CN108940285A - A kind of preparation method and application of flexibility electrolysis water catalysis material - Google Patents
A kind of preparation method and application of flexibility electrolysis water catalysis material Download PDFInfo
- Publication number
- CN108940285A CN108940285A CN201810804162.9A CN201810804162A CN108940285A CN 108940285 A CN108940285 A CN 108940285A CN 201810804162 A CN201810804162 A CN 201810804162A CN 108940285 A CN108940285 A CN 108940285A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- preparation
- catalysis material
- electrolysis water
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 39
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 34
- 239000010941 cobalt Substances 0.000 claims abstract description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960003351 prussian blue Drugs 0.000 claims abstract description 18
- 239000013225 prussian blue Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 16
- 239000002121 nanofiber Substances 0.000 claims abstract description 12
- 238000009987 spinning Methods 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- IDUKLYIMDYXQQA-UHFFFAOYSA-N cobalt cyanide Chemical compound [Co].N#[C-] IDUKLYIMDYXQQA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 241001062009 Indigofera Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 8
- 239000004917 carbon fiber Substances 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 6
- 238000010924 continuous production Methods 0.000 abstract description 3
- 235000013495 cobalt Nutrition 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000835 fiber Substances 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000002114 nanocomposite Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 5
- 239000002134 carbon nanofiber Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- -1 Transition Metal Sulfur Compound Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a kind of preparation method and applications of flexible electrolysis water catalysis material, belong to water electrolysis hydrogen production technical field.The preparation method includes: that (1) prepares the Prussian blue similar object nanoparticle of cobalt-based；(2) it disperses the Prussian blue similar object nanoparticle of cobalt-based in organic solvent, adds polyacrylonitrile and spinning solution is made, Co-PBA/PAN composite nano-fiber membrane is made in electrostatic spinning；(3) pre-oxidation treatment is carried out to Co-PBA/PAN composite nano-fiber membrane, then carries out carbonization treatment in an inert atmosphere, the flexible electrolysis water catalysis material is made.Cobalt carbide is dispersed in porous carbon fiber in electrolysis water catalysis material prepared by the present invention, increase catalytic site, the problem of porous carbon fiber provides the carrier of catalytic site and enhances electric conductivity, improve conventional powder catalysis material easy to fall off, easy loss simultaneously；Production method is easy, green safe, it can be achieved that large area continuous production.
Description
Technical field
The present invention relates to water electrolysis hydrogen production technical fields, and in particular to a kind of preparation method of flexibility electrolysis water catalysis material
And application.
Background technique
Currently, energy problem is most severe one of the problem that the world today faces.It relies on fossil fuel and obtains the energy pair
Economic impact is huge, and excessive use of fossil fuel not only pollutes air, more exacerbates global warming.It would therefore be highly desirable to seek
Cleaning, sustainable new energy is looked for carry out substitute fossil fuels.In the various energy, efficient, cleaning, reproducible hydrogen are not only
A kind of energy, and be the carrier of storage and the transfer energy.It wherein, is considered as generating clean hydrogen to fire by water electrolysis hydrogen production
The very promising mode of material.
For water electrolysis hydrogen production, the key of research is to improve the activity and stability of electrocatalysis material, and reduce electrification
Learn the overpotential of liberation of hydrogen analysis oxygen.Noble metal platinum is most effective liberation of hydrogen analysis oxygen elctro-catalyst generally acknowledged so far, but due to it
Preparation cost is high, and resources reserve is limited, so platinum receives serious limitation as the large-scale production of catalyst.Therefore, it looks for
Have to a kind of stabilization, efficient, cheap and environmental-friendly electrocatalysis material with the utilization rate of electrical for improving electrolysis water and wastewater industry
There is very important meaning.
Recently, transition metal and its alloy, sulfide, carbide etc. cause the interest of researchers, Transition Metal Sulfur
Compound, selenides and carbide etc. are successfully synthesized and are applied to effective cathode hydrogen evolution catalyst, especially transition
Metal carbides, unique structure and good electrocatalysis characteristic receive very big attention.
As patent document CN105401167A discloses a kind of New Co3Mo3C elctro-catalyst, preparation method include: by
Ammonium Molybdate Tetrahydrate, four acetate hydrate cobalts and hexa are dissolved in ammonium hydroxide, are obtained magenta solution and are stirred at room temperature
Evaporation is mixed, pinkish red mill base material is obtained, vacuum drying is obtained powder, is passed through inert gas, is to slowly warm up to the speed of 5 DEG C/min
750-800 DEG C, 2-4h is kept the temperature, obtains Co after natural cooling3Mo3C elctro-catalyst.Further, by Co3Mo3C elctro-catalyst is negative
Be loaded on matrix and prepare catalytic hydrogen evolution electrode for electrolytic seawater hydrogen manufacturing, described matrix be selected from nickel foam, foam iron-nickel, titanium net,
One or more of nickel sheet, titanium sheet or electro-conductive glass.
At present in using research of the nano-carbon material as elctro-catalyst, used carbon material is macroscopically being mostly powder
Last shape.When powder catalyst is coated on conductive carrier by high polymer binder mixing, catalyst and interelectrode electricity
Sub- transport resistance will increase, while also mask the amount of activated site of catalyst, reduce its catalytic activity.Importantly,
These grained catalysts are easy to fall off from carrier during gas discharges, unstable so as to cause catalytic effect.Therefore, it grinds
Study carefully with high activity, high stability and is currently to be badly in need of for water electrolysis hydrogen production without the macroscopic three dimensional structure catalyst of binder
It solves the problems, such as.
