CN109607511A - A kind of drop coating the preparation method of multi-stage porous original position carbon electrode - Google Patents
A kind of drop coating the preparation method of multi-stage porous original position carbon electrode Download PDFInfo
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- CN109607511A CN109607511A CN201910049364.1A CN201910049364A CN109607511A CN 109607511 A CN109607511 A CN 109607511A CN 201910049364 A CN201910049364 A CN 201910049364A CN 109607511 A CN109607511 A CN 109607511A
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
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- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The present invention provides a kind of drop coating preparation method of multi-stage porous original position carbon electrode, and the carbonaceous organic materials such as molybdenum salt, cobalt salt and Tx-100 are dissolved in volatilization nonaqueous solvents, and thiocarbamide is added as sulphur source, obtains body liquid before Mo-Co-C-S；Above-mentioned preceding body liquid is applied in carbon substrate, it is dry after in Ar air-flow or N2In air-flow, annealing vulcanization obtains porous original position CoMo2S4- C electrode, wherein CoMo2S4Be covered by hole, then by the electrode in diluted acid 80 DEG C reaction for 24 hours, the CoMo in lysis electrodes2S4Particle；Ultimately form multi-stage porous original position carbon electrode.The product that technical solution of the present invention obtains has that low equipment requirement, required low raw-material cost, reaction condition is easily controllable, simple production process, is formed by good product consistency, multiple advantages such as environmental pollution is small, can be used for the multi-functional elctro-catalyst of HER, OER and ORR.
Description
Technical field
The present invention relates to electrode in situ and its preparations, belong to energy stores and transition material and devices field.
Background technique
The specific surface area and volume ratio of porous material superelevation are its critical natures for being different from one-dimensional material, are conducive to
Quality and the diffusion of Heat transmission and ion.They are that the application in absorption, catalysis and the fields such as power storage provides chance.?
In various porous nanometer structure materials, carbon-based material is because of its extensive availability, excellent conductivity and thermal conductivity, chemical stabilization
Property and relatively easy functionalization or hydridization and be concerned.Nearly ten years, the fast development of synthetic strategy is that preparation has
Controllable thickness, adjustable aperture and surface area and the porous carbon materials of particular surface functional group provide possibility.Pore structure is shadow
Carbon-based material is rung in the key factor of the numerous areas performance such as absorption, catalysis, electronic device.In general, micropore is large surface
Product, the key factor of high-adsorption-capacity and high capacitance.However, for traditional porous carbon, since the dynamics problem of micropore hinders
It has been hindered to apply.It is the supplement that the method for porous carbon is prepared to tradition, by introducing mesoporous even macropore in total
To improve quality and heat transfer.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of drop coating preparation method of multi-stage porous original position carbon electrode, this method
Low raw-material cost low with equipment requirement, required, reaction condition are easily controllable, simple production process, are formed by product one
Cause property is good, the advantages that environmental pollution is small, can be used for adsorbing, be catalyzed and the fields such as power storage, raw for the batch of electrode in situ
Production is of great importance.
For this purpose, the present invention provides one kind using Mo-Co-C-S as precursor liquid, it is coated on after forming a film in substrate, then prepare
The method of multi-stage porous original position carbon electrode, includes the following steps:
Molybdenum salt, cobalt salt and Tx-100 or aniline and other organic matters under the conditions of being stirred at room temperature, are dissolved in N, N- bis- by the first step
Methylformamide isopolarity easy volatile solvent is added thiocarbamide as sulphur source, obtains body liquid before Mo-Co-C-S, wherein Mo, Co atom
Mixed solution concentration be 100 ~ 900 mM, the volume ratio of Tx-100 and nonaqueous solvents is 0.03 ~ 2.The meaning of the step is:
Tx-100 can not only provide carbon in precursor liquid, but also have certain viscosity, be easy to be coated with and can increase load capacity；Instead
Answer reagent evenly dispersed, obtaining mixed uniformly preceding body liquid is to prepare uniform multi-stage porous original position carbon electrode to lay good basis；
Air pollution can be effectively reduced using thiocarbamide as sulphur source, it is safely controllable easy to operate.
