CN108956730A - A kind of electrochemical sensor and its preparation method and application for direct alcohol fuel cell - Google Patents
A kind of electrochemical sensor and its preparation method and application for direct alcohol fuel cell Download PDFInfo
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- CN108956730A CN108956730A CN201810895140.8A CN201810895140A CN108956730A CN 108956730 A CN108956730 A CN 108956730A CN 201810895140 A CN201810895140 A CN 201810895140A CN 108956730 A CN108956730 A CN 108956730A
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- 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
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- 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
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Abstract
The present invention provides a kind of catalyst carrier for direct alcohol fuel cell, the electrochemical sensor for being used for direct alcohol fuel cell is also provided, it is that cleaned basal electrode is put into catalyst carrier prepared by the present invention to carry out electro-deposition, then places into potassium chloroplatinate aqueous solution and carry out what electro-deposition obtained.Graphene oxide and polyethyleneimine amino-group doping are formed intercalation composite material, obtain catalyst carrier by the present invention, and it is deposited onto glassy carbon electrode surface, then electro-deposition catalyst platinum, obtains electrochemical sensor, the catalytic oxidation of methanol is carried out using three-electrode system, catalytic effect is significant.It is detected using methanol solution of the electrode to various concentration, it is found that catalysis oxidation peak height and methanol concentration are in a linear relationship, linear good when methanol concentration is between 0.02M-2.0M, R2=0.996, it can be used as detection of the electrochemical sensor for methanol in solution.
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of electrochemical sensing for direct alcohol fuel cell
Device and its preparation method and application.
Background technique
Direct alcohol fuel cell (DAFC) belongs to one kind of Proton Exchange Membrane Fuel Cells, it directly uses alcohols material
Without reforming in advance.Alcohols is converted into carbon dioxide and hydrogen ion in cathode, then hydrogen ion is reacted with oxygen again.DAFC because
With no pollution, fuel source is extensive, energy density is high, conversion rate is fast, low operation temperature, storage are easy, convenient transportation etc.
Feature has a extensive future in energy field.Traditional noble metal catalyst platinum (Pt), it is expensive, it is easy inactivation, is seriously hindered
The development of DMFC.Excellent catalyst carrier can reduce noble metal dosage, improve catalyst activity, be to solve DAFC to develop
One of important channel.
Suitable catalyst carrier is due to being capable of providing high surface area, suitable porosity, high conductivity and high stability,
And fuel cell can be made to improve the tolerance of toxicity intermediate product, therefore inquire into support modification and ground in direct alcohol fuel cell
Immeasurable effect is played in hair.In many carrier materials, nano-carbon material (carbon nanotube, carbon fiber, carbon ball
Deng), because of its excellent physicochemical properties (strong acidproof, alkali resistance, strong electric conductivity, good metallicity and semiconductive etc.) and
Unique nanometer size effect has been a hot spot of research.Elctro-catalyst not only can be enhanced as electro-catalyst carrier in carbon material
Dispersion degree and activity, while the electron transmission in reaction process can be reinforced, improve the efficiency of catalysis oxidation.Graphene is mesh
Preceding most thin (being equivalent to atomic diameter), most hard two-dimentional carbon nanomaterial, it is considered to be most promising alcohol fuel battery
Carrier material.Graphene oxide (GO) is product of the graphene after oxidation processes, and graphene oxide still has graphene
Layer structure, but its monolithic surface layer and edge introduce many carboxyls, hydroxyl and oxygen-containing functional group.
Using carbon nanometer as base material, Pt is the alcohol fuel battery of catalyst, generally all by being doped into metal platinum
It is nano combined to enter other metals, metal oxide, metal composite nano particle, nitrogen and nano-complex, conducting polymer and carbon
Material etc. improves the electrochemical catalysis activity of noble metal electrocatalyst.Such as Xi Geng etc. utilizes polymer embedding techniques, by Pt
It is connected to PtSn nano particle on the polyelectrolyte polyethyleneimine of multi-walled carbon nanotube modification, is aoxidized for methanol, obtained
Excellent catalytic result and high poison tolerance.
