CN108258252A - N doping hierarchical porous structure carbon ball and preparation method thereof - Google Patents
N doping hierarchical porous structure carbon ball and preparation method thereof Download PDFInfo
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- CN108258252A CN108258252A CN201711312757.4A CN201711312757A CN108258252A CN 108258252 A CN108258252 A CN 108258252A CN 201711312757 A CN201711312757 A CN 201711312757A CN 108258252 A CN108258252 A CN 108258252A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to have electrochemical catalysis hydrogen reduction the present invention relates to a kind of（ORR）/ oxygen is precipitated（OER）Difunctional N doping hierarchical porous structure carbon ball（N‑HPCS）And preparation method thereof.The present invention is using polystyrene microsphere as template, and melamine/formaldehyde resin is carbon source and nitrogen source, and silica is pore former, through calcining, hydrofluoric acid corrosion, is had macropore, mesoporous and micropore hierarchical porous structure N doping carbon ball simultaneously.The carbon ball has good electrochemical catalysis ORR/OER performances.
Description
Technical field
The present invention relates to one kind to have electrochemical catalysis hydrogen reduction（ORR）/ oxygen is precipitated（OER）Difunctional N doping it is multistage
Pore structure carbon ball（N-HPCS）And preparation method thereof.
Background technology
Demand of the today's society to the energy is being continuously increased, and fossil energy far can not meet the needs of the mankind.Change
The storage of the stone energy on earth is fewer and fewer, and can generate pollution to environment during use.Therefore seeking green can hold
The continuous energy substitutes fossil energy, is necessary.Fuel cell, metal-air battery and water electrolysis hydrogen production be not
Come in green sustainable energy to play an important role.In fuel cell, metal-air battery and water electrolysis hydrogen production, electro-catalysis
ORR and OER are of great significance.The catalyst for being currently used primarily in ORR is Pt and its alloy, and the catalyst for OER is Ru
With the oxide of Ir.Since Pt, Ru and Ir are precious metal elements, they big of limited reserves and expensive price limit
Sizable application.Therefore find that reserves are high, ORR/OER elctro-catalysts at low cost, be conducive to fuel cell, metal-air battery and
The industrialization and commercialization of water electrolysis hydrogen production.
Nitrogen-doped carbon material, raw material are easy to get, cheap, can show preferable ORR OER electro catalytic activities.Have
Potentiality substitute noble metal, and for fuel cell, metal-air battery and water electrolysis hydrogen production, can substantially reduce these greens can hold
The cost of continuous energy device and technology.
Invention content
There is electrochemical catalysis hydrogen reduction one of the objects of the present invention is to provide a kind of（ORR）/ oxygen is precipitated（OER）'s
Difunctional N doping hierarchical porous structure carbon ball（N-HPCS）.
The second object of the present invention is to provide the preparation method of the N doping hierarchical porous structure carbon ball.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of N doping hierarchical porous structure carbon ball, it is characterised in that the carbon ball is the hollow-core construction that grain size is 200nm, hollow at this
The shell of structure is formed by the carbon of N doping, and micropore and meso-hole structure is distributed with, and wherein carbon content is 92.45%, nitrogen content
It is 2.94%.
2. the method for N doping hierarchical porous structure carbon ball according to claim 1, it is characterized in that this method is specific
Step is：
A. by polystyrene microsphere（PS）It is dispersed in the concentrated sulfuric acid that mass fraction is 98 %, 40oIt is stirred to react 8 under C~
For 24 hours, it is neutral to be washed with deionized after the completion of reaction up to being cleaning solution, obtains the polystyrene microsphere after sulfonation, and
The microballoon is dispersed in water, solid content is the polystyrene microsphere dispersion liquid SPS after the sulfonation of 2~4mg/mL；
B. by formalin that melamine and mass fraction are 37 % 60oC is mixed to obtain clear solution；Described
Melamine and the mass volume ratio of formalin are 2~3g：4.5~5.5ml；
C. it in the poly-vinyl alcohol solution for being 5 % by every 100 milliliters of mass percent concentrations, sequentially adds obtained by 25 milliliters of step a
The proportional arrangement of clear solution obtained by the colloidal silicon dioxide and 5 milliliters of step c that SPS, 5 milliliters of mass percent concentrations are 40%
Into reaction system, pH=4~5h of the reaction system is adjusted, 1-9min is mixed afterwards；Washing is until cleaning solution after the completion of reaction
For neutrality, obtained product is denoted as SPS@MF/SiO2；After the product is freeze-dried 800 under inert gas shieldingoC calcinings 2
H, cooled to room temperature remove silica using the hydrofluoric acid corrosion of 10 %, obtain N doping hierarchical porous structure carbon ball
N-HPCS。
The present invention uses the melamine/formaldehyde resin that raw material is easy to get, and for carbon source and nitrogen source, polystyrene microsphere is hard mold
Plate, silica corrode, obtained N doping hierarchical porous structure carbon ball, due to it as pore former by calcining and hydrofluoric acid
With big specific surface area and unique hierarchical porous structure, good difunctional electro catalytic activity is shown.Obtained nitrogen
Doping hierarchical porous structure carbon ball N-HPCS has macropore, mesoporous and microcellular structure simultaneously.Hierarchical porous structure not only causes carbon ball to have
There is big specific surface area, and be conducive to the rapid diffusion of reactants and products.This N-HPCS shows ORR and OER
Good electro catalytic activity.
