CN108063266A - A kind of preparation method of the Prussian blue similar object modified electrode of high-performance - Google Patents
A kind of preparation method of the Prussian blue similar object modified electrode of high-performance Download PDFInfo
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- CN108063266A CN108063266A CN201711335243.0A CN201711335243A CN108063266A CN 108063266 A CN108063266 A CN 108063266A CN 201711335243 A CN201711335243 A CN 201711335243A CN 108063266 A CN108063266 A CN 108063266A
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
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Abstract
The invention discloses a kind of preparation methods of the Prussian blue similar object modified electrode of high-performance, are under ultrasound condition, K2Zn3[Fe(CN)6]2•xH2O electrode materials are dissolved in Nafion aqueous solutions, are then modified on glass-carbon electrode, obtain Prussian blue similar object K2Zn3[Fe(CN)6]2•xH2O modified electrodes.Prussian blue similar object K prepared by the present invention2Zn3[Fe(CN)6]2•xH2O has the monocrystalline pros block structure of uniform form, can substantially increase in oxygen evolution reaction（OER）And oxygen reduction reaction（ORR）Etc. electrocatalysis characteristic.So as to be prepared applied to electrode.
Description
Technical field
The present invention relates to technical fields such as electrolysis water, metal-air battery and fuel cells, more particularly to a kind of high-performance
The preparation method of Prussian blue similar object modified electrode.
Background technology
People increasingly pay close attention to energy demand and environmental pollution caused by fossil fuel exhausts, which results in people to many
The strong interest of energy conversion and stocking system particularly reacts field, such as rechargeable metal-air electricity in energy conversion
Pond, fuel cell, lithium ion battery, ultracapacitor.Green and sustainable energy are currently a national research theme.For
Solve the active demand to cleaning and sustainable energy, electro-chemical water decomposition method for generating hydrogen and oxygen is from can be again
The raw energy obtains the environment-friend substitution scheme of clean fuel.However, efficiently the realization of water decomposition is subject to oxygen evolution reaction（OER）It is tight
It hinders again, this is the involved bottleneck half-reaction of multistage proton couple electronic transfer, and dynamics is slow.Therefore explore effective
OER elctro-catalysts be reduce activation barrier, accelerate reaction speed, so as to improve the key request of energy conversion efficiency, therefore
For oxygen evolution reaction（OER）And oxygen reduction reaction（ORR）The research of high activity and high stability elctro-catalyst be still main
It challenges.
It is Prussian blue（PB）It is a kind of ancient electrode material, there is cubic crystal structure.For decades, to battery and super
PB and its derivative in grade capacitor（PBA, metal oxide, metal sulfide etc.）Electrochemical properties carried out many and ground
Study carefully.PB and Prussian blue similar object（PBAs）It is a kind of important multi-nuclear metal cyanide, they have zeolite characteristic, Ke Yi
Alkali metal ion is quickly substituted in aqueous solution, and the metal ion of different valence state can be generated, therefore generates redox reaction.
PB and PBAs is easily prepared because having many advantages, such as excellent electrochemical reversibility, has very big application in terms of electro-catalysis
Potentiality.However, when PB and its PBAs modified electrodes are as electro catalytic electrode material, performance is stablized not enough, and electrode warp is made
After preserving for a long time, performance can change.
The content of the invention
For the more than prior art and defect, it is an object of the invention to propose a kind of Prussian blue similar object of high-performance
（K2Zn3[Fe(CN)6]2•xH2O）The preparation method of the preparation method of modified electrode further improves PBAs modified electrode materials
Stability.
In order to solve the above technical problem, the present invention provides following technical solutions：
A kind of preparation method of the Prussian blue similar object modified electrode of high-performance, specifically includes following steps：
1）Solution A：Divalent zinc salt and PVP (K-30) are dissolved in isopropanol, obtain absolute clear solution；Solution B：It will
K3Fe(CN)6It is dissolved in deionized water and obtains homogeneous solution；
2）Solution B is slowly added into solution A and carries out hydro-thermal reaction, obtains sediment；
3）It is dried after sediment is washed with deionized water and ethyl alcohol to get to white K2Zn3[Fe(CN)6]2•xH2O electrode materials
Material；
4）Under ultrasound condition, K2Zn3[Fe(CN)6]2•xH2O electrode materials are dissolved in Nafion aqueous solutions, are then modified
On glass-carbon electrode, Prussian blue similar object K is obtained2Zn3[Fe(CN)6]2•xH2O modified electrodes.