The nano-particle catalysts such as cheap pallium-on-carbon, palladium, by the pattern of carrier and the change of physicalchemical structure property
Change and obtain excellent electrocatalytic oxidation activity, always is the hot spot of research.Graphene is one kind by sp2Hydbridized carbon atoms group
At two-dimensional atomic crystal.Since its brilliant electronic conduction ability and big specific surface area become ideal carrier material.Pt/
GO composite material has much as the document report of fuel-cell catalyst, but most of material uniformities are poor, Pt nano particle
The problems such as bad dispersibility, particle size range is wider, is generally existing, to limit the ability of catalyst Oxidation of Methanol.
Polyethyleneimine (PEI) is also known as polyethylene imine, is a kind of water soluble polymer cationic polymer.Graphene
The PEI composite material of doping has extensive research as catalytic carrier and bio-carrier.The organic compatibility of graphene oxide is very
By force, multi-solvents, especially water are dissolved in, its surface there are many groups, and such as hydroxycarboxyl group and epoxy group, these groups are deposited
A large amount of chemical reaction site is being provided, is providing prerequisite for the chemical modification of graphene oxide, graphene oxide can
To be grafted by bonding action of building together, hydrogen bond, intermolecular force, π-π superposition etc. and polymer, point of polymer is improved
Dissipate property；Meanwhile the huge specific surface area of graphene oxide, can be used as carrier support, improve high molecular polymer load capacity,
Dispersion performance, thermal conductivity and mechanical performance.
Summary of the invention
In order to solve the problems in the existing technology, the present invention provides a kind of electricity for direct alcohol fuel cell
Chemical sensor and its preparation method and application.
The first purpose of the invention is to provide the preparation methods of the catalyst carrier for direct alcohol fuel cell, use
Ultrapure water prepares graphene oxide dispersion and aq. polyethyleneimine, adds graphene oxide dispersion under stirring
Enter into aq. polyethyleneimine, continue stirring 60-72 hours, be then separated by solid-liquid separation, leave precipitating, washed to
It is neutral and dry, graphene oxide-polyethyleneimine composite material is obtained, addition ultrapure water progress ultrasound is dispersed into water-soluble
Glue；
Preferably, the concentration of the graphene oxide dispersion is 1mgmL-1, pH 10；
Preferably, the concentration of the aq. polyethyleneimine is 3mgmL-1；
Preferably, the drying condition are as follows: vacuum oven is dry, and 60 DEG C, 6 hours；
Preferably, be added ultrapure water carry out ultrasound graphene oxide-polyethyleneimine composite material is dispersed into it is water-soluble
When glue, the additional amount and graphene oxide dispersion of ultrapure water and the volume ratio of polyethylenimine solution are 7:20:24.
Ultrapure water, graphene oxide dispersion and polyethylenimine solution are in above-mentioned volume ratio, the catalysis that is prepared
The effect of agent carrier catalysis methanol is best.
It is to use a second object of the present invention is to provide a kind of catalyst carrier for direct alcohol fuel cell
State what preparation method was prepared.
Third object of the present invention is to provide the preparation method of the electrochemical sensor for direct alcohol fuel cell,
Cleaned basal electrode is put into above-mentioned catalyst carrier and carries out electro-deposition, then placed into potassium chloroplatinate aqueous solution
Carry out electro-deposition.
Subsequent electrochemical reaction electrolyte addition is 0.1M KC1, so considering not introduce other interfering ions
In the case of, use potassium chloroplatinate.
Common electrochemical working electrode has carbon paste electrode, glass-carbon electrode, platinum electrode, Ti electrode, other metal electrodes etc..
The characteristics of glass-carbon electrode is to conduct electricity very well, and chemical stability is high, and coefficient of thermal expansion is small, and quality is hard, and air-tightness is good, and potential is applicable in
Range is wide, and surface cleaning is easier to, and price is also not expensive, therefore, the preferred glass-carbon electrode of basal electrode.
Electro-deposition is carried out preferably, cleaned basal electrode is put into catalyst carrier as claimed in claim 2
When, it is that cyclic voltammetry scan is carried out in the range of 0.1V to 0.9V, scanning speed 100mVs–1, 30 circle of scanning；
Preferably, described be put into potassium chloroplatinate aqueous solution carries out electro-deposition, be within the scope of -0.25V to 0.5V into
Row cyclic voltammetry scan, scanning speed 100mVs–1, 30 circle of scanning.
