CN109187677A - A kind of Pt/g-C3N4Composite material, electrochemical sensor and preparation method thereof, purposes - Google Patents
A kind of Pt/g-C3N4Composite material, electrochemical sensor and preparation method thereof, purposes Download PDFInfo
- Publication number
- CN109187677A CN109187677A CN201810745384.8A CN201810745384A CN109187677A CN 109187677 A CN109187677 A CN 109187677A CN 201810745384 A CN201810745384 A CN 201810745384A CN 109187677 A CN109187677 A CN 109187677A
- Authority
- CN
- China
- Prior art keywords
- preparation
- suspension
- electrochemical sensor
- solution
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/307—Disposable laminated or multilayered electrodes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
Inventor provide a kind of Pt/g-C3N4Composite material, chemical sensor and preparation method thereof, purposes, inventor is by a kind of simple synthetic method, by Pt combination g-C3N4Composite material is formed, and is applied in electrochemical sensor as electrode base materials, the electrochemical sensor of building is, it can be achieved that quick, sensitive, the efficient Electrochemical Detection of phenol.Composite material Pt/g-C3N4, the electro catalytic activity with precious metals pt, and because g-C3N4Large specific surface area, so that Pt/g-C3N4The electron transfer capacity during oxidation of phenol, Pt and g-C can be improved in compound3N4The detection sensitivity that the synergy of the two makes electrochemical signals that Pyrogentisinic Acid be remarkably reinforced is high.Meanwhile Pt/g-C3N4Electrochemical sensor without apparent response current, has good selectivity the chaff interferents such as ethyl alcohol, ethylene glycol, toluene, acetic acid and acetone.
Description
Technical field
The present invention relates to electrochemical field, in particular to a kind of Pt/g-C3N4Composite material, electrochemical sensor and its system
Preparation Method, purposes.
Background technique
In recent years, nanosecond science and technology develop very fast, and wherein nano-noble metal material not only has the general character of general nano material
(small-size effect, macroscopic quantum dimensional effect, skin effect), and their distinctive catalytic activity, can be according to actual needs
The photoelectric characteristic of adjusting, Electromagnetism Characteristics make them become the ideal material of Multi-way analysis detection.Carbonitride (g-C3N4) it is a kind of
It is stable without metal semiconductor material, since its is at low cost, synthesis is simple, catalytic performance is good, good biocompatibility, specific surface area
The advantages that big, in recent years g-C3N4Also have extensively in fields such as biosensor, water pollutant degradation and carbon dioxide reductions
Application.
Phenol can enter people's by number of ways such as respiratory tract, skin and oral cavities as a kind of toxic pollutant
Cell magma protein in body, with human body chemically reacts, and stimulates central nervous system, causes seriously to human health
Injury.Phenol is classified as one of priority pollutant by Environmental Defense (EPA).Therefore, it develops a kind of sensitive, fast
It is very urgent that fast, economic method carrys out quantitative analysis phenol.Traditional detection method has high performance liquid chromatography, Capillary Electrophoresis
Method, chemoluminescence method etc., but these methods usually time-consuming and laborious, complicated for operation, expensive equipment, it is difficult to realize scene inspection in real time
It surveys.Electrochemical method has many advantages, such as that high sensitivity, stability are good, easy to operate, at low cost and be easily achieved on-site test.Cause
This, develops phenol electrochemical sensor and has become a hot topic of research.However, unmodified carbon paper Pyrogentisinic Acid is almost without electrochemistry
Response.Carbon paper is modified so finding suitable material, becomes the pass for constructing highly sensitive phenol electrochemical sensor
Key.
Summary of the invention
For this purpose, the present invention provides a kind of Pt/g-C3N4Composite material, the Pt/g-C3N4Composite material be chloroplatinic acid with
g-C3N4Pass through precipitating reduction method preparation.
Inventor additionally provides a kind of Pt/g-C3N4The preparation method of composite material, which comprises the following steps:
g-C3N4Suspension preparation: the g-C for being 1-10 μm by partial size3N4Powder is added in deionized water, ultrasonic 25-
35min obtains g-C3N4Suspension；
Pt/g-C3N4Suspension preparation: to g-C in 10-15 minutes3N4Platinum acid chloride solution is slowly added in suspension, and
Continue ultrasound 3-8min after platinum acid chloride solution is added, obtains the first suspension；
Sodium citrate solution is added into the first suspension, ultrasonic 15-20min obtains the second suspension；Sodium citrate
The Pt nano particle dispersion that subsequent reactions can be made to generate is more evenly；
The second suspension is added in sodium borohydride solution in 3s, is obtained after persistently stirring 30-50min containing Pt/g-C3N4
Third suspension；
Separation drying: third suspension is separated by solid-liquid separation, with deionized water and ethanol washing sediment and is done
It is dry, obtain Pt/g-C3N4Powder；
The g-C3N4It is prepared for melamine high-temperature calcination,
The platinum acid chloride solution, sodium citrate solution and sodium borohydride solution are configured using deionized water.Use deionized water
Configuration can be effectively prevented and introduce interference impurity in electrode preparation.
