CN109718809A - A kind of foamed nickel supported Ag doping cobaltosic oxide nano piece and its preparation method and application - Google Patents
A kind of foamed nickel supported Ag doping cobaltosic oxide nano piece and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of foamed nickel supported Ag doping cobaltosic oxide nano pieces and its preparation method and application.The foamed nickel supported Ag doping cobaltosic oxide nano piece, including nickel foam and growth in situ are in the Ag doping cobaltosic oxide nano piece of foam nickel surface.It is synchronous to realize silver in the doping of cobaltosic oxide nano on piece and growth in situ in nickel foam by the reduction of boron hydrohalogenic acid salt in the aqueous solution existing for polyvinylpyrrolidone (PVP) in the preparation method.The present invention overcomes the prior arts the problems such as material preparation method is complicated, at high cost and electro-catalysis analysis oxygen (hereinafter referred to as: OER) performance is poor, preparation method is simple, economical and efficient, the cobaltosic oxide material morphology of gained Ag doping is controllable, conductivity with higher, long-term stability, lower overpotential simultaneously, with excellent OER performance, it is highly suitable to be applied in electro-catalysis oxygen evolution reaction.
Description
Technical field
The invention belongs to field of inorganic nano material, and in particular to a kind of foamed nickel supported Ag doping cobaltosic oxide nano
Piece and its preparation method and application.
Background technique
Oxygen evolution reaction (OER) is as one of all multiple-energy-source related keyword processes as half-reaction important in electrolysis water
The key component for solving energy crisis, has been obtained extensive concern.But there are still a series of in current research
Insoluble problem, wherein most it is difficult to solve its kinetics, due to OER reaction energy barrier with higher itself,
Be related to 4 electronic processes in the reaction, determine its biggish reaction overpotential, slower reaction rate and it is higher it is economical at
This, therefore OER is the rate-limiting reaction in water splitting processes, efficient elctro-catalyst of the exploitation for OER will undoubtedly promote electrolysis water
Industrialization.
Currently, the oxide nano-particles based on Ir and Ru are applied, but their fancy prices and lower
Cyclical stability makes it not be able to satisfy the growing energy, environmental demand.Therefore, alternative RuO is explored2、IrO2It is cheap,
Efficiently and the OER catalyst of long-time stability is extremely urgent.In recent years, raw material sources are abundant, cheap, the simple mistake of preparation process
Crossing metallic catalyst is popular research object, the quilts such as transition metal hydroxide, oxide, sulfide, nitride, phosphate
Very promising elctro-catalyst as substitution Ir and Ru.Wherein, theory of the Co base oxide elctro-catalyst in alkaline medium
It is upper receive more and more attention with high OER activity and high stability.
However prepared Co oxide electrocatalyst in the prior art, there are conductivity deficiency, catalysis effects in performance
Rate is low, the problems such as in preparation process to be even more that there are synthesis process conditions harsh, operation possibility is poor, energy consumption is high.
Summary of the invention
In view of the deficiencies of the prior art, the first purpose of this invention is to provide a kind of morphology controllable, has high conductance
The foamed nickel supported Ag doping cobaltosic oxide nano piece (Ag-Co of rate, excellent catalytic performance3O4/NF)。
Second object of the present invention is to provide a kind of system of foamed nickel supported porous Ag doping cobalt/cobalt oxide nanometer sheet
Preparation Method, the preparation method is simply controllable, low in cost.
Third object of the present invention is to provide answering for above-mentioned foamed nickel supported porous Ag doping cobalt/cobalt oxide nanometer sheet
With.
To achieve the goals above, the invention provides the following technical scheme:
A kind of foamed nickel supported Ag doping cobaltosic oxide nano piece of the present invention, including nickel foam (NF), and it is in situ raw
It is longer than the Ag doping cobaltosic oxide nano piece (Ag-Co of foam nickel surface3O4)。
It is synchronous to realize that silver is received in cobaltosic oxide the present invention provides foamed nickel supported Ag doping cobaltosic oxide nano piece
The doping of rice on piece and growth in situ are grown up compound by the original position, can be obviously improved before three in nickel foam
Synergistic effect, promoted material property.Simultaneously in application process, due to Ag-Co3O4Nanometer sheet is being steeped by growth in situ
In foam nickel substrate, it can make to generate stronger adhesion strength between foam nickel base and nanometer sheet, effectively prevent nanometer sheet application process
In, the problem that falls off in electrocatalytic reaction.