Fourth object of the present invention is to provide a kind of electrochemical sensor for direct alcohol fuel cell, be on
State what preparation method was prepared.
Fifth object of the present invention is to provide above-mentioned electrochemical sensors in catalysis oxidation methanol or quantitative detection solution
Application in middle methanol content.
Preferably, the application is in three-electrode system, using the electrochemical sensor described in claim 5 as work
The sulfuric acid buffer solution containing methanol is added, with 25-500mVs in electrode-1Sweep speed carry out cyclic voltammetry scan.
Preferably, the concentration of the methanol is 0.02mol/L-2.0mol/L.
Sixth object of the present invention is to provide a kind of direct alcohol fuel cells, including with the electricity described in claim 5
Chemical sensor is the three-electrode system and working solution of working electrode；The working solution is the sulfuric acid buffer solution containing methanol.Directly
Connecing alcohol fuel battery further includes other the necessary components for constituting battery, these components are well known to those skilled in the art,
This is not repeated one by one.
Graphene oxide and polyethyleneimine amino-group doping are formed intercalation composite material, obtain catalyst carrier by the present invention, and
It is deposited onto glassy carbon electrode surface, then electro-deposition catalyst platinum, obtains electrochemical sensor, carried out using three-electrode system
The catalytic oxidation of methanol, catalytic effect are significant.It is detected using methanol solution of the electrode to various concentration, discovery catalysis
It aoxidizes peak height and methanol concentration is in a linear relationship, linear good when methanol concentration is between 0.02M-2.0M, R2=0.996,
It can be used as detection of the electrochemical sensor for methanol in solution.
Graphene oxide prepared by the present invention/polyethyleneimine intercalation composite material does not precipitate in aqueous solution, is good
Suspension dispersion, good environment can be provided for the load of platinum grain.As seen from Figure 7: the platinum grain of load point
Scattered property is good, and granular size is uniform.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the outside drawing of GO and the GO-PEI compound hydrosol.
Fig. 2 is the infrared spectrum of the compound hydrosol of GO-PEI.
Fig. 3 is graphene oxide-polyethyleneimine amine compound X-ray diffractogram.
Fig. 4 is graphene oxide and graphene oxide-polyethyleneimine intercalation composite material Raman spectrogram.
Fig. 5 is graphene oxide-polyethyleneimine composite material transmission electron microscope picture.
Fig. 6 is graphene oxide-polyethyleneimine composite material scanning electron microscope (SEM) photograph.
Fig. 7 is graphene oxide-polyethyleneimine composite material Supported Pt Nanoparticles scanning electron microscope (SEM) photograph.
Fig. 8 is different sensors in KC1 containing the 0.1M, [Fe (CN) containing 2mM6]3–/4–In the 0.1M phosphate buffer of (1:1)
CV figure.
Fig. 9 is bare electrode and different sensors in KC1 containing 0.1M and 2mM [Fe (CN)6]3–/4–The 0.1M phosphoric acid of (1:1) is slow
Rush the AC impedance figure in solution.
Figure 10 is i-t curve of the different sensors in the 0.5M sulfuric acid solution of the methanol containing 1M.
Figure 11 is the CV curve of different modifying material sensors catalysis methanol in sulfuric acid buffer solution.
Figure 12 is the cyclic voltammetry curve of sensor catalysis methanol in sulfuric acid buffer solution.
Figure 13 is oxidation peak current and sweeps speed (25-500mVs-1) linear relationship.
Figure 14 is the methanol solution cyclic voltammetry curve figure on a sensor of various concentration.
Figure 15 is oxidation peak current and concentration linear relationship figure.
Specific embodiment
Embodiment below facilitates a better understanding of the present invention, but does not limit the present invention.Experiment in following embodiments
Method is unless otherwise specified conventional method.Test material as used in the following examples is unless otherwise specified city
It sells.