Second step by above-mentioned preceding body drop-coated or is spun in substrate, such as carbon paper, carbon cloth, copper or nickel foil, in air or true
Be heated to 70 ~ 100 DEG C of rapid draings in the air, the meaning of the step is: n,N-Dimethylformamide left after quickly volatilizing by
Mo salt, Co salt, Tx-100 and the mixed uniformly forerunner's film layer of thiocarbamide still obtain and uniformly contain after guaranteeing subsequent high temperature annealing reaction
The porous carbon membranes of molybdenum cobalt sulfide.
Third step, by precursor film in step 2 in Ar air-flow or N2In air-flow, through 600 ~ 1000 DEG C of 30 min of sintering ~
The composite in-situ electrode that the porous carbon membranes of molybdenum cobalt sulfide can be obtained is taken out in 4h, furnace cooling.
4th step, by the porous carbon membranes composite in-situ electrode of the sulfide of cobalt containing molybdenum obtained by step 3 in diluted acid in 60 ~ 100
DEG C 10 ~ 24 hours (being reacted for 24 hours at preferably 80 DEG C) of reaction, to dissolve the molybdenum cobalt sulfide that is wrapped by.
Diluted acid used in the dissolution includes 0.5 ~ 2 M HNO3, 0.5 ~ 2 M HCl or 0.5 ~ 2 M H2SO4。
Multi-stage porous original position carbon electrode using in Mo-Co-C-S precursor liquid Tx-100 or the carbon sources such as aniline in carbonisation
In formed due to the dispersion by molybdenum salt and cobalt salt and disperse tiny carbon particle, to form tiny hole；It is high at 900 degree
Under temperature, molybdenum salt and cobalt salt react the sulfide recrystallization generated with thiocarbamide and are precipitated from carbon backbone structure at larger particles, with acid
Dissolution leaves biggish hole after cleaning, to form the carbon electrode in situ of multi-stage porous.
Detailed description of the invention
The SEM of molybdenum cobalt sulfide multi-stage porous original position carbon electrode prepared by Fig. 1 embodiment 1.
The SEM of molybdenum cobalt sulfide multi-stage porous original position carbon electrode prepared by Fig. 2 embodiment 2.
The SEM of molybdenum cobalt sulfide multi-stage porous original position carbon electrode prepared by Fig. 3 embodiment 3.
The SEM of molybdenum cobalt sulfide multi-stage porous original position carbon electrode prepared by Fig. 4 embodiment 4.
The SEM of molybdenum cobalt sulfide multi-stage porous original position carbon electrode prepared by Fig. 5 embodiment 5.
The SEM of molybdenum cobalt sulfide multi-stage porous original position carbon electrode prepared by Fig. 6 embodiment 6.
The SEM of multi-stage porous original position carbon electrode prepared by Fig. 7 embodiment 7.
The SEM of molybdenum cobalt sulfide multi-stage porous original position carbon electrode prepared by Fig. 8 embodiment 8.
The SEM of molybdenum cobalt sulfide multi-stage porous original position carbon electrode prepared by Fig. 9 embodiment 9.
The SEM of multi-stage porous original position carbon electrode prepared by Figure 10 embodiment 10.
The SEM of multi-stage porous original position carbon electrode prepared by Figure 11 embodiment 11.
The SEM of multi-stage porous original position carbon electrode prepared by Figure 12 embodiment 12.
The SEM of multi-stage porous original position carbon electrode prepared by Figure 13 embodiment 13.
The SEM of multi-stage porous original position carbon electrode prepared by Figure 14 embodiment 14.
The XRD of electrode prepared by Figure 15 embodiment 8,10,11,12,13.
Specific embodiment
Embodiment 1:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.0 mLN, dinethylformamide
Solution, the concentration of molybdenum pentachloride are 100 mM, and the concentration of six water of cobalt chloride is 300 mM, and the amount of Tx-100 is 1.0 mL, sulphur
The concentration of urea is 1000mM.Taken out after carbon paper is impregnated the preceding body liquid 30min, after 80 DEG C of 10 min of drying in thermal station again will before
The uniform drop coating of liquid is driven on carbon paper, then proceedes to dry 30min.Cated substrate is put into tube furnace, 600 under Ar air-flow
DEG C reaction 1h, continue thereafter with and be warming up to 900 DEG C of reaction 30min, after natural cooling taking-up.
Fig. 1 is the SEM figure of multi-stage porous original position electrode prepared by embodiment 1.Electricity prepared by the embodiment as seen from the figure
Extremely middle molybdenum cobalt sulfide is covered by hole, and hole homoepitaxial is on the fiber stick of carbon paper.