Preferred scheme, the Ag doping cobaltosic oxide nano piece are porous two-dimensional sheet structure, are evenly distributed on
In nickel foam；Aperture is 0.5-1.5nm, diameter 100-200nm；With a thickness of 1-2nm.
Preferred scheme, in the Ag doping cobaltosic oxide nano piece, Co, Ag, O Elemental redistribution are uniform, in molar ratio
Meter, Ag:Co=1~2:5~50.
Preferred scheme, the nickel foam with a thickness of 1.5mm-2mm.Further preferably 1.7mm.
The present invention provides a kind of preparation method of foamed nickel supported Ag doping cobaltosic oxide nano piece, including walks as follows
It is rapid:
Contain divalent cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, be added nickel foam, first set reaction, obtain
Ag-Co3O4/ NF presoma, then by Ag-Co3O4/ NF presoma is added in boron hydrohalogenic acid salt, and the second secondary response is to get Ag-
Co3O4/NF。
Preparation method of the invention passes through the regulation of PVP, elder generation in each reaction raw materials with PVP jointly existing aqueous solution
Obtain Ag-Co3O4Then the presoma of/NF recycles boron hydrohalogenic acid salt synchronous reducing metal precursor (cobalt source, Yin Yuan) directly steeping
The cobaltosic oxide nano piece of Ag doping is prepared on foam nickel.
That the present invention overcomes transition metal preparation method of nano material in the prior art is complicated, at high cost and electrochemistry is steady
The problems such as qualitative difference, to provide a kind of Cheap highly effective, preparation method easy to operate.The cobaltosic oxide of gained Ag doping
Material morphology is controllable, conductivity with higher, long-term stability, lower overpotential simultaneously, is highly suitable to be applied for electricity
It is catalyzed in oxygen evolution reaction.
In the present invention, the molecular weight ranges that PVP can choose are very wide, and since PVP molecular weight is different, PVP is to each raw material
Viscosity it is different, it is therefore desirable to its mass fraction is regulated and controled, its viscosity is controlled, so that each raw material is preferably attached to bubble
On foam nickel.
Preferred scheme, the molecular weight of the PVP are 40000-60000.Inventors have found that when molecular weight is in the range
When interior, the cobaltosic oxide nano piece stable appearance of gained Ag doping is controllable and has higher catalytic efficiency.
As a further preference, the molecular weight of the PVP is 54000.
Preferred scheme, it is described containing divalent cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, the quality point of the PVP
Number is 1.5%-36%.
Preferred scheme, it is described containing divalent cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, the concentration of divalent cobalt source
For 0.2-0.5mol/L.
Preferred scheme, it is described containing divalent cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, while according to the molar ratio,
Divalent cobalt ion: trivalent cobalt ions=1.6-2.2:1.
In the present invention, Ag-Co is smoothly obtained3O4/ NF needs effectively to control divalent cobalt source, the mole of trivalent cobalt source
The ratio between, for inventor by many experiments, the ratio between mole of cobaltosic oxide can be efficiently generated by just obtaining, and the later period passes through analysis hair
Existing, in the above-mentioned technical solutions, divalent cobalt ion hydrolyzes during the reaction generates cobalt hydroxide, and partial cobalt hydroxide exists
The high cobalt of aqua oxidation is slowly oxidized in air.Trivalent cobalt a part i.e. in cobaltosic oxide derives from trivalent cobalt source cobalt cyanogen
Change potassium, oxidation of a part from cobalt hydroxide in reaction process.