Description of the drawings
Fig. 1 is the TEM figures of N-HPCS；
Fig. 2 is the x-ray photoelectron spectroscopy of N-HPCS；
Fig. 3 is nitrogen adsorption-desorption isotherm of N-HPCS；
Fig. 4 is the pore size distribution curve of N-HPCS；
Fig. 5 is N-HPCS and linear scan curves of the commercialization Pt/C in the KOH solution of 0.1 M of oxygen saturation；
Fig. 6 is N-HPCS, commercialization Pt/C and RuO2Linear scan curve in the KOH solution of 0.1 M of nitrogen saturation.
Specific embodiment
With reference to specific example, the present invention is described in detail：
Embodiment one：It is as follows：
The first step：Polystyrene microsphere is prepared by emulsifier-free emulsion polymerization method（PS）, a diameter of 200 nm.By 2 g PS
In the 40 mL concentrated sulfuric acids for being 98 % in mass fraction by ultrasonic disperse, 40o12 h are stirred to react under C.It is used after the completion of reaction
Deionized water washing is until for neutrality.The PS microballoons of the sulfonation of gained are dispersed in water, solid content is 4 mg/mL, is denoted as
SPS。
Second step：By formalin that 2.8 g melamines and 5.3 mL mass fractions are 37 % 60oC mixing is stirred
It mixes to obtain transparent solution.
Third walks：The poly-vinyl alcohol solution that mass fraction is 5 % is placed in flask, sequentially adds 25 mL SPS, 5 mL
The prepolymer that silica and second step obtain.Add glacial acetic acid adjust reaction system pH value be approximately equal to 4.5 after mix and stir
Mix 7 min.It is washed with deionized after the completion of reaction until neutral.Obtained product is denoted as SPS@MF/SiO2.Product is freezed
After drying 800 under inert gas shieldingoC calcines 2 h, and cooled to room temperature is corroded using the hydrofluoric acid of 10 % and removed
Silica obtains N doping hierarchical porous structure carbon ball.
Using Hg/HgO as reference electrode, platinum filament is used as to electrode, the glass-carbon electrodes of N-HPCS modifications as working electrode,
The KOH solution of 0.1 M carries out N-HPCS the characterization of electrochemistry ORR and OER performance as electrolyte.Fig. 4 is N-HPCS and quotient
With linear sweep voltammetry curve of the disc electrode of Pt/C modifications in 0.1 M KOH solutions of saturation oxygen；Fig. 5 be N-HPCS,
Pt/C and RuO2Linear scan curve in the KOH solution of 0.1 M of nitrogen saturation（vs. Hg/HgO）.Prove N-HPCS
There is preferable catalytic activity to hydrogen reduction, although onset potential and limitation current density ratio Pt/C are slightly lower, N-HPCS
Advantage be that raw material is easy to get, cost can be greatly lowered.N-HPCS also has excellent OER catalytic activity simultaneously, hence it is evident that
It is better than Pt/C, relative to RuO2Catalyst, onset potential are much smaller.Fully show that N-HPCS can be with by above example
As ORR and OER bifunctional catalysts, and it is better than noble metal catalyst in some aspects, it is entirely possible to be replaced.
Embodiment two：It is as follows：
The first step：Polystyrene microsphere is prepared by emulsifier-free emulsion polymerization method（PS）, a diameter of 200 nm.By 2 g PS
In the 40 mL concentrated sulfuric acids for being 98 % in mass fraction by ultrasonic disperse, 40o8 h are stirred to react under C.It is used after the completion of reaction
Deionized water washing is until for neutrality.The PS microballoons of the sulfonation of gained are dispersed in water, solid content is 4 mg/mL, is denoted as
SPS。
Second step：By formalin that 2 g melamines and 5 mL mass fractions are 37 % 60oC is mixed
To transparent solution.