Embodiment 2:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.7 mLN, dinethylformamide
Solution, wherein the concentration of molybdenum pentachloride is 100 mM, and the concentration of six water of cobalt chloride is 300mM, and the amount of Tx-100 is 0.3mL,
The concentration of thiocarbamide is 1000mM.It takes out after carbon paper is impregnated the preceding body liquid 30min, again will after 80 DEG C of 10 min of drying in thermal station
The uniform drop coating of precursor liquid then proceedes to dry 30min on carbon paper.Cated substrate is put into tube furnace, under an ar atmosphere
600 DEG C of reaction 1h are continued thereafter with and are warming up to 900 DEG C of reaction 30min, take out after cooled to room temperature.
Fig. 2 is the SEM figure of multi-stage porous original position electrode prepared by embodiment 2.As can be seen from the figure metal in the electrode
Sulfide is wrapped in carbon pores.
Embodiment 3:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.0 mLN, dinethylformamide
Solution, wherein the concentration of molybdenum pentachloride is 267 mM, and the concentration of six water of cobalt chloride is 133mM, and the amount of Tx-100 is 1.0mL,
The concentration of thiocarbamide is 1000mM.It takes out after carbon paper is impregnated the preceding body liquid 30min, again will after 80 DEG C of 10 min of drying in thermal station
The uniform drop coating of precursor liquid then proceedes to dry 30min on carbon paper.Cated substrate is put into tube furnace, under an ar atmosphere
600 DEG C of reaction 1h are continued thereafter with and are warming up to 900 DEG C of reaction 30min, take out after cooled to room temperature.
Fig. 3 is the SEM figure of multi-stage porous original position electrode prepared by embodiment 3.As can be seen from the figure metal in the electrode
Sulfide is wrapped in carbon pores, and by containing mesoporous, micropore and macropore in the electrode from the point of view of carbon pores size, and pore structure is distributed
It is intensive uniform.
Embodiment 4:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.7 mLN, dinethylformamide
Solution, wherein the concentration of molybdenum pentachloride is 200 mM, and the concentration of six water of cobalt chloride is 200mM, and the amount of Tx-100 is 0.3mL,
The concentration of thiocarbamide is 1000mM.It takes out after carbon paper is impregnated the preceding body liquid 30min, again will after 80 DEG C of 10 min of drying in thermal station
The uniform drop coating of precursor liquid then proceedes to dry 30min on carbon paper.Cated substrate is put into tube furnace, under an ar atmosphere
600 DEG C of reaction 1h are continued thereafter with and are warming up to 900 DEG C of reaction 30min, take out after cooled to room temperature.
Fig. 4 schemes for the SEM of electrode in situ prepared by embodiment 4.As can be seen from the figure metal sulfide in the electrode
There is precipitation phenomenon in carbon pores, but carbon pores overall distribution is uniform.
Embodiment 5:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.7 mLN, dinethylformamide
Solution, wherein the concentration of molybdenum pentachloride is 100 mM, and the concentration of six water of cobalt chloride is 300mM, and the amount of Tx-100 is 0.3mL,
The concentration of thiocarbamide is 1000mM.It takes out after carbon paper is impregnated the preceding body liquid 30min, again will after 80 DEG C of 10 min of drying in thermal station
The uniform drop coating of precursor liquid then proceedes to dry 30min on carbon paper.Cated substrate is put into tube furnace, under an ar atmosphere
600 DEG C of reaction 1h are continued thereafter with and are warming up to 900 DEG C of reaction 45min, take out after cooled to room temperature.
Fig. 5 schemes for the SEM of electrode in situ prepared by embodiment 5.As can be seen from the figure metal sulfide in the electrode
It is wrapped in carbon pores, carbon pores dense distribution.
Embodiment 6:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.0 mLN, dinethylformamide
Solution, wherein the concentration of molybdenum pentachloride is 267 mM, and the concentration of six water of cobalt chloride is 133 mM, and the amount of Tx-100 is 1.0mL,
The concentration of thiocarbamide is 1000mM.It takes out after carbon paper is impregnated the preceding body liquid 30min, again will after 80 DEG C of 10 min of drying in thermal station
The uniform drop coating of precursor liquid then proceedes to dry 30min on carbon paper.Cated substrate is put into tube furnace, under an ar atmosphere
600 DEG C of reaction 1h are continued thereafter with and are warming up to 900 DEG C of reaction 45min, take out after cooled to room temperature.