Inventors have found that when the molar ratio of divalent cobalt ion and trivalent cobalt ions is close to 2:1, it can be more smoothly more controllable
Acquisition cobaltosic oxide, and molar ratio, closer to the ratio of 2:1, gained reduzate is purer, as when divalent cobalt ion
It can be nearly pure cobaltosic oxide when ratio is 1.95-2.05:1.As a further preference, described to contain divalent
Cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, according to the molar ratio, divalent cobalt ion: trivalent cobalt ions=1.95-2.05:1.
As it is further preferably, it is described containing divalent cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, by mole
Than meter, divalent cobalt ion: trivalent cobalt ions=2:1.
In the present invention, for the selection of divalent cobalt source, not excessive limitation only needs to ionize out in aqueous solution
The cobalt source of trivalent cobalt ions.
Preferred scheme, the divalent cobalt source are selected from cobalt chloride, cobalt nitrate.
As further preferably, the divalent cobalt source is selected from cobalt nitrate.Inventors have found that when divalent cobalt source be selected from
When cobalt nitrate, on the one hand can react generation precipitating to avoid silver ion and chloride ion, another aspect cobalt nitrate (divalent cobalt)
When cooperating with potassium cobalticyanide (trivalent cobalt), the pattern of the cobaltosic oxide nano piece of gained Ag doping is more preferable, and catalytic efficiency is higher.
Preferred scheme, the trivalent cobalt source are selected from potassium cobalticyanide.Inventors have found that when trivalent cobalt source is selected from potassium cobalticyanide
When, it more can smoothly obtain cobaltosic oxide.
Preferred scheme, the silver source are selected from the silver salt that can ionize out silver ion in aqueous solution.
As further preferably, the silver source is selected from silver nitrate.Inventors have found that when silver-colored source is selected from silver nitrate,
The stable appearance of the cobaltosic oxide nano piece of gained Ag doping is controllable and has greater catalytic efficiency.
Preferred scheme, it is described containing divalent cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, the concentration in silver-colored source is
0.01-0.5mol/L。
As a further preference, described containing divalent cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, silver-colored source it is dense
Degree is 0.1-0.21mol/L.
Since most of silver-colored sources may be decomposed because of illumination, reaction process of the invention is all made of the condition of being protected from light, including but
It is not limited to masking foil shading.
In the above-mentioned technical solutions, the boron hydrohalogenic acid salt can be screened in a wider scope, can be in aqueous solution
The middle boron hydrohalogenic acid salt for ionizing out boron hydracid radical ion.
Preferred scheme, the boron hydrohalogenic acid salt are selected from least one of sodium borohydride, potassium borohydride and lithium borohydride.
As a further preference, the boron hydrohalogenic acid salt is sodium borohydride.
Preferred scheme, the temperature of first set reaction are 25-45 DEG C, and the time of first set reaction is 4-7h.
As further preferably, the temperature of first set reaction is 40 DEG C, and the time of first set reaction is 6h.
Preferred scheme, the temperature of the second secondary response are 70-90 DEG C, and the time of the second secondary response is 3-6h.
As further preferably, the temperature of first set reaction is 80 DEG C, and the time of the second secondary response is 5h.
Inventors have found that the temperature and time provided by further preferred embodiment, can obtain, the four of Ag doping
Co 3 O nanometer sheet pattern is best, and catalytic performance is optimal.
When configuring aqueous solution, the present inventor can the order of addition to raw material freely adjust, can Xiang Shuizhong sequentially add original
Material can also respectively mix the solution after dissolution of raw material.It is controllable and with greater catalytic efficiency in order to prepare stable appearance
The cobaltosic oxide nano piece of Ag doping, as most preferred scheme, specific specific step is as follows: 1. in a brown bottle by divalent
Cobalt source, trivalent cobalt source, silver-colored source and PVP are added to the water abundant dissolution, and nickel foam is added, in 40 DEG C heating water bath 6 hours；2. by boron
Sodium hydride is soluble in water, after completely dissolution to it, takes out step 1. middle gained nickel foam, is put into sodium borohydride solution, then
It is put in 80 DEG C of oil baths and heats 5 hours.