A kind of preferred embodiment of preparation method as the Prussian blue similar object modified electrode of high-performance of the present invention,
In：The divalent zinc salt is Zn (NO3)2•6H2O、ZnSO4•7H2O or Zn (CH3COO)2•2H2O, the experiment proved that, since this is several
The acid group of kind metal salt institute band is easily sloughed, and is more easy to obtain required product, therefore preferential using these types of metal salt.
A kind of preferred embodiment of preparation method as the Prussian blue similar object modified electrode of high-performance of the present invention,
In：Product morphology is optimal and best performance in order to obtain, and the volume ratio of the isopropanol and deionized water is 1: 1.Be because
Under this ratio, zinc salt, K3Fe(CN)6Etc. can be completely dissolved.
A kind of preferred embodiment of preparation method as the Prussian blue similar object modified electrode of high-performance of the present invention,
In：The divalent zinc salt and K3Fe(CN)6Molar ratio be 3: 2.K under this ratio2Zn3[Fe(CN)6]2•xH2The pattern of O
And better performances, it is because of raw material divalent zinc salt and K under the ratio3Fe(CN)6It can the reaction was complete.
A kind of preferred embodiment of preparation method as the Prussian blue similar object modified electrode of high-performance of the present invention,
In：The temperature conditionss of the hydro-thermal reaction are 80 DEG C -120 DEG C.Through that it is demonstrated experimentally that under this hydrothermal temperature, can synthesize repeatedly
The higher K of well-grown, purity2Zn3[Fe(CN)6]2•xH2O is optimal process conditions.Below or above this temperature model
It encloses, sample topography can change.
A kind of preferred embodiment of preparation method as the Prussian blue similar object modified electrode of high-performance of the present invention,
In：In order to obtain the target product with preferable pattern, the divalent zinc salt and the mass ratio that feeds intake of PVP (K-30) are 1: 20
.The amount of PVP is controlled in experiment discovery, and the amount of PVP is to Prussian blue similar object K2Zn3[Fe(CN)6]2•xH2The pattern of O has larger
Influence, be verified by experiments the Prussian blue similar object have uniform form monocrystalline square structure, if the amount of PVP is tied less
The easy heap of structure square is to together；Amount is more, and square can be deteriorated.
A kind of preferred embodiment of preparation method as the Prussian blue similar object modified electrode of high-performance of the present invention,
Wherein：The Nafion aqueous solutions refer to by H2O、 C2H5The solution of OH and Nafion compositions,
A kind of preferred embodiment of preparation method as the Prussian blue similar object modified electrode of high-performance of the present invention, wherein：
The detailed process modified on glass-carbon electrode includes using the method for coating modifying 5 μ L mixed solutions a diameter of 3 mm's
Clean glassy carbon electrode surface, up to block Prussian blue similar object K after naturally dry2Zn3[Fe(CN)6]2•xH2O modification electricity
Pole.
Principle analysis：
Prussian blue similar object K prepared by the present invention2Zn3[Fe(CN)6]2•xH2O has the monocrystalline pros agllutination of uniform form
Structure can be substantially increased in oxygen evolution reaction（OER）And oxygen reduction reaction（ORR）Etc. electrocatalysis characteristic.It therefore can
It is applied to the technical fields such as electrolysis water, metal-air battery and fuel cell as modified electrode.Oxygen evolution reaction（OER）With
Oxygen reduction reaction（ORR）It is considered as environmentally friendly and reproducible energy resource system.
Advantageous effect possessed by the present invention：
1st, K prepared by the present invention2Zn3[Fe(CN)6]2•xH2O electrode materials are prepared by simple hydro-thermal method.It uses
The cost of raw material is relatively low, and preparation process is simple, easily operated control, is mass produced suitable for serialization, preparation process green ring
It protects.
2nd, through the present invention it is experimentally confirmed that this Prussian blue similar object K2Zn3[Fe(CN)6]2•xH2O has uniform form
Monocrystalline square structure substantially increases the performance in electro-catalysis due to the excellent electrochemistry such as its excellent electrical conductivity
Can, available for electro-catalysis.
3rd, Prussian blue similar object is used in electro-catalysis, is friendly to bad border, free of contamination renewable energy system bad border；
4th, using electron-transport, electronics can be reached on carrier electrode by very thin square block, contribute to the progress of reaction.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing work simply introduce, it should be apparent that, the accompanying drawings in the following description is only some embodiments of the present invention, for
For those of ordinary skill in the art, without having to pay creative labor, it can also be obtained according to these attached drawings
Its attached drawing.Wherein：
Fig. 1 is K prepared by the present invention2Zn3[Fe(CN)6]2•xH2The scanning electron microscope (SEM) photograph of O（SEM）.