Third walks：The poly-vinyl alcohol solution that mass fraction is 5 % is placed in flask, sequentially adds 25 mL SPS, 5 mL
The prepolymer that silica and second step obtain.Add glacial acetic acid adjust reaction system pH value be approximately equal to 4.5 after mix and stir
Mix 7 min.It is washed with deionized after the completion of reaction until neutral.Obtained product is denoted as SPS@MF/SiO2.Product is freezed
After drying 800 under inert gas shieldingoC calcines 2 h, and cooled to room temperature is corroded using the hydrofluoric acid of 10 % and removed
Silica obtains N doping hierarchical porous structure carbon ball.
Using Hg/HgO as reference electrode, platinum filament is used as to electrode, the glass-carbon electrodes of N-HPCS modifications as working electrode,
The KOH solution of 0.1 M carries out N-HPCS the characterization of electrochemistry ORR and OER performance as electrolyte.
Embodiment three：It is as follows：
The first step：Polystyrene microsphere is prepared by emulsifier-free emulsion polymerization method（PS）, a diameter of 200 nm.By 2 g PS
In the 40 mL concentrated sulfuric acids for being 98 % in mass fraction by ultrasonic disperse, 40o8 h are stirred to react under C.It is used after the completion of reaction
Deionized water washing is until for neutrality.The PS microballoons of the sulfonation of gained are dispersed in water, solid content is 2 mg/mL, is denoted as
SPS。
Second step：By formalin that 2.5 melamines and 4.5 mL mass fractions are 37 % 60oC is mixed
Obtain transparent solution.
Third walks：The poly-vinyl alcohol solution that mass fraction is 5 % is placed in flask, sequentially adds 25 mL SPS, 5 mL
The prepolymer that silica and second step obtain.Add glacial acetic acid adjust reaction system pH value be approximately equal to 4.5 after mix and stir
Mix 7 min.It is washed with deionized after the completion of reaction until neutral.Obtained product is denoted as SPS@MF/SiO2.Product is freezed
After drying 800 under inert gas shieldingoC calcines 2 h, and cooled to room temperature is corroded using the hydrofluoric acid of 10 % and removed
Silica obtains N doping hierarchical porous structure carbon ball.
Using Hg/HgO as reference electrode, platinum filament is used as to electrode, the glass-carbon electrodes of N-HPCS modifications as working electrode,
The KOH solution of 0.1 M carries out N-HPCS the characterization of electrochemistry ORR and OER performance as electrolyte.
Example IV：It is as follows：
The first step：Polystyrene microsphere is prepared by emulsifier-free emulsion polymerization method（PS）, a diameter of 200 nm.By 2 g PS
In the 40 mL concentrated sulfuric acids for being 98 % in mass fraction by ultrasonic disperse, 40o24 h are stirred to react under C.It is used after the completion of reaction
Deionized water washing is until for neutrality.The PS microballoons of the sulfonation of gained are dispersed in water, solid content is 3 mg/mL, is denoted as
SPS。
Second step：By formalin that 2.5 melamines and 4.5 mL mass fractions are 37 % 60oC is mixed
Obtain transparent solution.
Third walks：The poly-vinyl alcohol solution that mass fraction is 5 % is placed in flask, sequentially adds 25 mL SPS, 5 mL
The prepolymer that silica and second step obtain.Add glacial acetic acid adjust reaction system pH value be approximately equal to 4.5 after mix and stir
Mix 3 min.It is washed with deionized after the completion of reaction until neutral.Obtained product is denoted as SPS@MF/SiO2.Product is freezed
After drying 800 under inert gas shieldingoC calcines 2 h, and cooled to room temperature is corroded using the hydrofluoric acid of 10 % and removed
Silica obtains N doping hierarchical porous structure carbon ball.
Using Hg/HgO as reference electrode, platinum filament is used as to electrode, the glass-carbon electrodes of N-HPCS modifications as working electrode,
The KOH solution of 0.1 M carries out N-HPCS the characterization of electrochemistry ORR and OER performance as electrolyte.