Preferred scheme, by Ag-Co3O4/ NF presoma is added in boron hydrohalogenic acid salt, the second secondary response, takes out gained reaction
Object is dried in vacuo to get Ag-Co3O4/ NF, the vacuum drying temperature are 40-70 DEG C, and the vacuum drying time is 5-10h.
In addition, inventor is also to gained Ag-Co3O4/ NF has carried out the assessment of electro-catalysis oxygen evolution reaction performance, invention human hair
Existing, described Ag-Co3O4/ NF has good electric conductivity, biggish specific surface area and aperture, can be used as electro-catalysis water decomposition
The catalyst of oxygen evolution reaction.
A kind of application of foamed nickel supported Ag doping cobaltosic oxide nano piece of the present invention, the foamed nickel supported silver is mixed
Miscellaneous cobaltosic oxide nano piece, which is applied, is used as oxygen evolution reaction catalysts.
The present inventor is in test Ag-Co3O4Instrument and equipment type and model used in nanometer sheet electrocatalysis characteristic include but
It is not limited to following several: electrochemical workstation, single chamber constant temperature electrolytic cell, platinum electrode, reference electrode, nickel foam working electrode, institute
Electrolyte is alkaline electrolyte, including but not limited to potassium hydroxide, sodium hydroxide, concentration 1mol/L.
The inventors discovered that the Ag-Co3O4Overpotential of the nanometer sheet in electro-catalysis oxygen evolution reaction be low, current density
Greatly, stability is strong, better than generally acknowledged at present noble metal catalyst Ru base and Ir base catalyst.
Compared with the prior art, technical solution of the present invention characteristic:
A kind of what the present invention initiated provide morphology controllable, with high conductivity, excellent catalytic performance it is foamed nickel supported
Ag doping cobaltosic oxide nano piece, the foamed nickel supported Ag doping cobaltosic oxide nano piece, including nickel foam (NF), with
And growth in situ is in the Ag doping cobaltosic oxide nano piece (Ag-Co of foam nickel surface3O4).It is negative that the present invention provides nickel foams
Carry Ag doping cobaltosic oxide nano piece, it is synchronous realize silver cobaltosic oxide nano on piece doping and growth in situ in
Compound by the growth in situ in nickel foam, the synergistic effect that can be obviously improved before three promotes material property.Together
When in application process, due to Ag-Co3O4Nanometer sheet be through growth in situ in foam nickel base, can make foam nickel base and
Stronger adhesion strength is generated between nanometer sheet, is effectively prevent in nanometer sheet application process, the problem that falls off in electrocatalytic reaction.
In preparation process of the invention, Ag-Co is first obtained first with the regulation of PVP3O4/ NF presoma, it is then sharp again
The cobaltosic oxide nano of Ag doping is directly prepared in nickel foam with boron hydrohalogenic acid salt synchronous reducing metal precursor (cobalt source, Yin Yuan)
Piece, especially in reduction process, the present invention cleverly pass through divalent cobalt source, trivalent cobalt source selection and they between
Proportionate relationship, synchronous to realize, silver-colored reduction and the formation of cobaltosic oxide, i.e. a step obtain Ag doping cobaltosic oxide
Nanometer sheet and the load in nickel foam.As can be seen that compared with the existing technology, preparation method of the invention is extremely simple,
Inexpensively, efficiently, be suitble to large-scale production preparation.
Foamed nickel supported Ag doping cobaltosic oxide nano piece provided by the present invention electric conductivity with higher and catalysis
Efficiency, can be applied to electro-catalysis water decomposition oxygen evolution reaction catalysts, and electro-catalysis moisture parses oxygen performance and is better than on the market
RuO2And IrO2Etc. noble metal-based catalysts, and have preferable stability.
The present invention provides a new platform to improve the electrocatalysis characteristic of transition metal nano material.