Further, the g-C3N4, chloroplatinic acid, sodium borohydride molar ratio be 200-800:1-5:200-800；
Further, the sodium citrate and g-C3N4Molar ratio be 1-4:3-7.
Inventor provides Pt/g-C again3N4Purposes of the composite material when preparing electrochemical sensor.
Further, the purposes of the electrochemical sensor detection phenol.
Inventor additionally provides a kind of electrochemical sensor, and the electrochemical sensor uses above-mentioned Pt/g-C3N4Composite wood
Material is used as electrode base materials.
Further, the electrochemical sensor electrodes preparation method the following steps are included:
Working solution preparation: by Pt/g-C3N4Powder is put into n,N-Dimethylformamide, and ultrasonic 60min or more is divided
Dissipate uniform working solution；
Working electrode preparation: it by the uniform drop coating of working solution on load electrode, is spontaneously dried at 20-30 DEG C, obtains work
Electrode.
Further, the load electrode is naked carbon paper.
The electrochemical sensor is inventor provided for detecting the purposes of phenol.
It is different from the prior art, the Pt/g-C that above-mentioned technical proposal provides3N4Composite material and point chemical sensor, pass through
A kind of simple synthetic method, by Pt combination g-C3N4Composite material is formed as electrode base materials and is applied to electrochemistry biography
In sensor, the electrochemical sensor of building is, it can be achieved that quick, sensitive, the efficient Electrochemical Detection of phenol.Composite material Pt/g-
C3N4, there is the good electro catalytic activity of noble metal nano, and because g-C3N4Large specific surface area, so that Pt/g-C3N4Compound
The electron transfer capacity during oxidation of phenol, Pt and g-C can be improved3N4The synergy of the two makes electrochemical signals bright
The detection sensitivity of aobvious enhancing Pyrogentisinic Acid is high.Meanwhile Pt/g-C3N4Electrochemical sensor to ethyl alcohol, ethylene glycol, toluene, acetic acid and
The chaff interferents such as acetone have good selectivity without apparent response current.
Detailed description of the invention
Fig. 1 is Pt/g-C3N4Scanning transmission electron microscope (STEM) figure；
Fig. 2 is Pt/g-C3N4X-ray diffraction (XRD) map；
Fig. 3 is naked CP (a), g-C3N4/CP(b),Pt/g-C3N4PBS (pH=3.0) solution of/CP (c) electrode in 0.1M
Cyclic voltammetry curve figure containing 50 μM of phenol, sweep speed 0.05Vs-1；
Fig. 4 be in the solution that 0.1M PBS contains 50 μM of phenol, under different pH (1.0-4.0), Pt/g-C3N4/ CP's
CV figure, what illustration indicated is in response to electric current and the relationship of pH；
Fig. 5 is Pt/g-C3N4The linear relationship chart of/CP oxidation of phenol spike potential and pH；
Fig. 6 is Pt/g-C3N4/ CP is in 0.1M PBS, 50 μM of phenol solution, different sweep speed (0.03-
Cyclic voltammogram under 0.12Vs-1)；
Fig. 7 is Pt/g-C3N4The subduplicate linear relationship chart of/CP peak point current and sweep speed；
Fig. 8 is Pt/g-C3N4Cyclic voltammetry curve of/the CP to various concentration phenol in 0.1M PBS (pH=3.0) solution
(from 2 μM to 20 μM)；
Fig. 9 is Pt/g-C3N4The linear relationship of/CP peak point current and concentration；
Figure 10 is that certain density phenol, Pt/g-C continuously is added into 0.1M PBS (pH=3.0) solution3N4/
The chrono-amperometric of CP electrode responds, and illustration is in response to the check and correction curve of electric current and concentration；
Figure 11 is that different substances is added into buffer solution (pH=3.0) to correspond to Pt/g-C3N4The ampere of/CP electrode is rung
Ying Tu.
Specific embodiment
Technology contents, construction feature, the objects and the effects for detailed description technical solution, below in conjunction with specific reality
It applies example and attached drawing is cooperated to be explained in detail.