Embodiment five：It is as follows：
The first step：Polystyrene microsphere is prepared by emulsifier-free emulsion polymerization method（PS）, a diameter of 200 nm.By 2 g PS
In the 40 mL concentrated sulfuric acids for being 98 % in mass fraction by ultrasonic disperse, 40o24 h are stirred to react under C.It is used after the completion of reaction
Deionized water washing is until for neutrality.The PS microballoons of the sulfonation of gained are dispersed in water, solid content is 3 mg/mL, is denoted as
SPS。
Second step：By formalin that 2.8 melamines and 5.3 mL mass fractions are 37 % 60oC is mixed
Obtain transparent solution.
Third walks：The poly-vinyl alcohol solution that mass fraction is 5 % is placed in flask, sequentially adds 25 mL SPS, 5 mL
The prepolymer that silica and second step obtain.Add glacial acetic acid adjust reaction system pH value be approximately equal to 5 after be mixed 5
min.It is washed with deionized after the completion of reaction until neutral.Obtained product is denoted as SPS@MF/SiO2.Product is freeze-dried
Afterwards 800 under inert gas shieldingoC calcines 2 h, and cooled to room temperature removes dioxy using the hydrofluoric acid corrosion of 10 %
SiClx obtains N doping hierarchical porous structure carbon ball.
Using Hg/HgO as reference electrode, platinum filament is used as to electrode, the glass-carbon electrodes of N-HPCS modifications as working electrode,
The KOH solution of 0.1 M carries out N-HPCS the characterization of electrochemistry ORR and OER performance as electrolyte.
Embodiment six：It is as follows：
The first step：Polystyrene microsphere is prepared by emulsifier-free emulsion polymerization method（PS）, a diameter of 200 nm.By 2 g PS
In the 40 mL concentrated sulfuric acids for being 98 % in mass fraction by ultrasonic disperse, 40o12 h are stirred to react under C.It is used after the completion of reaction
Deionized water washing is until for neutrality.The PS microballoons of the sulfonation of gained are dispersed in water, solid content is 3 mg/mL, is denoted as
SPS。
Second step：By formalin that 3 melamines and 5.5 mL mass fractions are 37 % 60oC is mixed
To transparent solution.
Third walks：The poly-vinyl alcohol solution that mass fraction is 5 % is placed in flask, sequentially adds 25 mL SPS, 5 mL
The prepolymer that silica and second step obtain.Add glacial acetic acid adjust reaction system pH value be approximately equal to 5 after be mixed 9
min.It is washed with deionized after the completion of reaction until neutral.Obtained product is denoted as SPS@MF/SiO2.Product is freeze-dried
Afterwards 800 under inert gas shieldingoC calcines 2 h, and cooled to room temperature removes dioxy using the hydrofluoric acid corrosion of 10 %
SiClx obtains N doping hierarchical porous structure carbon ball.
Using Hg/HgO as reference electrode, platinum filament is used as to electrode, the glass-carbon electrodes of N-HPCS modifications as working electrode,
The KOH solution of 0.1 M carries out N-HPCS the characterization of electrochemistry ORR and OER performance as electrolyte.
Claims (2)
1. a kind of N doping hierarchical porous structure carbon ball, it is characterised in that the carbon ball is the hollow-core construction that grain size is 200nm, in the sky
The shell of core structure is formed by the carbon of N doping, and micropore and meso-hole structure is distributed with, and wherein carbon content is 92.45%, and nitrogen contains
Measure is 2.94%.