Embodiment 1
Chemical reagent and equipment:
Graphene oxide, polyethyleneimine, dehydrated alcohol, hydrochloric acid, sodium hydroxide, ultrapure water.
PHS-3B precision pH meter, eddy mixer, centrifuge, ultrasonic cleaner.
Buffer solution: 0.1molL-1Potassium dihydrogen phosphate, 0.1molL-1The sodium hydroxide solution, [Fe containing 2mM
(CN)6]3–/4–0.1M phosphate buffer.
1. the preparation of graphene oxide-polyethyleneimine composite material
Polyethyleneimine (PEI) is also known as polyethylene imine, is a kind of part branch containing a large amount of primary amine, secondary amine, tertiary amine
Chain macromolecular water-soluble cationic polymer.The organic compatibility of graphene oxide is very strong, dissolves in multi-solvents, especially
There are many groups on water, its surface, and such as hydroxycarboxyl group and epoxy group, the presence of these groups provides a large amount of chemical reaction position
Point provides prerequisite for the chemical modification of graphene oxide, graphene oxide can by Covalently attached interaction, hydrogen bond,
Intermolecular force, π-π superposition etc. are grafted with polymer, improve the dispersibility of polymer；Meanwhile graphene oxide is huge
Specific surface area, can be used as carrier support, improve load capacity, dispersion performance, thermal conductivity and the machinery of high molecular polymer
Performance.
The present invention uses simple method, is tied using the polar group (amino) and hydrophobic group (vinyl) of polyethyleneimine
Structure and amino can be reacted with carboxyl generates hydrogen bond, ionic bond, the performance of covalent bond, is allowed to be doped with graphene oxide,
Form the hydrosol intercalation composite material of molecular structure solid.Method particularly includes:
There is the graphene oxide dispersion of good dispersion, concentration 1mgmL with ultrapure water preparation-1, with 0.1M's
Sodium hydroxide adjusts pH to 10.It is simultaneously 3mgmL with ultrapure water compound concentration-1Polyethyleneimine (PEI) aqueous solution.Room temperature
20ml graphene oxide dispersion is added dropwise in 24ml polyethylenimine solution in the case where magnetic agitation, liquor capacity ratio
For 1:1.2, state is kept stirring after adding 72 hours.Then lead to the method for excessive speeds centrifugation graphene oxide-polyethylene
Imines compound separates (parameter of noncentricity 10000r/min, 20min) from mixed liquor, gives up supernatant, leaves precipitating, use is secondary
Deionized water is washed repeatedly to neutral and drying, and drying means can use the conventional method of this field, as long as reaching dry
Dry effect, such as the drying condition that the present embodiment uses are as follows: vacuum oven is dry, 60 DEG C, 6 hours, obtains opposite
Pure graphene oxide-polyethyleneimine (GO-PEI) composite material.Finally pure GO-PEI composite material 7ml is surpassed
Pure water ultrasonic disperse is at the hydrosol, ultrasound condition are as follows: 40KHz, 200W, ultrasonic 30min.
If Fig. 1 is shown, compared with graphene oxide, GO-PEI composite material prepared by the present invention is a kind of uniformly mixed
Colloidal materials.
Fig. 1 is the outside drawing of GO and the GO-PEI compound hydrosol.Wherein, left side GO, right side GO-PEI.
The graphene oxide being prepared-polyethyleneimine composite material is characterized, specific as follows:
(1) Fig. 2 is the infrared spectrum of the compound hydrosol of GO-PEI.
As seen from Figure 2:
The characteristic absorption band of graphene oxide O-H is corresponding in 3407cm-1, peak value 2929cm-1And 2861cm-1It is CH2And CH
It is asymmetric stretch and symmetric vibration, the stretching vibration of carboxyl C=O is in 1729cm-1, the stretching vibration of C-OH is in 1218cm-1,
The deformation vibration of O-H is in 1399cm-1And the vibration of C-O is in 1052cm-1, 856cm-1The spike that place observes may be C-H's
Flat out-of-plane vibration.GO-PEI composite material C=O characteristic peak disappears.Vibration is in 2923cm-1And 2834cm-1It is attributed to CH2And CH,
This shows that C=C double bond opening is changed into CH2And CH, and carboxyl decreases, and is changed into CH2OH.However, C-N is extended in
1230cm-1And 1113cm-1It is obvious.1432cm-1And 1113cm-1The peak value that place observes is attributed to the fact that plane internal vibration.
