferred that the time of second of ultrasound is 25-35min in step b).Most preferably, described
The time of twice ultrasonic is 30min.
It is further preferred that in step b), the temperature of the reflux is 60~100 DEG C, the time of the reflux is 6~
10h.The reflux is acidified intermediate product, so that nano-carbon material surface is introduced the oxygen-containing groups such as carboxyl and hydroxyl, to increase material
The water solubility of material.
It is further preferred that the washing is using washing product to neutral (pH=7) in step b).
It is further preferred that in step b), the drying condition is：Drying device is vacuum oven, and drying temperature is
40-50 DEG C, drying time 10-30h.Most preferably, the drying condition is：Drying temperature is 45 DEG C, and drying time is
24h。
Second aspect of the present invention provides a kind of preparation method of function dough nano-carbon material, includes the following steps：
A1 H) is added in nano-carbon material2O2It after carrying out ultrasound for the first time, is filtered, washed, dries, obtain intermediate product；
A2 it after intermediate product addition mixed acid) is carried out second of ultrasound, flows back, wash, drying is received to get function dough
Rice carbon material.
Third aspect present invention provides a kind of function dough nano-carbon material, is made by above-mentioned preparation method.
Fourth aspect present invention provides a kind of preparation method of sensor based on function dough nano-carbon material, is in electricity
Drying after function dough nano-carbon material solution is added dropwise in pole surface, then after perfluorinated sulfonic acid (Nafion) solution is added dropwise in electrode surface
It is dry, it is made.
Fifth aspect present invention provides a kind of sensor based on function dough nano-carbon material, by above-mentioned preparation method system
?.
As described above, a kind of detection method for pentachlorophenol content in paper wrapper provided by the invention, tool
There is following beneficial effect：
(1) a kind of detection method for pentachlorophenol content in paper wrapper provided by the invention, using electrification
Method quickly measures pentachlorophenol substance in paper wrapper, and response is fast, high sensitivity, accuracy are good, anti-dry
It is strong to disturb ability, the features such as required equipment is simple, and because it directly measures electrical signal, it is easy to accomplish continuous analysis operation is suitble to
In the quick detection of actual sample.
(2) a kind of detection method for pentachlorophenol content in paper wrapper provided by the invention, with functional group
Change the sensor that nano-carbon material modified electrode is detection, mainly utilizes the biggish specific surface area of function dough nano-carbon material
Pentachlorophenol is effectively raised in the accumulation ability of electrode surface, meanwhile, the introducing of function dough nano-carbon material increases electricity
The electrocatalysis characteristic and electron transport rate of electrode are improved in the electroactive site of pole surface, so as to improve the sensitivity of detection.
(3) a kind of detection method for pentachlorophenol content in paper wrapper provided by the invention, using electrification
Learn the advantage that detection method has other methods incomparable：Analysis speed quick and easy (several seconds~a few minutes), be easy to minimize,
Instrument cost is low, is suitable for the features such as field assay detection.
(4) a kind of detection method for pentachlorophenol content in paper wrapper provided by the invention, using electrification
The advantage for learning detection pentachlorophenol is that it only records the substance with electro-chemical activity in the electron transmission mistake of electrode surface
Journey selects suitable current potential that can effectively evade the influence of external interference object, to improve the selectivity of detection.
Detailed description of the invention
Fig. 1 is shown as the modification schematic diagram of electrode surface in the present invention.
Fig. 2 is shown as pentachlorophenol Electrochemical Test Procedure and CV curve synoptic diagram in the present invention, wherein curve 1 is
CV curve in 0.05MPBS solution, curve 2 are that the CV after 10 μ L pentachlorophenol standard solution are added in 0.05M PBS solution is bent
Line.
Specific embodiment
The present invention is further explained combined with specific embodiments below, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Embodiment 1
1, the preparation of silk-screen printing carbon (SPCE) electrode
Printing conductive silver paste forms electrode strip on the pet substrate, and the heat cure 40min in 120 DEG C of baking ovens is led to be formed
Electric silver layer.Conductive carbon paste is printed on conductive silver layer, in 71 DEG C of heat cure 30min, to form carbon working lining.In conductive silver layer
In current-carrying part on printing covering dielectric ink, the heat cure 10min at 80 DEG C, to form insulating layer.Final preparation obtains
Obtain silk-screen printing carbon (SPCE) electrode.
2, the preparation of function dough MWCNTs
It weighs multi-walled carbon nanotube (MWCNTs) 1g and is added to 50mL30%H2O2In solution, ultrasonic 4h keeps MWCNTs uniform
Dispersion is in the solution.Then it is filtered with 0.45 μm of filter membrane, and with milli-Q water three times, in 45 DEG C of vacuum drying 12h.