Fig. 2 is K prepared by the present invention2Zn3[Fe(CN)6]2•xH2The transmission electron microscope picture of O（TEM）.
Fig. 3 is K prepared by the present invention2Zn3[Fe(CN)6]2•xH2The X-ray diffractogram of O（XRD）.
Fig. 4 is K prepared by the present invention2Zn3[Fe(CN)6]2•xH2The cyclic voltammetry curve figure of O（CV）.
Fig. 5 is K prepared by the present invention2Zn3[Fe(CN)6]2•xH2The linear scan graph of the OER of O.
Fig. 6 is K prepared by the present invention2Zn3[Fe(CN)6]2•xH2The linear scan graph of the ORR of O.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to specific embodiment pair
The specific embodiment of the present invention is described in detail.
Many details are elaborated in the following description to facilitate a thorough understanding of the present invention, still the present invention can be with
Implemented using other different from other manner described here, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is from the limitation of following public specific embodiment.
The present invention provides a kind of preparation method of the Prussian blue similar object modified electrode of high-performance, specifically includes following step
Suddenly：
1）Solution A：Divalent zinc salt and PVP (K-30) are dissolved in isopropanol, obtain absolute clear solution；Solution B：It will
K3Fe(CN)6It is dissolved in deionized water and obtains homogeneous solution；
The divalent zinc salt is Zn (NO3)2•6H2O、ZnSO4•7H2O or Zn (CH3COO)2•2H2O。
The volume ratio of the isopropanol and deionized water is 1: 1.
The divalent zinc salt and K3Fe(CN)6Molar ratio be 3: 2.
The divalent zinc salt and the mass ratio that feeds intake of PVP (K-30) are 1: 20.
2）Solution B is slowly added into solution A and carries out hydro-thermal reaction, obtains sediment；
The temperature conditionss of the hydro-thermal reaction are 80 DEG C -120 DEG C, when the reaction time is 12 small.
3）It is dried after sediment is washed with deionized water and ethyl alcohol to get to white K2Zn3[Fe(CN)6]2•xH2O electrodes
Material.
4）Under ultrasound condition, K2Zn3[Fe(CN)6]2•xH2O electrode materials are dissolved in Nafion aqueous solutions, then
Modification obtains Prussian blue similar object K on glass-carbon electrode2Zn3[Fe(CN)6]2•xH2O modified electrodes.
The Nafion aqueous solutions refer to by H2O、 C2H5The solution of OH and Nafion compositions,
The detailed process modified on glass-carbon electrode includes：5 μ L mixed solutions are modified using the method for coating a diameter of 3
The clean glassy carbon electrode surface of mm, up to block Prussian blue similar object K after naturally dry2Zn3[Fe(CN)6]2•xH2O is modified
Electrode.
Embodiment 1：
Preferred embodiment prepares Prussian blue similar object K2Zn3[Fe(CN)6]2•xH2O：
By 0.0461 g Zn (CH3COO)2•2H2O and 1g PVP (K-30) are dissolved in 20 mL isopropanols, stir 20 min,
Obtain absolute clear solution A.
Under stiring by 0.0461 g K3Fe(CN)6It is dissolved in 20 mL deionized waters and obtains homogeneous solution B.
Solution B is added in solution A, 10 min are stirred at room temperature.When hydro-thermal reaction 12 is small under the conditions of 120 DEG C,
Obtained precipitation is dried after washing 3 times respectively with ethyl alcohol with deionized water to get to Prussian blue similar object K2Zn3[Fe
(CN)6]2•xH2O materials.
Except above-mentioned divalent zinc salt l Zn (CH3COO)2•2H2Zn (NO also can be selected in O3)2•6H2O、ZnSO4•7H2O, through reality
It verifies bright, since the acid group of these types of metal salt institute band is easily sloughed, is more easy to obtain required product, thus it is preferential using these types
Metal salt, but it is not limited only to these types of metal salt.
Prussian blue similar object K2Zn3[Fe(CN)6]2•xH2The feature of O：
To K2Zn3[Fe(CN)6]2•xH2O carries out SEM tests：Fig. 1 is K2Zn3[Fe(CN)6]2•xH2O is in 1 μm and 100 nm sizes
Under electron scanning micrograph, show regular cube block structure.