Polyethyleneimine is successfully inserted into graphene oxide to IR Characterization as the result is shown, forms GO-PEI intercalation composite material.
(2) Fig. 3 is graphene oxide-polyethyleneimine amine compound X-ray diffractogram.
As seen from Figure 3:
In the XRD diagram of GO-PEI compound, at 2 θ=24.08 °, still there is 002 crystallographic plane diffraction peak of graphite, but the peak
Peak shape is wider, peak intensity is weaker.Since document report says that the decrease of (002) crystallographic plane diffraction peak or disappearance can illustrate graphite or stone
The ordered structure of black oxide has been destroyed.So the insertion of PEI causes one to the crystallization degree of graphite in this experiment
Fixing is rung but there is no the orders for destroying graphite crystalline structure completely.If measuring the 2 θ value of angle of XRD, Prague is utilized
Equation 2d sin θ=n λ, so that it may calculate the piece interlamellar spacing of adjacent two panels graphene oxide or derivatives thereof, usual 2 θ value indirectly
Smaller, piece interlamellar spacing is bigger, and vice versa.The 2 θ values of GO do not have diffraction maximum appearance at 10.5 in figure, this illustrates graphite oxide
Alkene piece interlamellar spacing further increases, and proves that GO-PEI intercalation composite material synthesizes successfully from side.
(3) Fig. 4 is graphene oxide and graphene oxide-polyethyleneimine intercalation composite material Raman spectrogram.
Raman spectrum is that the scattering spectrum based on Raman scattering effect, by analyzing different incident light frequencies obtains
To the method for the information such as molecular vibration and rotation, it is to be found by scientist C.V. Raman (Raman), is now widely used for point
The research of minor structure.
As seen from Figure 4:
The peak D and the peak G of GO is located at 1367cm-1And 1605cm-1Place, the peak D and the peak G of GO/PEI is located at
1353cm-1And 1597cm-1, significant change, I has occurred in Raman map peak value after GO modifies PEID/IGIt is worth from original 0.8950
1.0374 are risen to, since the peak D reflects sp2Hydridization defect or sp3Hybrid structure (positive tetrahedron structure), and the peak G is long-chain or ring
In sp2Carbon atom generates extensional motion, therefore is used to reflect the degree of order and symmetry of material.ID/IGRatio is bigger, table
The number in bright disadvantage site is more.Data show the sp3 hydbridized carbon atoms number ratio sp for illustrating GO/PEI2More, the surface of hydridization
Defect is more than GO and the degree of disorder is bigger, therefore sp3 hydbridized carbon atoms quantity rises, and sp2Hydbridized carbon atoms quantity is decreased obviously.
(4) Fig. 5 is graphene oxide-polyethyleneimine composite material transmission electron microscope picture.Wherein, A, B, C, D are respectively
Scale is under 5-200nm scale, graphene oxide-polyethyleneimine amine compound transmission electron microscope picture.
As seen from Figure 5:
A figure graphene oxide layer has apparent fold, and B schemes, is distributed with much in the layer structure of C figure graphene oxide
Fold, and three-dimensional sense is very strong, there are gauffers and crimp at laminar graphene oxide edge, this may be due to single layer oxygen
Caused by the inherent thermal stress of graphite alkene.The graphene oxide of lamella and cotton-shaped PEI are adjoining in D figure, but are individually present.
(5) Fig. 6 is graphene oxide-polyethyleneimine composite material scanning electron microscope (SEM) photograph.Wherein, A and B figure is amplification
The scanning electron microscope (SEM) photograph of the 5000 times and 30000 times lower electrode modification GO-PEI compound hydrosols.
As seen from Figure 6:
There is apparent flower-shaped pleated structure after being doped with PEI in the graphene oxide of lamelliform.