Embodiment 1Pt/g-C3N4Powder preparation
1. the preparation of carbonitride
It takes the melamine of 4g to be put into mortar to be fitted into crucible after grinding, guarantees that there are certain between crucible and lid
It is moved into Muffle furnace behind gap.So that in-furnace temperature is kept for 520 DEG C with the heating rate of 5 DEG C/min, calcines 4h.After the completion of calcining certainly
It is so cooled to room temperature, obtains faint yellow nitridation carbon dust.
2.Pt/g-C3N4Synthesis and powder preparation
Take 50mg, the carbonitride (g-C of 1-10 μm of granularity preparation3N4) powder is dissolved in the deionized water of 40mL, ultrasound
30min, then by the chloroplatinic acid H of 0.3mL in 15min2PtCl6·6H2O (0.01M) is slowly added dropwise into carbonitride suspension
In, continue ultrasound 5min, obtains mixing suspension；
By the anhydrous citric acid sodium C of 0.0645g6H5Na3O7It is dissolved in the deionized water of 5mL, is then added dropwise to above-mentioned
In mixing suspension, by suspension ultrasound 20min.The NaBH of brand-new is poured into 3s after mixing4(0.05M) solution
Reaction 40min is continuously sufficiently stirred in 10mL.To be centrifuged after the reaction was completed with supercentrifuge, supernatant is abandoned, collects precipitating, precipitating
It is washed respectively with deionized water and dehydrated alcohol and is placed in 60 DEG C of thermostatic drying chambers dry 10h three times to get Pt/g-C3N4Powder
End.
Embodiment 2
1. the preparation of carbonitride
It takes the melamine of 4g to be put into mortar to be fitted into crucible after grinding, guarantees that there are certain between crucible and lid
It is moved into Muffle furnace behind gap.So that in-furnace temperature is kept for 520 DEG C with the heating rate of 5 DEG C/min, calcines 4h.After the completion of calcining certainly
It is so cooled to room temperature, obtains faint yellow nitridation carbon dust.
2.Pt/g-C3N4Synthesis and powder preparation
Take 0.2mol, the carbonitride (g-C of 1-10 μm of granularity preparation3N4) powder is dissolved in the deionized water of 50mL, ultrasound
25min, then in 12min by platinum acid chloride solution (the 1mmol H of 0.5mL2PtCl6·6H2O configuration)It is slowly added dropwise outstanding into carbonitride
In supernatant liquid, continues ultrasound 8min, obtain mixing suspension；
By the anhydrous citric acid sodium C of 0.2mol6H5Na3O7It is dissolved in the deionized water of 10mL, is then added dropwise to above-mentioned
In mixing suspension, by suspension ultrasound 20min.The 0.2molNaBH of brand-new is poured into 3s after mixing4Solution 10mL,
Reaction 30min is continuously sufficiently stirred.To be centrifuged after the reaction was completed with supercentrifuge, supernatant is abandoned, collects precipitating, precipitating is used respectively
Deionized water and dehydrated alcohol washing are placed in 55 DEG C of thermostatic drying chambers dry 12h three times to get Pt/g-C3N4Powder.
Embodiment 3
1. the preparation of carbonitride
It takes the melamine of 4g to be put into mortar to be fitted into crucible after grinding, guarantees that there are certain between crucible and lid
It is moved into Muffle furnace behind gap.So that in-furnace temperature is kept for 520 DEG C with the heating rate of 5 DEG C/min, calcines 4h.After the completion of calcining certainly
It is so cooled to room temperature, obtains faint yellow nitridation carbon dust.
2.Pt/g-C3N4Synthesis and powder preparation
Take 0.8mol, the carbonitride (g-C of 1-10 μm of granularity preparation3N4) powder is dissolved in the deionized water of 100mL, surpass
Sound 35min, then 10-15min by 1mL platinum acid chloride solution (5mmol H2PtCl6·6H2O configuration) it is slowly added dropwise into nitridation
In carbon suspension liquid, continues super 8min, obtain mixing suspension；By the anhydrous citric acid sodium C of 0.5mol6H5Na3O7It is dissolved in 10mL's
It in deionized water, is then added dropwise in above-mentioned mixing suspension, by suspension ultrasound 20min.After mixing in 3s
Pour into the 0.8mol NaBH newly configured4Reaction 50min is continuously sufficiently stirred in the 15mL solution of configuration.To after the reaction was completed with height
Fast centrifuge centrifugation, abandons supernatant, collects precipitating, and precipitating is washed with deionized water and dehydrated alcohol respectively is placed on 60 DEG C of perseverances three times
Dry 10h is in warm drying box to get Pt/g-C3N4Powder.
Embodiment 4
1. the preparation of carbonitride
It takes the melamine of 4g to be put into mortar to be fitted into crucible after grinding, guarantees that there are certain between crucible and lid
It is moved into Muffle furnace behind gap.So that in-furnace temperature is kept for 520 DEG C with the heating rate of 5 DEG C/min, calcines 4h.After the completion of calcining certainly
It is so cooled to room temperature, obtains faint yellow nitridation carbon dust.