Detailed description of the invention
Fig. 1 is Ag-Co in embodiment 13O4The SEM of/NF nanometer sheet schemes；
Fig. 2 is Ag-Co in embodiment 13O4The TEM of/NF nanometer sheet schemes；
Fig. 3 is Ag-Co in comparative example 13O4The TEM of nanometer sheet schemes；
Fig. 4 is Co in comparative example 23O4The TEM of/NF nanometer sheet schemes；
Fig. 5 is Ag-Co in embodiment 13O4Co in/NF and comparative example 23O4/ NF chemical property comparison diagram；
Fig. 6 is Ag-Co in embodiment 13O4Ag-Co in/NF and comparative example 13O4Chemical property comparison diagram；
Fig. 7 is Ag-Co in embodiment 13O4/ NF and RuO2/ NF chemical property comparison diagram.
Specific embodiment
Embodiment 1:
Step is 1.: Ag-Co3O4The preparation of/NF nanometer sheet:
Before synthesis, the salt acid soak nickel foam of 1mol/L is first used, ultrasound removes the oxide layer on surface for 15 minutes, then
It is cleaned up with water and ethyl alcohol, is then dried in vacuo.
To 3ml mixed aqueous solution include 0.1gPVP, 0.34mol/L cobalt nitrate, 0.17mol/L potassium cobalticyanide and
Dried nickel foam is added in 0.11mol/L silver nitrate, subsequent 40 degree of heating water baths remain the condition of being protected from light, and reaction 6 is small
When.
Nickel foam is carefully taken out with tweezers, being put into 10ml includes subsequent 80 degree of heating in 3.5mol/L sodium borohydride solution,
Reaction 5 hours.
Nickel foam is carefully taken out with tweezers, is rinsed with deionized water, is put into vacuum oven, 50 degree are dried overnight.I.e.
Obtain Ag-Co3O4/NF。
Fig. 1 is Ag-Co in embodiment 13O4The SEM of/NF nanometer sheet schemes, and Fig. 2 is Ag-Co in embodiment 13O4/ NF nanometer sheet
TEM figure, it can be seen from the figure that Ag doping cobaltosic oxide nano piece be two-dimensional sheet structure, be evenly distributed on nickel foam
On, average diameter 150nm, average thickness 1.5nm, nanometer sheet are porous structure, and aperture is about 1nm, have biggish ratio
Surface area.
Step is 2.: Ag-Co3O4/ NF nanometer sheet electro-catalysis moisture parses oxygen performance test:
With the single compartment electrolytic cell for filling 1mol/L potassium hydroxide solution, three-electrode system is assembled, connects electrochemical workstation,
Debugging is completed.
Specific test process is as follows: IR compensation is carried out to test macro first, then test respectively EIS, CV, LSV,
The parameters such as Tafel slope, ECSA.
From figure 7 it can be seen that Ag-Co3O4/NF nanometer sheet oxygen evolution reaction overpotential is relative to RuO2Low 50mV, and electric current
Density is larger, shows superior electro-catalysis oxygen evolution reaction performance.
Embodiment 2:
Ag-Co3O4/NF nanometer sheet is prepared according to the method for embodiment 1, unlike, silver nitrate molar concentration is
0.01mol/L.Purpose is the influence explored for the ratio of cobalt carbonate and silver to product morphology and performance, the experimental results showed that,
Its electro-catalysis oxygen evolution reaction overpotential is 23mV high relative to embodiment 1, that is, illustrates that its electro-catalysis oxygen evolution reaction overpotential is slightly above
Embodiment 1, catalytic performance are slightly below embodiment 1.
Embodiment 3:
Ag-Co3O4/NF nanometer sheet is prepared according to the method for embodiment one, unlike, silver nitrate molar concentration is
0.21mol/L.Purpose is the influence in order to explore the ratio of cobalt carbonate and silver to product morphology and performance, the experimental results showed that,
Its electro-catalysis oxygen evolution reaction overpotential is 15mV high relative to embodiment 1, that is, illustrates that its electro-catalysis oxygen evolution reaction overpotential is slightly above
Embodiment 1 illustrates that its electro-catalysis oxygen evolution reaction overpotential is slightly above embodiment 1, and catalytic performance is slightly below embodiment 1.