2. the preparation of graphene oxide-polyethyleneimine composite material sensor (i.e. Pt/GO-PEI sensor)
Firstly, cleaning glass-carbon electrode: successively using 1.0,0.3,0.05 μm of aluminum oxide polishing powder to be thrown glass-carbon electrode
Light processing, then the ultrasound 2min in ultrapure water and ethyl alcohol respectively, makes into mirror surface with ultrapure water, then in the sulfuric acid of 0.5M
Activated electrode 10min, scanning speed 100mVs are scanned with cyclic voltammetry in solution–1, scanning range -0.5V to+1.2V,
After voltammogram to be recycled is stablized, taking-up is cleaned with ultrapure water, is dried with nitrogen dry rear spare.
Then, it prepares sensor: cleaned glass-carbon electrode is put into 10mL graphene oxide-poly- second prepared by step 1
In the alkene imines compound hydrosol, cyclic voltammetry scan, scanning speed 100mVs are carried out in 0.1V to 0.9V range–1,
Then 30 circle of scanning uses ultrapure water, nitrogen drying.Continue to be placed on electrode in the potassium chloroplatinate aqueous solution of 3mM, in -0.25V
Cyclic voltammetry scan, scanning speed 100mVs are carried out within the scope of to 0.5V–1, 30 circle of scanning, then simultaneously with ultrapure water
It is dried with nitrogen.
Fig. 7 is graphene oxide-polyethyleneimine composite material Supported Pt Nanoparticles scanning electron microscope (SEM) photograph.
As seen from Figure 7:
A large amount of Pt nano particle has been inlayed in graphene oxide-polyethyleneimine composite skin.By supported platinum nano
The GO-PEI modification sensor surface of particle carries out EDS elemental analysis, it is found that the total load amount atomic percent of Pt accounts for 1.03%.
The electrochemical behavior of 3.Pt/GO-PEI sensor
(1) with [Fe (CN)6]3–/4–For probe molecule, with cyclic voltammetry Electrode electrochemical behavior.Fig. 8 is difference
Sensor is in KC1 containing the 0.1M, [Fe (CN) containing 2mM6]3–/4–CV figure in the 0.1M phosphate buffer of (1:1), sweeping speed is
100mV·s-1.Wherein, a:Pt/GO-PEI modifies sensor, and b:Pt modifies sensor, and c:GO-PEI modifies sensor, d: naked electricity
Pole.
As seen from Figure 8:
Compared with bare electrode, sensor peak current increases, and spike potential is shuffled.That is decorative layer can change
The electron transfer rate of probe molecule.The insertion of PEI makes the surface of graphene oxide form a large amount of fold, and material is made to have height
Specific surface area, it is possible to provide more reactivity sites.In Fig. 8, the anodizing reduction peak current of GO-PEI is only modified
It is less than bare electrode instead, this may is that the non-conductive property due to PEI hinders the transmitting of electronics.But Pt nano particle is modified
Electrode is increased slightly redox peaks due to the unique catalytic action of noble metal.Only when Pt/GO-PEI collective effect,
Electrode shows excellent electro-chemical activity, and peak current obviously increases.
(2) AC impedance figure be using sine wave potential signal as expression way, can effective detection sensor surface chemistry
The electrochemical measuring technology of change procedure and conductive process, abbreviation EIS.The present invention is with [Fe (CN)6]3–/4–(1:1) is electrochemistry
Probe applies constant voltage to working electrode, draws ac impedance spectroscopy.Concentration polarization is negligible when positioned at high frequency region, electrification
It learns reaction and belongs to rate-determining steps, half circular diameter is equivalent to electrode surface electron transmission resistance.Concentration polarization is not when positioned at low frequency range
It can ignore, electroactive material redox diffusion coefficient can be deduced by the intercept of straight line.Therefore high frequency region semicircle
Diameter is approximately equal to the impedance value of electron transmission.
Fig. 9 is bare electrode and different sensors in KC1 containing 0.1M and 2mM [Fe (CN)6]3–/4–The 0.1M phosphoric acid of (1:1) is slow
Rush the AC impedance figure in solution.Wherein, a:Pt/GO-PEI modifies sensor, b:GO-PEI modifies sensor, c: bare electrode,
D:GO modifies sensor, e:Pt/GO modifies sensor.