2.Pt/g-C3N4Synthesis and powder preparation
Take 0.7mol, the carbonitride (g-C of 1-10 μm of granularity preparation3N4) powder is dissolved in the deionized water of 100mL, surpass
Sound 35min, then in 10-15min by platinum acid chloride solution (the 3mmol H of 1mL2PtCl6·6H2O configuration) it is slowly added dropwise into nitridation
In carbon suspension liquid, continues super 8min, obtain mixing suspension；By the anhydrous citric acid sodium C of 0.4mol6H5Na3O7It is dissolved in 10mL's
It in deionized water, is then added dropwise in above-mentioned mixing suspension, by suspension ultrasound 20min.After mixing in 3s
Pour into the 0.6mol NaBH newly configured4Reaction 40min is continuously sufficiently stirred in the 15mL solution of configuration.To after the reaction was completed with height
Fast centrifuge centrifugation, abandons supernatant, collects precipitating, and precipitating is washed with deionized water and dehydrated alcohol respectively is placed on 60 DEG C of perseverances three times
Dry 10h is in warm drying box to get Pt/g-C3N4Powder.
Embodiment 5
1. the preparation of carbonitride
It takes the melamine of 4g to be put into mortar to be fitted into crucible after grinding, guarantees that there are certain between crucible and lid
It is moved into Muffle furnace behind gap.So that in-furnace temperature is kept for 520 DEG C with the heating rate of 5 DEG C/min, calcines 4h.After the completion of calcining certainly
It is so cooled to room temperature, obtains faint yellow nitridation carbon dust.
2.Pt/g-C3N4Synthesis and powder preparation
Take 0.3mol, the carbonitride (g-C of 1-10 μm of granularity preparation3N4) powder is dissolved in the deionized water of 100mL, surpass
Sound 35min, then in 10-15min by platinum acid chloride solution (the 2mmol H of 1mL2PtCl6·6H2O configuration) it is slowly added dropwise into nitridation
In carbon suspension liquid, continues super 8min, obtain mixing suspension；By the anhydrous citric acid sodium C of 0.1mol6H5Na3O7It is dissolved in 10mL's
It in deionized water, is then added dropwise in above-mentioned mixing suspension, by suspension ultrasound 20min.After mixing in 3s
Pour into the 0.8mol NaBH newly configured4Reaction 30min is continuously sufficiently stirred in the 15mL solution of configuration.To after the reaction was completed with height
Fast centrifuge centrifugation, abandons supernatant, collects precipitating, and precipitating is washed with deionized water and dehydrated alcohol respectively is placed on 65 DEG C of perseverances three times
Dry 10h is in warm drying box to get Pt/g-C3N4Powder.
Pt/g-C3N4(preparation of embodiment 1) performance test:
1, Pt/g-C is analyzed3N4The shape characteristic of compound:
The Pt/g-C that will be prepared in embodiment 13N4Compound analyzes Pt/g- by scanning transmission electron microscope (STEM)
C3N4The shape characteristic of compound, is specifically shown in Fig. 1.
From left figure it can be seen that in g-C3N4Dispersion on surface tiny Pt nanoparticle, illustrate that Pt successfully adheres to
In g-C3N4On.In addition, different colours represent different elements in right figure, display nano-complex only contained only
Thus tri- kinds of elements of C, N and Pt prove it can be concluded that Pt and g-C3N4It coexists and Pt is distributed in g-C well3N4On surface, with
On show successfully to synthesize the higher Pt/g-C of purity3N4Composite material.Pt/g-C3N4Composite material is with g-C3N4For kernel,
Pt is the composite construction of outer layer.
2, to Pt/g-C3N4Compound carries out XRD analysis:
By Pt/g-C prepared by embodiment 13N4Compound carries out X-ray diffraction, and diffracting spectrum is as shown in Figure 2.
There is a very strong diffraction maximum at 2 θ=27.73 ° in Fig. 2 spectrogram, corresponds to g-C3N4(002) crystal face, 2 θ
Diffraction maximum at=12.98 ° corresponds to g-C3N4(100) crystal face；In addition, in XRD spectrum figure, 2 θ=17.89 °, 2 θ=21.76 °
With also occur faint diffraction maximum at 2 θ=57.04 ° in succession, due under hot conditions, melamine is forming g-C3N4's
Corresponding intermediate is produced in the process.In addition there are two diffraction maximums at 2 θ=39.54 ° and 2 θ=44.5 °, respectively corresponds
In (111) and (200) crystal face of Pt nanoparticle.