Embodiment 4:
Ag-Co3O4/NF nanometer sheet is prepared according to the method for embodiment one, unlike, slightly change divalent cobalt ion and three
The molar ratio of valence cobalt ions is controlled in divalent cobalt ion: trivalent cobalt ions=1.95:1.It is by the concentration of cobalt nitrate
0.3315mol/L, in order to explore influence of the ratio of divalent cobalt ion and trivalent cobalt ions to product property, experiment knot
Fruit shows that its electro-catalysis oxygen evolution reaction overpotential is 8mV high relative to embodiment 1, that is, illustrates its electro-catalysis oxygen evolution reaction overpotential
Slightly above embodiment 1, catalytic performance are slightly below embodiment 1.
Embodiment 5:
Ag-Co3O4/NF nanometer sheet is prepared according to the method for embodiment one, unlike, slightly change divalent cobalt ion and three
The molar ratio of valence cobalt ions is controlled in divalent cobalt ion: trivalent cobalt ions=2.05:1.It is by the concentration of cobalt nitrate
0.3485mol/L, in order to explore influence of the ratio of divalent cobalt ion and trivalent cobalt ions to product property, experiment knot
Fruit shows that its electro-catalysis oxygen evolution reaction overpotential is 11mV high relative to embodiment 1, that is, illustrates its electro-catalysis oxygen evolution reaction overpotential
Slightly above embodiment 1 illustrates that its electro-catalysis oxygen evolution reaction overpotential is slightly above embodiment 1, and catalytic performance is slightly below embodiment 1.
Embodiment 6:
Ag-Co3O4/NF nanometer sheet is prepared according to the method for embodiment one, unlike, change the additional amount of PVP, controls
The quality of PVP is 1g.Purpose is the influence in order to explore the mass fraction of PVP to product morphology and performance, the experimental results showed that,
Pattern is shown slightly irregularly relative to embodiment 1, and electro-catalysis oxygen evolution reaction overpotential is 16mV high relative to embodiment 1, that is, is illustrated
Its electro-catalysis oxygen evolution reaction overpotential is slightly above embodiment 1, and catalytic performance is slightly below embodiment 1.
Comparative example 1:
Step is 1.: Ag-Co3O4The preparation of nanometer sheet:
Configure 3ml mixed aqueous solution include 0.1gPVP, 0.34mol/L cobalt nitrate, 0.17mol/L potassium cobalticyanide and
0.11mol/L silver nitrate, subsequent 40 degree of heating water baths remain the condition of being protected from light, and react 6 hours.
Under intense agitation, by above-mentioned reaction solution be slowly added to 250ml include 3.5mol/L sodium borohydride solution in,
Reaction 5 hours.
It is centrifugated product, and is cleaned repeatedly with deionized water, is put into vacuum oven, 50 degree are dried overnight.
Step is 2.: Ag-Co3O4Nanometer sheet electro-catalysis moisture parses oxygen performance test:
With the single compartment electrolytic cell for filling 1mol/L potassium hydroxide solution, three-electrode system is assembled, connects electrochemical workstation,
Debugging is completed.
Specific test process is as follows: IR compensation is carried out to test macro first, then test respectively EIS, CV, LSV,
The parameters such as Tafel slope, ECSA.
From fig. 6, it can be seen that its electro-catalysis oxygen evolution reaction overpotential is 35mV high relative to embodiment 1, current density is smaller,
Therefore its catalytic performance is lower than embodiment 1.
Comparative example 2:
Step is 1.: Co3O4The preparation of/NF nanometer sheet:
Before synthesis, the salt acid soak nickel foam of 1mol/L is first used, ultrasound removes the oxide layer on surface for 15 minutes, then
It is cleaned up with water and ethyl alcohol, is then dried in vacuo.
It is dry comprising being added in 0.1gPVP, 0.34mol/L cobalt nitrate, 0.17mol/L potassium cobalticyanide to 3ml mixed aqueous solution
Dry good nickel foam, subsequent 40 degree of heating water baths remain the condition of being protected from light, and react 6 hours.