As seen from Figure 9:
Impedance diagram is approximately straight line after the modification of bare glassy carbon electrode Pt/GO-PEI composite material, shows electrode to [Fe
(CN)6]3–/4–Probe molecule shows that lower resistance, electrode surface chemically react quickly, it was demonstrated that electricity can be improved in the composite material
Sub- delivery rate.But simple modification GO cannot reach effect, this may be to hinder electrification since GO is not reduced
Learn reaction.But in the presence of the PEI, one side PEI can be used as reducing agent reduction GO, another aspect PEI and GO be mixed to form it is slotting
Layer structure can change material morphology and electrochemical properties, achieve the effect that collaboration optimization.Sensor has more preferably than bare electrode
Electro-chemical activity, electrode modified material is a kind of outstanding conductive material and accelerates electronics in the transmitting of electrode surface.
(3) chronoamperometry can be used to assess the stability of electrode material electrocatalytic properties and electrode.
Test system is 0.5M sulfuric acid, 1.0M methanol, initial potential 600mV, testing time 400s.
Figure 10 is i-t curve of the different sensors in the 0.5M sulfuric acid solution of the methanol containing 1M.Wherein, a:Pt/GO-PEI
Sensor, b:Pt-PEI sensor, c:Pt/GO sensor, d: bare electrode.
As seen from Figure 10:
The electrode activity of GO-PEI modification and supporting Pt nano particle is significantly larger than other electrodes, which has excellent
Methanol electro catalytic activity.
(4) electrochemical behavior of methanol on a sensor in different supporting electrolytes is studied.Specific medium has: NH3-
NH4Cl、NaHPO4-NaH2PO4Buffering, KH2PO4- NaOH buffering, HAc-NaAc buffering, KCl-HCl buffering, KNO3-HNO3Buffering,
HClO4Buffering and H2SO4Buffering.The results show that oxidation peak current value is maximum in sulfuric acid medium, therefore select 0.5M sulfuric acid
As supporting electrolyte.
(5) Figure 11 is the CV curve of different modifying material sensors catalysis methanol in sulfuric acid buffer solution, sweeps speed
100mV·s-1, the 0.5M sulfuric acid solution of the methanol containing 1M.Wherein, a:Pt/GO-PEI modifies sensor, b:Pt-PEI modification sensing
Device, c:Pt/GO modify sensor, d: bare electrode.
As seen from Figure 11:
For bare electrode to methanol without response, graphene oxide-loaded Pt electrode electro Chemical responds also very low, the electricity of PEI supporting Pt
Chemical response is slightly higher, but responds best still Pt/GO-PEI composite material sensor.GO-PEI is presumably due to provide greatly
Specific surface area and binding site, conducive to the load of metallic, while PEI has certain reducing power to metal, more mentions
The high catalytic capability of Pt, furthermore PEI viscosity is larger, be also material can adhesion in electrode surface, keep the stability of sensor
Important function is played.
The dynamic behavior of 4.Pt/GO-PEI sensor
It is to electrode, using silver/silver chloride electrode as reference with platinum electrode using Pt/GO-PEI sensor as working electrode
Electrode forms three-electrode system, in the 0.5M sulfuric acid buffer solution of the methanol containing 1M, cyclic voltammetry scan is carried out, wherein scanning
Speed a-i is followed successively by 25,50,75,100,150,200,250,300,350,400,450,500mVs-1.2 He of the result is shown in Figure 1
Figure 13.
Figure 12 is the cyclic voltammetry curve of Pt/GO-PEI sensor catalysis methanol in sulfuric acid buffer solution.
The further catalysis oxidation behavior of research methanol on a sensor, using following for different scanning speed operation sensor
Ring voltammetric scan.Peak current increases as sweep speed increases, and sweeps fast 25-500mVs-1Between when, oxidation peak current and current potential
Sweep speed is linear related (see Figure 13), Ipa (μ A)=0.1622v+39.05 (mVs-1, R2=0.997), this illustrates first
The electrode process of alcohol on a sensor is the reaction process of adsorption.