(HNO in mixed acid is added in the intermediate product of above-mentioned processing3:H2SO4=1:3), after ultrasonic 30min at 80 DEG C
Reflux carries out acidification reaction 8h, so that multi-wall carbon nano-tube pipe surface is introduced the oxygen-containing groups such as carboxyl and hydroxyl, to increase the water of material
Dissolubility, product milli-Q water to neutrality, to get functional group's multi-walled carbon nano-tube after drying in 45 DEG C of vacuum ovens
Material.
3, the preparation of the SPCE electrode based on function dough MWCNTs
It weighs 2mg functional group multi-walled carbon nano-tube (MWCNTs) material to be scattered in 1mL ultrapure water, ultrasonic 2h is divided
Dissipate uniform black liquor, i.e. functional group's multi-walled carbon nano-tube (MWCNTs) material solution.Above-mentioned 5 μ L of dispersion liquid is taken to be added dropwise
SPCE electrode surface, natural drying at room temperature, then 2 μ L 0.05wt%Nafion solution are added dropwise in SPCE electrode surface, and do naturally
It is dry, the SPCE electrode based on function dough MWCNTs is made, concrete outcome is shown in Fig. 1.As shown in Figure 1, function dough MWCNTs material
Material is modified by Electrostatic Absorption to electrode surface.It is molten that SPCE electrode based on function dough MWCNTs is stored in 0.05mol/LPBS
In liquid (pH=7.4) or dry environment.
Embodiment 2
1, the preparation of function dough single-layer graphene
It weighs single-layer graphene 1g and is added to 50mL30%H2O2In solution, ultrasonic 3h is dispersed in single-layer graphene
In solution.Then it is filtered with 0.45 μm of filter membrane, and with milli-Q water three times, in 45 DEG C of vacuum drying 12h.It will be above-mentioned
(HNO in mixed acid is added in the intermediate product of processing3:H2SO4=1:3) it, is flowed back at 70 DEG C after ultrasonic 30min
Row acidification reaction 7h makes single-layer graphene surface introduce the oxygen-containing groups such as carboxyl and hydroxyl, to increase the water solubility of material, product
With milli-Q water to neutrality, it is dry in 45 DEG C of vacuum ovens after to get function dough single-layer graphene material.
2, the preparation of the graphite electrode based on single-layer graphene
It weighs 2mg function dough single-layer graphene material to be scattered in 1mL ultrapure water, ultrasonic 2h obtains finely dispersed black
Color liquid, i.e. function dough single-layer graphene material solution.Above-mentioned 5 μ L of dispersion liquid is taken to be added dropwise in graphite electrode surface, room temperature is certainly
It is so dry, then 2 μ L 0.05wt%Nafion solution are added dropwise in graphite electrode surface, and spontaneously dry, it is made and is based on function dough
The graphite electrode of single-layer graphene.Graphite electrode based on function dough single-layer graphene is stored in 0.05mol/LPBS solution
(pH=7.4) or in dry environment.
Embodiment 3
1, the preparation of function dough active carbon nanoparticles
It weighs active carbon nanoparticles 1g and is added to 50mL30%H2O2In solution, ultrasonic 5h is dispersed in active carbon nanoparticles
In solution.Then it is filtered with 0.45 μm of filter membrane, and with milli-Q water three times, in 45 DEG C of vacuum drying 12h.It will be above-mentioned
(HNO in mixed acid is added in the intermediate product of processing3:H2SO4=1:3) it, is flowed back at 90 DEG C after ultrasonic 30min
Row acidification reaction 9h makes nano active carbon surface introduce the oxygen-containing groups such as carboxyl and hydroxyl, to increase the water solubility of material, product
With milli-Q water to neutrality, it is dry in 45 DEG C of vacuum ovens after to get function dough active carbon nanoparticles material.
2, the preparation of the glass-carbon electrode based on active carbon nanoparticles
It weighs 2mg function dough active carbon nanoparticles material to be scattered in 1mL ultrapure water, ultrasonic 2h obtains finely dispersed black
Color liquid, i.e. function dough active carbon nanoparticles material solution.Above-mentioned 5 μ L of dispersion liquid is taken to be added dropwise in glassy carbon electrode surface, room temperature is certainly
It is so dry, then 2 μ L 0.05wt%Nafion solution are added dropwise in glassy carbon electrode surface, and spontaneously dry, it is made and is based on function dough
The glass-carbon electrode of active carbon nanoparticles.Glass-carbon electrode based on function dough active carbon nanoparticles is stored in 0.05mol/LPBS solution
(pH=7.4) or in dry environment.