Nickel foam is carefully taken out with tweezers, being put into 10ml includes subsequent 80 degree of heating in 3.5mol/L sodium borohydride solution,
Reaction 5 hours.
Nickel foam is carefully taken out with tweezers, is rinsed with deionized water, is put into vacuum oven, 50 degree are dried overnight.
Step is 2.: Co3O4/ NF nanometer sheet electro-catalysis moisture parses oxygen performance test:
With the single compartment electrolytic cell for filling 1mol/L potassium hydroxide solution, three-electrode system is assembled, connects electrochemical workstation,
Debugging is completed.
Specific test process is as follows: IR compensation is carried out to test macro first, then test respectively EIS, CV, LSV,
The parameters such as Tafel slope, ECSA.
From fig. 5, it can be seen that its electro-catalysis oxygen evolution reaction overpotential is 100mV high relative to embodiment 1, current density compared with
It is small, therefore its catalytic performance is lower than embodiment 1.
Comparative example 3:
Ag-Co is prepared according to the method for embodiment 13O4/ NF nanometer sheet, what is different from the first embodiment is that being added without hydroboration
Sodium, obtained product do not have apparent catalytic performance.
Comparative example 4:
Ag-Co3O4/NF nanometer sheet is prepared according to the method for embodiment 1, what is different from the first embodiment is that in reaction process
Temperature remain at 20 DEG C, obtained product electrolysis water catalytic performance relative to the high 100mV of overpotential in embodiment one,
Its electro-catalysis oxygen evolution reaction performance can be poor.
Comparative example 5:
Ag-Co3O4/NF nanometer sheet is prepared according to the method for embodiment 1, unlike the first embodiment, is added without PVP, is obtained
The product morphology that arrives is irregular, in block structure, and obtained product electrolysis water catalytic performance is relative to excessively electric in embodiment one
The high 66mV in position, electro-catalysis oxygen evolution reaction performance are poor.
Comparative example 6
Ag-Co3O4/NF nanometer sheet is prepared according to the method for embodiment 1, unlike the first embodiment, 0.17mol/ is added
L cobalt nitrate, 0.34mol/L potassium cobalticyanide do not obtain pure cobaltosic oxide through detecting, wherein obtained product electrolysis water is urged
Change performance relative to the high 137mV of overpotential in embodiment one, electro-catalysis oxygen evolution reaction performance is poor.
Claims (10)
1. a kind of foamed nickel supported Ag doping cobaltosic oxide nano piece, it is characterised in that: including nickel foam and growth in situ
In the Ag doping cobaltosic oxide nano piece of foam nickel surface.
2. a kind of foamed nickel supported Ag doping cobaltosic oxide nano piece according to claim 1, it is characterised in that: described
Ag doping cobaltosic oxide nano piece is porous two-dimensional sheet structure, is evenly distributed in nickel foam；Aperture is 0.5-
1.5nm, diameter 100-200nm；With a thickness of 1-2nm.
3. a kind of foamed nickel supported Ag doping cobaltosic oxide nano piece according to claim 1, it is characterised in that: described
In Ag doping cobaltosic oxide nano piece, Co, Ag, O Elemental redistribution are uniform, according to the molar ratio, Ag:Co=1~2:5~50.
4. preparing a kind of side of foamed nickel supported Ag doping cobaltosic oxide nano as described in claims 1 to 3 any one
Method includes the following steps:
Contain divalent cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, be added nickel foam, first set reaction, obtain Ag-
Co3O4/ NF presoma, then by Ag-Co3O4/ NF presoma is added in boron hydrohalogenic acid salt, and the second secondary response is to get Ag-Co3O4/
NF。
5. a kind of preparation method of foamed nickel supported Ag doping cobaltosic oxide nano according to claim 4, feature
Be: it is described containing divalent cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, the mass fraction of the PVP is 1.5%-
The molecular weight of 36%, the PVP are 40000-60000.