This result again demonstrates Pt and g-C3N4Composite material has been successfully synthesized.
The preparation of 6. working electrode of embodiment and electric transducer
Working solution preparation: the Pt/g-C that 5mg embodiment 1 prepares is weighed3N4Powder is dispersed in the N of 1mL, N- diformazan
In base formamide (DMF), ultrasonic 1h is to obtain finely dispersed suspension.Working electrode preparation: the mixing drop of 5 μ L is pipetted
It is coated in cut-and-dried carbon paper (0.3*0.5cm2) on, it spontaneously dries at room temperature, with its preparation work electrode.
2, the preparation of electric transducer:
Electric transducer is three-electrode system.Wherein supporting Pt and g-C on carbon paper3N4Composite material is working electrode, silver/chlorine
Change silver electrode is reference electrode, and platinum electrode is to electrode.Above-mentioned electrode is connected on electrochemical workstation.
Pt/g-C3N4Electrode electro Chemical test:
In this experimental system, electrochemistry experiment is carried out under the three-electrode system of standard.By Pt/g-C3N4/CP
Working electrode be immersed in phenol solution, using cyclic voltammetry (CV) test sensor performance, setting experiment parameter such as
Under；Scanning voltage 0.7-1.2V, sweep speed 0.05Vs-1, time of repose 2s.Ampere response fixed voltage be set as+
0.95V, sampling interval 0.02s.
Performance test:
1, to CP, g-C3N4/ CP and Pt/g-C3N4/ C is that the electric transducer of electrode is tested for the property
Respectively with CP, g-C3N4/ CP and Pt/g-C3N4/ CP electrode is working electrode, is placed on containing 50 μM of phenol
In PBS (pH=3.0) solution of 0.1M, scanning voltage is from 0.7 to 1.2V, sweep speed 0.05Vs-1.
As a result see Fig. 3, the curve (a) in Fig. 3 is the CV figure of unmodified CP, and current-responsive is very faint, explanation
Naked CP is almost without electro-chemical activity.That curve (b) indicates is g-C3N4/ CP electrode, oxidation peak current are apparently higher than not
Modified CP, the result shows g-C3N4With catalytic activity.Curve (c) is Pt/g-C3N4The CV of/CP electrode schemes.
Pass through the comparison of three kinds of different modifying electrodes, in figure 5 it can be seen that as Pt nanoparticle combination g-C3N4Common modification CP electricity
When pole, Pt/g-C3N4The oxidation peak current of/CP electrode is compared with CP and g-C3N4/ CP is significantly increased, this is because Pt nanoparticle is good
Good electric conductivity and g-C3N4Large specific surface area, so that Pt/g-C3N4The electronics turn during oxidation of phenol can be improved in compound
Shifting ability, Pt and g-C3N4Electrochemical signals are remarkably reinforced in the synergy of the two.
2, condition of different pH is to detection Pt/g-C3N4The influence of/C electrode
When the value of pH is adjusted to 3 by 1, the current strength of oxidation peak is gradually enhancing, but with the further increasing of pH
Greatly, the peak point current of oxidation peak declines instead, therefore pH=3.0 is buffer optimal pH.It is surveyed with cyclic voltammetry (CA)
Determine electrochemical characteristic of the working electrode under condition of different pH, it is specific as shown in Figure 4.
The relationship of oxidation spike potential and pH, linear equation are as follows: Epa (V)=- 0.04838V/pH+ is shown in Fig. 5
Negative transfer has occurred with the increase of pH in the current potential of 1.10015 (R=0.9996), oxidation peak.
It is above to prove: Pt/g-C3N4/ C electrode buffer pH=3.0 is best.
3、Pt/g-C3N4Influence of the different sweep speed of/CP electrode to current-responsive:
Test result is shown in Fig. 6: in 0.1M PBS, 50 μM of phenol solution, different sweep speed (0.03-0.12Vs-1) under cyclic voltammogram.
Fig. 7 is the subduplicate linear relationship sweep speed of peak point current and sweep speed.As seen from Figure 7 in 0.03-
0.12Vs-1In the range of, Pt/g-C3N4The oxidation peak current (Ipa) of/CP modified electrode and the square root (v1/2) of surface sweeping rate
In a linear relationship, with the increase of sweep speed, the electric current at anode peak is gradually increased.
Equation of linear regression: Ipa (μ A)=52.539v1/2 (Vs-1) 1/2-3.7975 (R=0.9953).The result shows that
Phenol is in Pt/g-C3N4Oxidation behavior on/CP sensing surface is a kind of diffusion controlled process.