2. the method for N doping hierarchical porous structure carbon ball according to claim 1, it is characterized in that the specific steps of this method
For：
A. by polystyrene microsphere（PS）It is dispersed in the concentrated sulfuric acid that mass fraction is 98 %, 40oIt is stirred to react 8 under C~
For 24 hours, it is neutral to be washed with deionized after the completion of reaction up to being cleaning solution, obtains the polystyrene microsphere after sulfonation, and
The microballoon is dispersed in water, solid content is the polystyrene microsphere dispersion liquid SPS after the sulfonation of 2~4mg/mL；
B. by formalin that melamine and mass fraction are 37 % 60oC is mixed to obtain clear solution；Described
Melamine and the mass volume ratio of formalin are 2~3g：4.5~5.5ml；
C. it in the poly-vinyl alcohol solution for being 5 % by every 100 milliliters of mass percent concentrations, sequentially adds obtained by 25 milliliters of step a
The proportional arrangement of clear solution obtained by the colloidal silicon dioxide and 5 milliliters of step c that SPS, 5 milliliters of mass percent concentrations are 40%
Into reaction system, pH=4~5h of the reaction system is adjusted, 1-9min is mixed afterwards；Washing is until cleaning solution after the completion of reaction
For neutrality, obtained product is denoted as SPS@MF/SiO2；After the product is freeze-dried 800 under inert gas shieldingoC calcinings 2
H, cooled to room temperature remove silica using the hydrofluoric acid corrosion of 10 %, obtain N doping hierarchical porous structure carbon ball
N-HPCS。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993537A (en) * | 2018-08-03 | 2018-12-14 | 苏州大学 | A kind of carbon-based sulfonic acid microballoon in the multistage gradient hole of uniform particle diameter, preparation method and its application |
| CN109126858A (en) * | 2018-11-05 | 2019-01-04 | 湖南科技大学 | Preparation method of bifunctional catalyst that is a kind of while generating diglycolic acid and hydrogen and products thereof and application |
| CN109759044A (en) * | 2019-01-23 | 2019-05-17 | 河南师范大学 | A kind of method of prepare with scale for the cathod catalyst of electrochemistry formated ammonia |
| CN110690458A (en) * | 2019-08-23 | 2020-01-14 | 安徽力普拉斯电源技术有限公司 | Preparation method and application of bamboo-shaped carbon nanotube oxygen reduction electrocatalyst |
| CN110729480A (en) * | 2019-10-25 | 2020-01-24 | 南开大学 | Nitrogen-doped porous hollow carbon sphere and preparation method and application thereof |
| CN114883553A (en) * | 2022-05-11 | 2022-08-09 | 兰州理工大学 | Preparation of porous nano Li by alkali liquor selective corrosion 2 FeSiO 4 Method for preparing/C |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961121A (en) * | 2015-06-24 | 2015-10-07 | 上海大学 | Preparation method for nitrogen-doped nuclear shell hollow carbon |
| CN105692590A (en) * | 2016-03-17 | 2016-06-22 | 南京理工大学 | Method for preparing nitrogen-doped hollow mesoporous core-shell carbon spheres |
| CN107032321A (en) * | 2017-06-14 | 2017-08-11 | 山东科技大学 | The hollow carbon sphere material of a kind of nitrogen-phosphor codoping and shell with classification macropore meso-hole structure and its preparation method and application |
-
2017
- 2017-12-12 CN CN201711312757.4A patent/CN108258252B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961121A (en) * | 2015-06-24 | 2015-10-07 | 上海大学 | Preparation method for nitrogen-doped nuclear shell hollow carbon |
| CN105692590A (en) * | 2016-03-17 | 2016-06-22 | 南京理工大学 | Method for preparing nitrogen-doped hollow mesoporous core-shell carbon spheres |
| CN107032321A (en) * | 2017-06-14 | 2017-08-11 | 山东科技大学 | The hollow carbon sphere material of a kind of nitrogen-phosphor codoping and shell with classification macropore meso-hole structure and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| JINPENG HAN等: "Porous nitrogen-doped hollow carbon spheres derived from polyaniline for high performance supercapacitors", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
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| CN108993537A (en) * | 2018-08-03 | 2018-12-14 | 苏州大学 | A kind of carbon-based sulfonic acid microballoon in the multistage gradient hole of uniform particle diameter, preparation method and its application |
| CN108993537B (en) * | 2018-08-03 | 2021-07-27 | 苏州大学 | Multi-stage gradient pore carbon-based sulfonic acid microsphere with uniform particle size, and preparation method and application thereof |
| CN109126858A (en) * | 2018-11-05 | 2019-01-04 | 湖南科技大学 | Preparation method of bifunctional catalyst that is a kind of while generating diglycolic acid and hydrogen and products thereof and application |
| CN109126858B (en) * | 2018-11-05 | 2021-03-26 | 湖南科技大学 | Preparation method of bifunctional catalyst capable of simultaneously generating diglycolic acid and hydrogen, product and application thereof |
| CN109759044A (en) * | 2019-01-23 | 2019-05-17 | 河南师范大学 | A kind of method of prepare with scale for the cathod catalyst of electrochemistry formated ammonia |
| CN110690458A (en) * | 2019-08-23 | 2020-01-14 | 安徽力普拉斯电源技术有限公司 | Preparation method and application of bamboo-shaped carbon nanotube oxygen reduction electrocatalyst |
| CN110729480A (en) * | 2019-10-25 | 2020-01-24 | 南开大学 | Nitrogen-doped porous hollow carbon sphere and preparation method and application thereof |
| CN114883553A (en) * | 2022-05-11 | 2022-08-09 | 兰州理工大学 | Preparation of porous nano Li by alkali liquor selective corrosion 2 FeSiO 4 Method for preparing/C |
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