Fig. 6 schemes for the SEM of electrode in situ prepared by embodiment 6.As can be seen from the figure metal sulfide in the electrode
It is wrapped in carbon pores, and pore structure is evenly distributed.
Embodiment 7:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.0 mL N, N- dimethyl formyls
Amine aqueous solution, the concentration of molybdenum pentachloride are 100 mM, and the concentration of six water of cobalt chloride is 300 mM, and the amount of Tx-100 is 1.0 mL,
The concentration of thiocarbamide is 1000 mM.It is taken out after carbon paper is impregnated preceding 30 min of body liquid, after 80 DEG C of 10 min of drying in thermal station again
By the uniform drop coating of precursor liquid on carbon paper, dry 30 min are then proceeded to.Cated substrate is put into tube furnace, in Ar air-flow
1 h of lower 600 DEG C of reactions is continued thereafter with and is warming up to 900 DEG C of reaction 30min, takes out after natural cooling.Then, by the sample of taking-up
In 0.5M HSO4In reacted 24 hours in 80 DEG C, it is dry by sample distilled water flushing after pickling.
Fig. 7 schemes for the SEM of electrode in situ prepared by embodiment 7.As can be seen from the figure carbon pores distribution is equal in the electrode
It is even.
Embodiment 8:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100, thiocarbamide and aniline are dissolved in 2.0 mL N, N- dimethyl
Formamide solution, wherein the concentration of molybdenum pentachloride is 100 mM, and the concentration of six water of cobalt chloride is 300 mM, and the amount of Tx-100 is
1.0 mL, the concentration of thiocarbamide are 1000 mM, and concentration of aniline is 50 μ L.It is taken out after carbon paper is impregnated preceding 30 min of body liquid, in
Again by the uniform drop coating of precursor liquid on carbon paper after 80 DEG C of 10 min of drying in thermal station, dry 30 min are then proceeded to.There to be coating
Substrate be put into tube furnace, 600 DEG C of 1 h of reaction under Ar air-flow are continued thereafter with and are warming up to 900 DEG C of reaction 30min, natural cooling
After take out.
Fig. 8 schemes for the SEM of electrode in situ prepared by embodiment 8.As can be seen from the figure metal sulfide in the electrode
It is wrapped in carbon pores, by containing mesoporous, micropore and macropore in the electrode from the point of view of carbon pores size, pore structure is densely distributed
It is even.
Embodiment 9
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100, thiocarbamide and CTAB are dissolved in 2.0 mL N, N- dimethyl
Formamide solution, wherein the concentration of molybdenum pentachloride is 100 mM, and the concentration of six water of cobalt chloride is 300 mM, and the amount of Tx-100 is
1.0 mL, the concentration of thiocarbamide are 1000 mM, and CTAB mass is 0.05 g.It is taken out after carbon paper is impregnated preceding 30 min of body liquid, in
Again by the uniform drop coating of precursor liquid on carbon paper after 80 DEG C of 10 min of drying in thermal station, dry 30 min are then proceeded to.There to be coating
Substrate be put into tube furnace, 600 DEG C of 1 h of reaction under Ar air-flow are continued thereafter with and are warming up to 900 DEG C of reaction 30min, natural cooling
After take out.
Fig. 9 schemes for the SEM of electrode in situ prepared by embodiment 9.As can be seen from the figure metal sulfide in the electrode
It is wrapped in carbon pores, by containing mesoporous, micropore and macropore in the electrode from the point of view of carbon pores size, and pore structure is evenly distributed.
Embodiment 10:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100, thiocarbamide and aniline are dissolved in 2.0 mL N, N- dimethyl
Formamide solution, wherein the concentration of molybdenum pentachloride is 100 mM, and the concentration of six water of cobalt chloride is 300 mM, and the amount of Tx-100 is
1.0 mL, the concentration of thiocarbamide are 1000 mM, and concentration of aniline is 50 μ L.It is taken out after carbon paper is impregnated preceding 30 min of body liquid, in
Again by the uniform drop coating of precursor liquid on carbon paper after 80 DEG C of 10 min of drying in thermal station, dry 30 min are then proceeded to.There to be coating
Substrate be put into tube furnace, 600 DEG C of 1 h of reaction under Ar air-flow are continued thereafter with and are warming up to 900 DEG C of reaction 30 min, naturally cold
But it takes out afterwards.Then, by the sample of taking-up in 1.0 M HNO3In in 80 DEG C react 24 hours, by sample distilled water after pickling
It rinses, it is dry.