In Fig. 7 represented by illustration, the relationship of spike potential and lnv.As sweep speed is constantly increasing, anode peak
Current potential (Epa) also gradually mobile to anode, linear relationship is as follows: Epa (V)=0.024881lnv (Vs-1)+
0.99998 (R=0.9948).As a result the electrocatalysis oxidation reaction for also further illustrating phenol is by dynamics Controlling.Root
Linear relation and Laviron ' s equation accordingly, can calculate the electron number shifted in oxidation process.Laviron ' s equation
It is as follows:
Epa=E0-[RT/ (1- α) nF] ln [RTKs/ (1- α) nF]+[RT/ (1- α) nF] lnv
E0 is standard oxidationreduction potential in formula, and Ks is standard speed coefficient, and F is Faraday constant, and T is Kelvin's temperature
Degree, α are transfer ratios, and n is that the electron number of transfer calculates (1- α) n and be equal to according to spike potential (Epa) to the slope of lnv
1.032, α can find out according to following equation, and what Ep/2-Ep=1.875 (RT/ α F), Ep/2 were indicated is half spike, thus count
It calculates α and is equal to 0.5250, the electron number of transfer is about 2.
It is above to prove Pt/g-C3N4/ CP electrode Pyrogentisinic Acid's oxidation process has good electrocatalysis, can be used for phenol
Detection.
4、Pt/g-C3N4The electrochemical analysis performance of/CP electrode detection phenol.
It is 0.05Vs in sweep speed-1In the case where, as the concentration of phenol increases to 20 μM by 2 μM, response current by
Cumulative big, there is maximum peak current, this illustrates the biography as shown in figure 8, can be observed from Fig. 8 at+0.95V in concrete outcome
Sensor Pyrogentisinic Acid's oxidation process has good electrocatalysis.
Fig. 9 shows the linear relationship between peak current and concentration, and linear equation can state are as follows: Ipa (μ A)=
1.21084C (μM) -0.97465 (R=0.9923), the sensitivity of the sensor are 1.21084mA μM -1, minimum detection limit
0.667 μM of concentration (S/N=3).
It is above to prove Pt/g-C3N4/ CP electrode Pyrogentisinic Acid's oxidation process has good electrocatalysis, can be used for phenol
Detection.
5, under the best experimental conditions, the Pt/g-C under low concentration3N4/ CP sensor Pyrogentisinic Acid detection.
In the case where detection voltage is set as+0.95V, by Pt/g-C3N4It is molten that/CP electrode is placed on 100mL0.1M PBS
In liquid (pH=3.0), certain density phenol, Pt/g-C are added dropwise into the buffer solution being stirred continuously every 40s3N4/ CP electrode
Energy quick response, electric current can sharply increase in a short time and quickly reach stable state.
Testing result is shown in Figure 10, Pt/g-C3N4The ampere response curve of/CP electrode；What illustration indicated is in response to electric current and benzene
Linear relationship between phenol concentration, linear equation are as follows: I (μ A)=0.04276C (μM)+0.1893 (R=0.9980), linearly
Range is 1 μM to 10 μM, and corresponding sensitivity is 0.04276mA μM -1, and detection is limited to 0.333 μM (S/N=3).
It is above to prove Pt/g-C3N4/ CP sensor Pyrogentisinic Acid detection has high sensitivity.
6, anti-interference ability detects:
In order to study Pt/g-C3N4The selectivity of/CP electrode is added in experimentation in the buffer solution being stirred continuously
Some substances that may generate interference, measure Pt/g-C with Amperometric3N4The anti-interference ability of modified electrode.Present invention choosing
The chaff interferent selected is ethyl alcohol, ethylene glycol, toluene, parahydroxyben-zaldehyde, acetic acid and the acetone that concentration is 0.1M.
The result is shown in Figure 11, it can be seen from fig. 11 that the addition of ethyl alcohol, ethylene glycol, toluene, acetic acid and acetone does not cause
Response current significantly changes, and illustrates Pt/g-C3N4Electrode has selectivity well.But the addition of parahydroxyben-zaldehyde, immediately
There is current-responsive.Therefore, interference of this substance of hydroxy benzaldehyde to detection should be avoided in detection phenol process.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or the terminal device that include a series of elements not only include those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or end
The intrinsic element of end equipment.In the absence of more restrictions, being limited by sentence " including ... " or " including ... "
Element, it is not excluded that there is also other elements in process, method, article or the terminal device for including the element.This
Outside, herein, " being greater than ", " being less than ", " being more than " etc. are interpreted as not including this number；" more than ", " following ", " within " etc. understand
Being includes this number.