To K2Zn3[Fe(CN)6]2•xH2O carries out TEM tests：Fig. 2 is K2Zn3[Fe(CN)6]2•xH2The transmission electron microscope picture of O,
It shows that sample is the block structure without apparent hole.
To K2Zn3[Fe(CN)6]2•xH2O carries out XRD tests：Fig. 3 is K2Zn3[Fe(CN)6]2•xH2The x-ray powder of O spreads out
Figure is penetrated, peak can be with base peak to upper, so as to show that synthesized sample is required sample.
The present invention be by one step hydro thermal method synthesize PBAs, it is environmentally protective, it is pollution-free, and synthesize PBAs square blocks compared with
It is thin, so as to be conducive to carry out oxygen evolution reaction, improve electrocatalysis characteristic.
Embodiment 2：
The influence of hydrothermal temperature：
Other conditions with embodiment 1 adjust hydrothermal temperature be respectively 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C,
120 DEG C, 130 DEG C, 140 DEG C, through it is demonstrated experimentally that find temperature at 80-120 DEG C, can synthesize repeatedly well-grown, purity compared with
High K2Zn3[Fe(CN)6]2•xH2O, below or above this temperature range, sample topography can change.Simultaneously in this temperature
Under, the time of hydro-thermal reaction is also greatly reduced.
Embodiment 3：
The influence of solvent ratios：
Other conditions adjust the volume ratio of solvent isopropanol and deionized water with embodiment 1, when discovery ratio is 1: 1, zinc salt,
PVP (K-30) 、K3Fe(CN)6Etc. can be completely dissolved, and solvent does not waste, and side reaction is few.
Embodiment 4
It has also been found that divalent zinc salt and K in experimentation3Fe(CN)6Molar ratio sample topography is directly affected, most
Good ratio divalent zinc salt and K3Fe(CN)6Molar ratio for 3: 2, be because raw material divalent zinc salt and K under the ratio3Fe
(CN)6It can the reaction was complete.
Embodiment 5
It has also been found that control divalent zinc salt and the amount of PVP in PVP (K-30) have final products pattern larger shadow in experimentation
It rings, optimal proportion divalent zinc salt and the mass ratio that feeds intake of PVP (K-30) are about 1: 20, and it is Prussian blue similar to be verified by experiments this
Object has the monocrystalline square structure of uniform form, if the amount of PVP lacks the easy heap of structure square to together；Amount is more, and square can quilt
It destroys.
Embodiment 6：
Prussian blue similar object K2Zn3[Fe(CN)6]2•xH2The preparation of O modified electrodes：
1）By the glass-carbon electrode of a diameter of 3 mm sand paper sanding and polishing for the aluminum oxide suspension for having adsorbed 50 nm.
2）The good glass-carbon electrode of sanding and polishing is successively placed on after being cleaned by ultrasonic 2 minutes in deionized water, in 0.5M KCl+
K3[Fe(CN)6] scan cycle volt-ampere curve in solution, with test electrode whether milled, finally obtain clean glass-carbon electrode, dry in the air
It does with for use.
3）The K that 6 mg steps is taken to prepare2Zn3[Fe(CN)6]2•xH2O is added in by 666 μ L H2O、334 µL C2H5OH and
In the solution of 200 μ L Nafion compositions, mixed solution is made in ultrasound, then by 5 μ L mixed solutions using the method for coating
The clean glassy carbon electrode surface in a diameter of 3 mm is modified, up to block Prussian blue similar object K after naturally dry2Zn3[Fe
(CN)6]2•xH2O electro catalytic electrodes.
5）, configuration electrolyte：
Using KOH as electrolyte, wherein, the concentration of KOH is 1 mol/L.
6）, detecting electrode electrocatalysis characteristic：
By Prussian blue similar object K2Zn3[Fe(CN)6]2•xH2O electro catalytic electrodes are placed in the KOH solution of 1 mol/L and carry out
It measures.
Utilize electrochemical workstation（CHI 760E, Shanghai Chenhua）, the electrode to be measured of preparation is led in advance
Enter in the about electrolyte solution of half an hour nitrogen, under the current potential between -0.75~0.05 V, sweep speed control is 0.1
V/s first carries out cyclic voltammetry scan, and then under the current potential between 0.2~1.2 V, sweep speed control is 5 mV/s, is carried out
Linear voltammetric scan, the OER performances of test sample.