Figure 10 schemes for the SEM of electrode in situ prepared by embodiment 10.As can be seen from the figure the electrode after pickling contains
Mesoporous, micropore and macropore, pore structure are evenly distributed, and can have a clear superiority as electrode.
Embodiment 11:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100, thiocarbamide and aniline are dissolved in 2.0 mL N, N- dimethyl
Formamide solution, wherein the concentration of molybdenum pentachloride is 267 mM, and the concentration of six water of cobalt chloride is 133 mM, and the amount of Tx-100 is
1.0 mL, the concentration of thiocarbamide are 1000 mM, and concentration of aniline is 50 μ L.It is taken out after carbon paper is impregnated preceding 30 min of body liquid, in
Again by the uniform drop coating of precursor liquid on carbon paper after 80 DEG C of 10 min of drying in thermal station, dry 30 min are then proceeded to.There to be coating
Substrate be put into tube furnace, 600 DEG C of 1 h of reaction under Ar air-flow are continued thereafter with and are warming up to 900 DEG C of reaction 30 min, naturally cold
But it takes out afterwards.Then, by the sample of taking-up in 1.0 M HSO4In in 80 DEG C react 24 hours, by sample distilled water after pickling
It rinses, it is dry.
Figure 11 schemes for the SEM of electrode in situ prepared by embodiment 11.As can be seen from the figure the electrode contains mesoporous, micro-
Hole and macropore, pore structure are evenly distributed, and can have a clear superiority as electrode.
Embodiment 12:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100, thiocarbamide and CTAB are dissolved in 2.0 mL N, N- dimethyl
Formamide solution, wherein the concentration of molybdenum pentachloride is 100 mM, and the concentration of six water of cobalt chloride is 300 mM, and the amount of Tx-100 is
1.0 mL, the concentration of thiocarbamide are 1000 mM, and CTAB mass is 0.05 g.It is taken out after carbon paper is impregnated preceding 30 min of body liquid, in
Again by the uniform drop coating of precursor liquid on carbon paper after 80 DEG C of 10 min of drying in thermal station, dry 30 min are then proceeded to.There to be coating
Substrate be put into tube furnace, 600 DEG C of 1 h of reaction under Ar air-flow are continued thereafter with and are warming up to 900 DEG C of reaction 30 min, naturally cold
But it takes out afterwards.Then, by the sample of taking-up in 1.0 M HNO3In in 80 DEG C react 24 hours, by sample distilled water after pickling
It rinses, it is dry.
Figure 12 schemes for the SEM of electrode in situ prepared by embodiment 12.As can be seen from the figure the electrode contains mesoporous, micro-
Hole and macropore, pore structure are evenly distributed, and carbon material has obvious lamination, may be the multi-stage porous of multilayer.
Embodiment 13:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, thiocarbamide and CTAB are dissolved in 3.0 mL n,N-Dimethylformamide
Solution, wherein the concentration of molybdenum pentachloride is 100 mM, and the concentration of six water of cobalt chloride is 300 mM, and the concentration of thiocarbamide is 1000
MM, CTAB mass are 0.2 g.It is taken out after carbon paper is impregnated preceding 30 min of body liquid, after 80 DEG C of 10 min of drying in thermal station again
By the uniform drop coating of precursor liquid on carbon paper, dry 30 min are then proceeded to.Cated substrate is put into tube furnace, in Ar air-flow
1 h of lower 600 DEG C of reactions is continued thereafter with and is warming up to 900 DEG C of 30 min of reaction, takes out after natural cooling.Then, by the sample of taking-up
In 1.0 M HNO3In reacted 24 hours in 80 DEG C, it is dry by sample distilled water flushing after pickling.
Figure 13 schemes for the SEM of electrode in situ prepared by embodiment 13.As can be seen from the figure the electrode contains mesoporous, micro-
Hole and macropore, pore structure are evenly distributed, and can have a clear superiority as electrode.