It should be noted that being not intended to limit although the various embodiments described above have been described herein
Scope of patent protection of the invention.Therefore, it based on innovative idea of the invention, change that embodiment described herein is carried out and is repaired
Change, or using equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content, it directly or indirectly will be with
Upper technical solution is used in other related technical areas, is included within scope of patent protection of the invention.
Claims (10)
1. a kind of Pt/g-C3N4Composite material, which is characterized in that the Pt/g-C3N4Composite material is with g-C3N4For kernel, Pt
For the composite construction of outer layer.
2. a kind of Pt/g-C3N4The preparation method of composite material, which comprises the following steps:
g-C3N4Suspension preparation: the g-C for being 1-10 μm by partial size3N4Powder is added in deionized water, and ultrasonic 25-35min is obtained
g-C3N4Suspension；
Pt/g-C3N4Suspension preparation: to g-C in 10-15 minutes3N4It is slowly added to platinum acid chloride solution in suspension, and is adding
Continue ultrasound 3-8min after entering platinum acid chloride solution, obtains the first suspension；
Sodium citrate solution is added into the first suspension, ultrasonic 15-20min obtains the second suspension；
The second suspension is added in sodium borohydride solution in 3s, is obtained after persistently stirring 30-50min containing Pt/g-C3N4?
Three suspensions；
Separation drying: third suspension is separated by solid-liquid separation, with deionized water and ethanol washing sediment and is dried, obtains
To Pt/g-C3N4Powder；
The g-C3N4It is prepared for melamine high-temperature calcination,
The platinum acid chloride solution, sodium citrate solution and sodium borohydride solution are configured using deionized water.
3. preparation method according to claim 2, which is characterized in that the g-C3N4, chloroplatinic acid, sodium borohydride mole
Than for 200-800:1-5:200-800.
4. preparation method according to claim 2, which is characterized in that the sodium citrate and g-C3N4Molar ratio be 1-
4:3-7。
5. Pt/g-C described in claim 13N4Purposes of the composite material when preparing electrochemical sensor.
6. purposes according to claim 5, which is characterized in that the purposes of the electrochemical sensor detection phenol.
7. a kind of electrochemical sensor, which is characterized in that the electrochemical sensor uses Pt/g-C described in claim 13N4
Composite material is as electrode base materials.
8. electrochemical sensor according to claim 7, which is characterized in that the preparation method of the electrochemical sensor electrodes
The following steps are included:
Working solution preparation: by Pt/g-C3N4Powder is put into n,N-Dimethylformamide, ultrasonic 60min or more, and it is equal to obtain dispersion
Even working solution；
Working electrode preparation: it by the uniform drop coating of working solution on load electrode, is spontaneously dried at 20-30 DEG C, obtains working electrode.
9. electrochemical sensor according to claim 8, which is characterized in that the load electrode is naked carbon paper.
10. the purposes that any electrochemical sensor of claim 7-9 is used to detect phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810745384.8A CN109187677B (en) | 2018-07-09 | 2018-07-09 | Pt/g-C3N4Composite material, electrochemical sensor, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810745384.8A CN109187677B (en) | 2018-07-09 | 2018-07-09 | Pt/g-C3N4Composite material, electrochemical sensor, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109187677A true CN109187677A (en) | 2019-01-11 |
| CN109187677B CN109187677B (en) | 2020-07-21 |
Family
ID=64936361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810745384.8A Expired - Fee Related CN109187677B (en) | 2018-07-09 | 2018-07-09 | Pt/g-C3N4Composite material, electrochemical sensor, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109187677B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110729495A (en) * | 2019-11-08 | 2020-01-24 | 广东伟的新材料股份有限公司 | CNSs-Ni@Pt/PM-g-C3N4Electrocatalyst and method of making |
| CN113930203B (en) * | 2021-10-15 | 2023-08-08 | 广东电网有限责任公司 | Adhesive with high barrier property, preparation method and application thereof in composite insulator |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586064A (en) * | 2013-11-26 | 2014-02-19 | 中国科学院福建物质结构研究所 | Metal/graphite-like carbon nitride compound catalyst and preparing method thereof |
| CN106984354A (en) * | 2017-04-26 | 2017-07-28 | 福州大学 | A kind of preparation method and applications of palladium doped graphite phase carbon nitride nano material |
-
2018