Using electrochemical workstation, the electrode to be measured of preparation is being passed through 1 mol/L of about half an hour oxygen in advance
In KOH solution, sweeping speed as 5 mV/s, voltage range is followed successively by 400 for -0.7~0.1V and rotating speed, 625,900,1225,
1600th, its ORR performance is tested in the case of 2025 rpm.
To sample K2Zn3[Fe(CN)6]2•xH2O carries out CV tests：Fig. 4 is K2Zn3[Fe(CN)6]2•xH2O is in N2With O2 gas
Cyclic voltammetry curve figure under atmosphere, in O2It is lower that we can see an apparent cathode also in 0.68 V (compared with RHE)
Redox peaks are not present in parent peak under N2.
Fig. 5 shows sample K2Zn3[Fe(CN)6]2•xH2The electrode of O modifications is shown in 1 mol/L KOH electrolyte solutions
Good OER performances are shown, are 10 mA cm in current density-2When corresponding voltage be 1.56 V.
Fig. 6 shows sample K2Zn3[Fe(CN)6]2•xH2The electrode of O modifications is shown in 1 mol/L KOH electrolyte solutions
Good ORR performances are shown, the absolute value of limiting current density is bigger and half wave potential is smaller, and performance is better.With
Exemplified by 1600 rpm, limiting current density is -1.4 mA cm in figure-2 , half wave potential is 0.73 V or so.
It should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferable
The present invention is described in detail in embodiment, it will be understood by those of ordinary skill in the art that, it can be to the technology of the present invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of technical solution of the present invention, should all be covered in this hair
Among bright right.
Claims (9)
1. a kind of preparation method of the Prussian blue similar object modified electrode of high-performance, which is characterized in that under ultrasound condition,
K2Zn3[Fe(CN)6]2•xH2O electrode materials are dissolved in Nafion aqueous solutions, are then modified on glass-carbon electrode, obtain Pu Lu
Scholar's indigo plant analog K2Zn3[Fe(CN)6]2•xH2O modified electrodes.
2. the preparation method of the Prussian blue similar object modified electrode of high-performance according to claim 1, which is characterized in that institute
State K2Zn3[Fe(CN)6]2•xH2O electrode materials are to be prepared by the following method and obtain：
1）Solution A：Divalent zinc salt and PVP (K-30) are dissolved in isopropanol, obtain absolute clear solution；Solution B：It will
K3Fe(CN)6It is dissolved in deionized water and obtains homogeneous solution；
2）Solution B is slowly added into solution A and carries out hydro-thermal reaction, obtains sediment；
3）It is dried after sediment is washed with deionized water and ethyl alcohol to get to white K2Zn3[Fe(CN)6]2•xH2O electrode materials
Material.
3. the preparation method of the Prussian blue similar object modified electrode of high-performance according to right wants 2, which is characterized in that described
Divalent zinc salt is Zn (NO3)2•6H2O、ZnSO4•7H2O or Zn (CH3COO)2•2H2O。
4. the preparation method of the Prussian blue similar object modified electrode of high-performance according to right wants 2, which is characterized in that described
The volume ratio of isopropanol and deionized water is 1: 1.
5. the preparation method of the Prussian blue similar object modified electrode of high-performance according to right wants 2, which is characterized in that described
Divalent zinc salt and K3Fe(CN)6Molar ratio be 3: 2.
6. the preparation method of the Prussian blue similar object modified electrode of high-performance according to right wants 2, which is characterized in that described
The temperature conditionss of hydro-thermal reaction are 80 DEG C -120 DEG C.
7. the preparation method of the Prussian blue similar object modified electrode of high-performance according to right wants 2, which is characterized in that described
Divalent zinc salt and the mass ratio that feeds intake of PVP (K-30) are 1: 20.
8. wanting the preparation method of 1 ~ 7 any Prussian blue similar object modified electrode of high-performance according to right, feature exists
In the Nafion aqueous solutions refer to by H2O、 C2H5The solution of OH and Nafion compositions.
9. wanting the preparation method of 1 ~ 7 any Prussian blue similar object modified electrode of high-performance according to right, feature exists
In the detailed process modified on glass-carbon electrode includes：5 μ L mixed solutions are modified using the method for coating a diameter of 3
The clean glassy carbon electrode surface of mm, up to block Prussian blue similar object K after naturally dry2Zn3[Fe(CN)6]2•xH2O is modified
Electrode.
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