Figure 13 is oxidation peak current and sweeps speed (25-500mVs-1) linear relationship.Wherein, buffer solution is first containing 1.0M
The 0.5M sulfuric acid solution of alcohol.
The methanol oxidation efficiency of 5.Pt/GO-PEI sensor
It is to electrode, using silver/silver chloride electrode as reference with platinum electrode using Pt/GO-PEI sensor as working electrode
Electrode forms three-electrode system, is sweeping fast 100mVs-1, circulation volt is carried out in the 0.5M sulfuric acid solution of the methanol containing various concentration
Peace scanning, scanning result and equation of linear regression are shown in Figure 14 and Figure 15 respectively.
Figure 14 is the methanol solution cyclic voltammetry curve figure on a sensor of various concentration, wherein a-h methanol concentration difference
It is 0.02M, 0.05M, 0.1M, 0.25M, 0.5M, 0.6M, 1.0M, 2.0M.
Figure 15 is oxidation peak current and concentration linear relationship figure.
As seen from Figure 14: oxidation peak current gradually rises with the increase of methanol concentration.
As seen from Figure 15: corresponding equation of linear regression is Ipa (μ A)=5.91+58.02C (molL-1, R2=
0.996)。
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (9)
1. the preparation method of the catalyst carrier for direct alcohol fuel cell, it is characterised in that: prepared and aoxidized with ultrapure water
Graphene oxide dispersion is added to polyethyleneimine under stirring by graphene dispersing solution and aq. polyethyleneimine
In aqueous solution, continue stirring 60-72 hours, be then separated by solid-liquid separation, leave precipitating, is washed to neutral and drying, obtained
To graphene oxide-polyethyleneimine composite material, ultrapure water progress ultrasound is added and is dispersed into the hydrosol；
Preferably, the concentration of the graphene oxide dispersion is 1mgmL-1, pH 10；
Preferably, the concentration of the aq. polyethyleneimine is 3mgmL-1；
Preferably, the drying condition are as follows: vacuum oven is dry, and 60 DEG C, 6 hours；
Preferably, when graphene oxide-polyethyleneimine composite material is dispersed into the hydrosol by addition ultrapure water progress ultrasound,
The additional amount and graphene oxide dispersion of ultrapure water and the volume ratio of polyethylenimine solution are 7:20:24.
2. a kind of catalyst carrier for direct alcohol fuel cell is prepared with preparation method described in claim 1
It obtains.
3. the preparation method of the electrochemical sensor for direct alcohol fuel cell, it is characterised in that: by cleaned substrate
Electrode, which is put into catalyst carrier as claimed in claim 2, carries out electro-deposition, then places into potassium chloroplatinate aqueous solution and carries out
Electro-deposition；Preferably, the concentration of the potassium chloroplatinate aqueous solution is 3mM.
4. preparation method according to claim 3, it is characterised in that: cleaned basal electrode is put into claim 2
It is that cyclic voltammetry scan is carried out in the range of 0.1V to 0.9V when carrying out electro-deposition in the catalyst carrier, scanning speed
Degree is 100mVs–1, 30 circle of scanning；
Preferably, described be put into potassium chloroplatinate aqueous solution carries out electro-deposition, it is to be followed within the scope of -0.25V to 0.5V
Ring voltammetric scan, scanning speed 100mVs–1, 30 circle of scanning.
5. a kind of electrochemical sensor for direct alcohol fuel cell is the preparation method described in claim 3 or 4
It is prepared.
6. the answering in methanol content in catalysis oxidation methanol or quantitative detection solution of electrochemical sensor described in claim 5
With.
7. application according to claim 6, it is characterised in that: the application is in three-electrode system, with claim 5
The electrochemical sensor is working electrode, the sulfuric acid buffer solution containing methanol is added, with 25-500mVs-1Scanning speed
Rate carries out cyclic voltammetry scan.
8. application according to claim 6, it is characterised in that: the concentration of the methanol is 0.02mol/L-2.0mol/L.
9. a kind of direct alcohol fuel cell, it is characterised in that: including using the electrochemical sensor described in claim 5 as work
The three-electrode system and working solution of electrode, the working solution are the sulfuric acid buffer solution containing methanol.
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