6. a kind of preparation method of foamed nickel supported Ag doping cobaltosic oxide nano according to claim 4, feature
Be: it is described containing divalent cobalt source, trivalent cobalt source, silver-colored source, PVP solution in, the concentration of divalent cobalt source is 0.2-0.5mol/L,
According to the molar ratio, divalent cobalt ion: trivalent cobalt ions=1.6-2.2:1, the concentration in silver-colored source are 0.01-0.5mol/L.
7. a kind of preparation method of foamed nickel supported Ag doping cobaltosic oxide nano according to claim 4, feature
Be: the divalent cobalt source is selected from cobalt chloride, cobalt nitrate, and the trivalent cobalt source is selected from potassium cobalticyanide, and the silver source is selected from can be
The silver salt of silver ion is ionized out in aqueous solution.
8. a kind of preparation method of foamed nickel supported Ag doping cobaltosic oxide nano according to claim 4, feature
Be: the boron hydrohalogenic acid salt is selected from least one of sodium borohydride, potassium borohydride and lithium borohydride.
9. a kind of preparation method of foamed nickel supported Ag doping cobaltosic oxide nano according to claim 4, feature
Be: the temperature of first set reaction is 25-45 DEG C, and the time of first set reaction is 4-7h, and the temperature of the second secondary response is 70-90
DEG C, the time of the second secondary response is 3-6h.
10. a kind of foamed nickel supported Ag doping cobaltosic oxide nano piece according to any one of claims 1 to 3 is answered
With, it is characterised in that: the foamed nickel supported Ag doping cobaltosic oxide nano piece is applied and is used as oxygen evolution reaction catalysts.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110120524A (en) * | 2019-05-21 | 2019-08-13 | 西南大学 | A kind of load cobalt protoxide/nitrogen-doped carbon nickel foam composite material and preparation method and application |
| CN110212199A (en) * | 2019-05-30 | 2019-09-06 | 江汉大学 | A kind of conducting matrix grain and preparation method thereof |
| CN110887890A (en) * | 2019-12-12 | 2020-03-17 | 淮北师范大学 | Method for electrochemically detecting heavy metal ions by doping modified reinforced nano material |
| CN111151281A (en) * | 2020-01-07 | 2020-05-15 | 山东师范大学 | C3N4Modified Co3O4Self-supported ultrathin porous nanosheet and preparation method and application thereof |
| CN114522707A (en) * | 2022-02-22 | 2022-05-24 | 中南大学 | Alkaline earth metal carbonate loaded nano ruthenium composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110120524A (en) * | 2019-05-21 | 2019-08-13 | 西南大学 | A kind of load cobalt protoxide/nitrogen-doped carbon nickel foam composite material and preparation method and application |
| CN110120524B (en) * | 2019-05-21 | 2022-04-15 | 西南大学 | Cobalt oxide/nitrogen-doped carbon-loaded foam nickel composite material and preparation method and application thereof |
| CN110212199A (en) * | 2019-05-30 | 2019-09-06 | 江汉大学 | A kind of conducting matrix grain and preparation method thereof |
| CN110887890A (en) * | 2019-12-12 | 2020-03-17 | 淮北师范大学 | Method for electrochemically detecting heavy metal ions by doping modified reinforced nano material |
| CN111151281A (en) * | 2020-01-07 | 2020-05-15 | 山东师范大学 | C3N4Modified Co3O4Self-supported ultrathin porous nanosheet and preparation method and application thereof |
| CN111151281B (en) * | 2020-01-07 | 2022-09-02 | 山东师范大学 | C 3 N 4 Modified Co 3 O 4 Self-supported ultrathin porous nanosheet and preparation method and application thereof |
| CN114522707A (en) * | 2022-02-22 | 2022-05-24 | 中南大学 | Alkaline earth metal carbonate loaded nano ruthenium composite material and preparation method and application thereof |
| CN114522707B (en) * | 2022-02-22 | 2023-07-21 | 中南大学 | Alkaline earth metal carbonate loaded nano ruthenium composite material and preparation method and application thereof |
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