Embodiment 4
Qualitative detection is carried out to pentachlorophenol using cyclic voltammetric (CV) method, initial potential (low potential) is -0.5V, eventually
Point current potential (high potential) is 1.0V.The pentachlorophenol mark of various concentration is successively added dropwise to 0.05mol/LPBS solution (pH=7.4)
The quasi- sub- liquid of solution, the SPCE electrode based on function dough MWCNTs for using embodiment 1 to prepare are measured in the case where sweeping speed as 50mV/s
CV curve.1.0V peak current is observed, finds to be gradually increased with the addition of pentachlorophenol, oxidation current, illustrates the electrode of preparation
There is good response to pentachlorophenol.
Embodiment 5
Quantitative detection, initial potential 1.0V, between sampling are carried out to pentachlorophenol standard solution using chronoamperometry
It is divided into 0.1s, experimental period 2000s.It is added not into the 0.05mol/LPBS solution (pH=7.4) at the uniform velocity stirred every 30s
With the pentachlorophenol standard solution of concentration, surveyed using the SPCE electrode based on function dough MWCNTs prepared by embodiment 1
It is fixed, it can be observed that will appear ladder figure after pentachlorophenol is added every time, it mutually should be with electric current and do coordinate, the time is abscissa
Standard curve can be drawn.Regression equation, related coefficient and the range of linearity of standard curve are shown in Table 1.
Table 1
| Compound | Standard curve | R2 | The range of linearity (μ g) |
| Pentachlorophenol | Y=106.8493x+0.7397 | 0.996 | 0.005~0.05 |
Embodiment 6
Cigarette paper is cut into the fragment of (0.50 × 0.50) cm, is uniformly mixed, is placed in clean hermetic bag for use, often
A sample is no less than 5g.1.0g sample to be tested is accurately weighed, 0.1mg is accurate to, is placed in 100mL triangular flask, is added
40mL methanol, ultrasonic extraction 30min.5min is stood, pipettes appropriate extract liquor in centrifuge tube, with the centrifugation of 5000r/min rate
5min.1mL supernatant is pipetted, is filtered through 0.22 μm of organic phase filter membrane, obtains filtrate as sample solution, filtrate is placed in brown sample
In product.50 μ L filtrates are added in the 0.05mol/LPBS solution (pH=7.4) that at the uniform velocity stirs, using embodiment 1 prepare based on
The SPCE electrode of function dough MWCNTs is detected, and records electric response using chronoamperometry, and by embodiment 5
Standard curve calculate sample solution in pentachlorophenol content, the experimental results showed that, pentachlorophenol content in paper wrapper
For 0.05mg/kg, detailed process is shown in Fig. 2.As shown in Figure 2.By the electro-catalysis of electrode surface function dough nano-carbon material, energy
It enough realizes the electron transmission between pentachlorophenol electrode, electric signal is collected by electrochemical workstation, be finally translated into electrochemistry song
Line.
So the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (14)
1. a kind of detection method for pentachlorophenol content in paper wrapper, includes the following steps：
1) paper wrapper after shredding is taken, is stood after methanol ultrasonic extraction is added, solution is centrifuged after pipetting extraction, is taken
Filtrate is obtained after supernatant liquid filtering, as sample solution；
2) pentachlorophenol standard items is taken to add methanol dissolution and constant volume, preparing standard solution mother liquor；
3) the standard solution mother liquor in the step 2) of different volumes is taken, is added separately in phosphate buffer, is made into different dense
The sub- liquid of the standard solution of degree is respectively adopted after the sensor based on function dough nano-carbon material carries out qualitative and quantitative detection and establishes
Standard curve, then the sample solution in step 1) is added in phosphate buffer, using based on function dough nano carbon material
After the sensor of material is detected, the content of pentachlorophenol in sample solution is obtained by the standard curve.
2. a kind of detection method for pentachlorophenol content in paper wrapper according to claim 1, feature
It is, in step 1), including any of the following conditions or multinomial：
A1) paper wrapper is uniformly mixed after being cut into the fragment of 0.49-0.51cm × 0.49-0.51cm；
A2 the ratio between the volume mL that the quality g and methanol that) paper wrapper is added are added is 1:20-60；
A3) time of the ultrasonic extraction is 20-60min；
A4) time of the standing is 1-10min；
A5) centrifugation time is 2-10min, and the centrifugation rate is 3000-8000r/min；
A6) described to be filtered into membrane filtration, the filter membrane is 0.22 μm of organic phase filter membrane.
3. a kind of detection method for pentachlorophenol content in paper wrapper according to claim 1, feature
It is, in step 2), the concentration of pentachlorophenol is 0.5-2.0g/mL in the standard solution mother liquor.