Embodiment 14:
At room temperature, molybdenum pentachloride, six water of cobalt chloride, Tx-100, thiocarbamide and sucrose are dissolved in 2.0 mL N, N- dimethyl
Formamide solution, wherein the concentration of molybdenum pentachloride is 267 mM, and the concentration of six water of cobalt chloride is 133 mM, and the amount of Tx-100 is
1.0 mL, the concentration of thiocarbamide are 1000 mM, and sucrose quality is 0.05 g.It is taken out after carbon paper is impregnated preceding 30 min of body liquid, in
Again by the uniform drop coating of precursor liquid on carbon paper after 80 DEG C of 10 min of drying in thermal station, dry 30 min are then proceeded to.There to be coating
Substrate be put into tube furnace, 600 DEG C of 1 h of reaction under Ar air-flow are continued thereafter with and are warming up to 900 DEG C of reaction 30 min, naturally cold
But it takes out afterwards.Then, by the sample of taking-up in 1.0 M HNO3In in 80 DEG C react 24 hours, by sample distilled water after pickling
It rinses, it is dry.
Figure 14 schemes for the SEM of electrode in situ prepared by embodiment 14.As can be seen from the figure the electrode contain it is mesoporous with
Micropore and carbon pores overall distribution is uniform.
Figure 15 is the XRD diagram of electrode in situ prepared by embodiment 8,10,11,12,13.Embodiment 8 is before pickling in figure
Electrode in situ, embodiment 8,10,11,12,13 be pickling after electrode in situ.Sample object is mutually CoMo before pickling2S4With carbon,
Only surplus porous carbon after pickling, it was demonstrated that the metallic compound in the original position electrode is complete under certain density acid and certain temperature
Portion's dissolution.
Claims (8)
1. a kind of drop coating preparation method of multi-stage porous original position carbon electrode, which is characterized in that it is specific the preparation method comprises the following steps:
(1) molybdenum salt, cobalt salt and Tx-100 or other carbonaceous organic materials are dissolved in volatilization nonaqueous solvents, and a certain amount of thiocarbamide is added and makees
For sulphur source, body liquid before Mo-Co-C-S is obtained；
(2) above-mentioned preceding body liquid is applied in the substrate containing pore structure, is placed in Ar air-flow after dry or N2The annealing of air-flow high temperature
Vulcanization, is then dissolved with diluted acid, multi-stage porous original position carbon electrode can be prepared.
2. the drop coating preparation method of the multi-stage porous original position carbon electrode according to claim 1, which is characterized in that volatilization is non-aqueous
Solvent, comprising: ethyl alcohol, n,N-Dimethylformamide.
3. the drop coating preparation method of the multi-stage porous original position carbon electrode according to claim 1, which is characterized in that molybdenum salt, cobalt salt
It is dissolved in volatilization nonaqueous solvents with Tx-100 and thiocarbamide, is formed by mixed solution, Mo atomic concentration, the mixing of Co atom are molten
The concentration of liquid is 100 ~ 900 mM, and the volume ratio of Tx-100 and nonaqueous solvents is 0.03 ~ 2.
4. the drop coating preparation method of the multi-stage porous original position carbon electrode according to claim 1, which is characterized in that the base
Bottom includes any one in carbon paper, carbon cloth, foam copper or nickel foam.
5. the drop coating preparation method of the multi-stage porous original position carbon electrode according to claim 1, which is characterized in that described is dry
Dry is in air or heating in vacuum to dry in 70 ~ 100 DEG C.
6. the drop coating preparation method of the multi-stage porous original position carbon electrode according to claim 1, which is characterized in that annealing temperature
It is 600 ~ 1000 DEG C, the reaction time is 0.5 ~ 4 h.
7. the drop coating preparation method of the multi-stage porous original position carbon electrode according to claim 1, which is characterized in that used in dissolution
Diluted acid includes 0.5 ~ 2 M HNO3, 0.5 ~ 2 M HCl or 0.5 ~ 2 M H2SO4。
8. the drop coating preparation method of the multi-stage porous original position carbon electrode according to claim 1, which is characterized in that acid dissolution institute
With temperature be 60 ~ 100 DEG C, the time be 10 ~ for 24 hours.
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| CN114703505B (en) * | 2022-04-04 | 2023-11-28 | 昆明理工大学 | Preparation method of metal atom electrocatalyst with stable carbon atom coordination |
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