- 2018-07-09 CN CN201810745384.8A patent/CN109187677B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586064A (en) * | 2013-11-26 | 2014-02-19 | 中国科学院福建物质结构研究所 | Metal/graphite-like carbon nitride compound catalyst and preparing method thereof |
| CN106984354A (en) * | 2017-04-26 | 2017-07-28 | 福州大学 | A kind of preparation method and applications of palladium doped graphite phase carbon nitride nano material |
Non-Patent Citations (3)
| Title |
|---|
| MEHMET LÜTFI YOLA等: "Electrochemical Detection of Atrazine by Platinum Nanoparticles/Carbon Nitride Nanotubes with Molecularly Imprinted Polymer", 《INDUSTRIAL AND ENGINEERING CHEMISTRY RESEARCH》 * |
| WEI FANG等: "Synthesis of Pd/Au bimetallic nanoparticle-loaded ultrathin graphitic carbon nitride nanosheets for highly efficient catalytic reduction of p-nitrophenol", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 胡红伟等: "g-C3N4和Pt /g-C3N4在常温常压电化学合成氨中的阴极催化性能", 《化学工业与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110729495A (en) * | 2019-11-08 | 2020-01-24 | 广东伟的新材料股份有限公司 | CNSs-Ni@Pt/PM-g-C3N4Electrocatalyst and method of making |
| CN113930203B (en) * | 2021-10-15 | 2023-08-08 | 广东电网有限责任公司 | Adhesive with high barrier property, preparation method and application thereof in composite insulator |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109187677B (en) | 2020-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cheng et al. | Facile synthesis of Co9S8 nanocages as an electrochemical sensor for luteolin detection | |
| Cao et al. | Electrochemical sensor for detecting pain reliever/fever reducer drug acetaminophen based on electrospun CeBiOx nanofibers modified screen-printed electrode | |
| Wang et al. | A novel sensitive nonenzymatic glucose sensor based on perovskite LaNi0. 5Ti0. 5O3-modified carbon paste electrode | |
| Mashhadizadeh et al. | Synergistic effect of magnetite and gold nanoparticles onto the response of a label-free impedimetric hepatitis B virus DNA biosensor | |
| Xia et al. | A novel bio-electrochemical ascorbic acid sensor modified with Cu4 (OH) 6SO4 nanorods | |
| CN109444230B (en) | Au/CeO2/g-C3N4Composite material, electrochemical sensor, preparation method and application thereof | |
| Dong et al. | A nonenzymatic L-cysteine sensor based on SnO2-MWCNTs nanocomposites | |
| CN102175735B (en) | Au NPs-CeO2@PANI (polyaniline) nanocomposite, preparation method thereof and glucose biological sensor manufactured by utilizing nanocomposite | |
| Garkani et al. | La3+-doped Co3O4 nanoflowers modified graphite screen printed electrode for electrochemical sensing of vitamin B6 | |
| CN109187677A (en) | A kind of Pt/g-C3N4Composite material, electrochemical sensor and preparation method thereof, purposes | |
| Ibrahim et al. | A novel sensor based on nanobiocomposite Au-In2O3-chitosan modified acetylene black paste electrode for sensitive detection of antimycotic ciclopirox olamine | |
| CN107311234A (en) | A kind of preparation method of zinc oxide/zinc ferrite nano composite material and application | |
| CN108844999B (en) | Utilization of g-C for detection of VOCs3N4Synthetic method of modified porous zinc oxide nanosheet composite gas-sensitive material | |
| Nataraj et al. | Samarium vanadate nanospheres integrated carbon nanofiber composite as an efficient electrocatalyst for antituberculosis drug detection in real samples | |
| Jahani et al. | Screen-printed graphite electrode modified with Co3O4 nanoparticles and 2D graphitic carbon nitride as an effective electrochemical sensor for 4-aminophenol detection | |
| Mohammadi et al. | Screen printed carbon electrode modified with magnetic core shell manganese ferrite nanoparticles for electrochemical detection of amlodipine | |
| Bai et al. | Acidification of manganese dioxide for ultrasensitive electrochemical sensing of hydrogen peroxide in living cells | |
| Faridan et al. | Simultaneous determination of Hg (II), Cd (II), Pb (II) and Zn (II) by anodic stripping voltammetry using modified carbon paste ionic liquid electrode | |
| CN110361431A (en) | A kind of combination electrode and preparation method thereof and method for ammonia nitrogen detection | |
| CN107525836B (en) | CeO2-x/ C/rGO nanocomposite and its preparation method and application | |
| CN106053562A (en) | Modified electrode for detecting sodium nitrite, preparation method and applications thereof | |
| Arvand et al. | Electrospun CeO 2–Au nanofibers/graphene oxide 3D nanonetwork structure for the electrocatalytic detection of amlodipine | |
| CN106568817B (en) | It is a kind of for the chemically modified electrode of quantitative detection of folic acid and the preparation method of electrochemical sensor | |
| Yin et al. | Electrochemical sensor for determination of Pb2+ based on Gold nanoparticles | |
| Fu et al. | Application of nickel cobalt oxide nanoflakes for electrochemical sensing of estriol in milk |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200721 Termination date: 20210709 |