4. a kind of detection method for pentachlorophenol content in paper wrapper according to claim 1, feature
Be, in step 3), the sensor that uses based on function dough nano-carbon material carry out the condition of qualitative detection for：Initially
Current potential, that is, low potential is -0.4~0.6V, and terminal current potential, that is, high potential is 0.8~1.2V, and scanning speed is 0.02~0.08V/s.
5. a kind of detection method for pentachlorophenol content in paper wrapper according to claim 1, feature
Be, in step 3), the sensor that uses based on function dough nano-carbon material carry out the condition of quantitative detection for：Initially
Current potential is 0.8~1.2V, and the sampling interval is 0.05~0.2s, and experimental period is 1000~3000s.
6. a kind of detection method for pentachlorophenol content in paper wrapper according to claim 1, feature
It is, in step 3), the concentration of the phosphate buffer PBS is 0.04-0.06mol/L, pH=7.4.
7. a kind of detection method for pentachlorophenol content in paper wrapper according to claim 1, feature
It is, in step 3), the sensor based on function dough nano-carbon material is that function dough nanometer is added dropwise in electrode surface
It is dry after carbon material solution, then the drying after perfluorinated sulfonic acid solution is added dropwise in electrode surface, it is made.
8. a kind of detection method for pentachlorophenol content in paper wrapper according to claim 7, feature
It is, the sensor based on function dough nano-carbon material, including any of the following conditions or multinomial：
B1) electrode is selected from glass-carbon electrode, gold electrode, graphite electrode, gold disc electrode, ito glass electrode, silk-screen printing carbon electricity
One of pole or silk-screen printing gold film electrode；
B2 it is 1-3mg/mL, function dough nano-sized carbon that) concentration of function dough nano-carbon material solution, which is added dropwise, in the electrode surface
The volume of material solution is 2-10 μ L；
B3) the function dough nano-carbon material solution needs ultrasonic disperse 1-3h；
B4) concentration that perfluorinated sulfonic acid solution is added dropwise in the electrode surface is 0.04-0.06wt%, and the volume of perfluorinated sulfonic acid solution is
1-3μL。
9. a kind of detection method for pentachlorophenol content in paper wrapper according to claim 7, feature
It is, the preparation of the function dough nano-carbon material includes the following steps：
A) H is added in nano-carbon material2O2It after carrying out ultrasound for the first time, is filtered, washed, dries, obtain intermediate product；
B) after second of ultrasound of mixed acid progress being added in intermediate product, reflux, washing, drying are to get function dough nano-sized carbon
Material.
10. a kind of detection method for pentachlorophenol content in paper wrapper according to claim 9, feature
It is, the preparation of the function dough nano-carbon material, including any of the following conditions or multinomial：
C1) in step a), the nano-carbon material is selected from mono-layer graphite piece, Multi-layer graphite piece, single-walled carbon nanotube, multi wall carbon
One of nanotube, single-layer graphene, multi-layer graphene, hollow Nano carbon ball, active carbon nanoparticles and its nitrating compound or
Multiple combinations；
C2) in step a), quality g and H that the nano-carbon material is added2O2The ratio between volume mL of addition is 1:45-1:55；
C3) in step a), the time of the first time ultrasound is 2-6h；
C4) in step a), the drying condition is：Drying device is vacuum oven, and drying temperature is 40-50 DEG C, dry
Time is 11-13h；
C5) in step b), the mixed acid is the mixed acid of nitric acid and sulfuric acid；
C6) in step b), the ratio between the volume mL that the quality g and mixed acid that the intermediate product is added are added is 1:10-1:30；
C7) in step b), the time of second of ultrasound is 25-35min；
C8) in step b), the temperature of the reflux is 60~100 DEG C, and the time of the reflux is 6~10h；
C9) in step b), the drying condition is：Drying device is vacuum oven, and drying temperature is 40-50 DEG C, dry
Time is 10-30h.
11. a kind of preparation method of function dough nano-carbon material, includes the following steps：
A H) is added in nano-carbon material2O2It after carrying out ultrasound for the first time, is filtered, washed, dries, obtain intermediate product；
B after second of ultrasound of mixed acid progress) is added in intermediate product, reflux, washing, drying are to get function dough nano-sized carbon
Material.
12. a kind of function dough nano-carbon material, the preparation method as described in claim 11 are made.
13. a kind of preparation method of the sensor based on function dough nano-carbon material is that function dough is added dropwise in electrode surface
It is dry after nano-carbon material solution, then the drying after perfluorinated sulfonic acid solution is added dropwise in electrode surface, it is made.
14. a kind of sensor based on function dough nano-carbon material, the preparation method as described in claim 13 are made.
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| CN113155919A (en) * | 2021-05-10 | 2021-07-23 | 南京海关工业产品检测中心 | Based on MnO2Method for detecting pentachlorophenol in wood product by using nano-rod |
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