Summary of the invention
The purpose of the present invention is to provide a kind of with high activity, high stability and urges without the water electrolysis hydrogen production of binder
Change material, to realize the large-scale production of water electrolysis hydrogen production.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of flexibility electrolysis water catalysis material, comprising the following steps:
(1) the Prussian blue similar object nanoparticle of cobalt-based is prepared；
(2) it disperses the Prussian blue similar object nanoparticle of cobalt-based in organic solvent, adds polyacrylonitrile and spinning is made
Co-PBA/PAN composite nano-fiber membrane is made in silk liquid, electrostatic spinning；
(3) pre-oxidation treatment is carried out to Co-PBA/PAN composite nano-fiber membrane, then carried out at carbonization in an inert atmosphere
The flexible electrolysis water catalysis material is made in reason.
In step (1), using cobalt acetate and six cyano cobalt acid potassium as raw material, it is Prussian blue that cobalt-based is prepared by chemical synthesis
Analog (Co-PBA) nanoparticle.It is Prussian blue and the like that there is good electrocatalysis characteristic, cobalt nanometer particle itself
Also there is good catalytic activity, and Prussian blue frame structure provides functional carbon source to material again.
The molar ratio of cobalt acetate and six cyano cobalt acid potassium is 0.15:0.08.
Surfactant is added in preparation process or the pH value by adjusting reaction system is big to control nanoparticle particle
It is small.
The surfactant is polyvinylpyrrolidone or neopelex.
Specifically, the Prussian blue similar object nanoparticle of cobalt-based, preparation method are prepared using chemical synthesis, comprising:
First by cobalt acetate obtained solution A soluble in water, six cyano cobalt acid potassium, polyvinylpyrrolidone or neopelex are dissolved in
B solution is obtained in water, then solution A is added into B solution while stirring, and reaction generates the Prussian blue similar object (Co- of cobalt-based
PBA) nanoparticle.
Preferably, solution A is added in B solution with the rate of 2~3mL/min, solution gradually becomes pink by colourless,
After all adding, continue 10~15min of stirring, stands 3~4h.
Preferably, the matter of cobalt acetate, six cyano cobalt acid potassium, polyvinylpyrrolidone or neopelex, water
Amount is than being 0.187~0.374:0.133~0.266:3~6:80.
The polyvinylpyrrolidonemolecules molecules amount is 58000.
More preferably, cobalt acetate, six cyano cobalt acid potassium, PVP and deionized water mass ratio are as follows: 0.374:0.266:6:
80。
Prussian blue similar object (Co-PBA) nanoparticle of cobalt-based is mixed with polyacrylonitrile (PAN) in step (2), Static Spinning
Co-PBA/PAN composite nano-fiber membrane is made in silk, and wherein Co-PBA nanoparticle is dispersed in tunica fibrosa.Again through step
(3) carbonization treatment obtains the cobalt-based carbon nanofiber membrane that cobalt carbide is dispersed in porous carbon fiber, the i.e. flexibility
Electrolysis water catalysis material.
Preferably, the organic solvent is n,N-Dimethylformamide in step (2).First by cobalt-based prussian blue
It is scattered in n,N-Dimethylformamide like object (Co-PBA) nanoparticle, polyacrylonitrile is added while stirring, continue stirring extremely
Polyacrylonitrile is completely dissolved, and obtains the opaque thick solution of blue, as spinning solution.
Preferably, the mass ratio of the Prussian blue similar object nanoparticle of cobalt-based and polyacrylonitrile is 0.1~1.5:10, spin
The mass percent of polyacrylonitrile is 6~12% in silk liquid.Co-PBA nanoparticle plays main catalytic action, and accounting is too small,
Then catalytic performance can be poor；Accounting is excessive, and carbon fiber is frangible, reduction of pliability, bad mechanical strength.More preferably, cobalt-based Prussia
The mass ratio of blue analog nanoparticle and polyacrylonitrile is 1:10.
Preferably, the condition of the electrostatic spinning are as follows: the internal diameter of metal needle is 0.6~0.7mm, and fltting speed is
0.8~1.5mL h-1, the distance between needle point and receiver board be 15~18cm, voltage be 25~30kV, environment temperature be 23~
30 DEG C, ambient humidity is 30~40%.
Vacuum drying under the conditions of 80 DEG C of spinning film made from electrostatic spinning.
The average diameter of the Co-PBA/PAN composite nano fiber is 200~400nm.
Preferably, in step (3), the condition of pre-oxidation treatment are as follows: 260-280 DEG C of 0.5~2h of processing under air atmosphere.
Preferably, in step (3), the condition of carbonization treatment are as follows: be warming up to 700~1100 DEG C with 5~10 DEG C/min, protect
1~6h of temperature.
More preferably, the condition of carbonization treatment is to be warming up to 1000 DEG C with 5 DEG C/min, 3h is kept the temperature.Result of study shows: carbon
Changing temperature is 1000 DEG C, and the time is under the conditions of 3 hours, and the electrocatalysis characteristic of obtained material is best.
Preferably, the inert atmosphere is nitrogen or argon gas, gas flow rate 100sccm in step (3).
The present invention also provides flexibility electrolysis water catalysis materials made from the preparation method described in one kind.Cobalt-based carbon Nanowire
The average diameter of dimension is 100~300nm, and cobalt carbide is dispersed in porous carbon fiber, have excellent catalytic properties and
Good structural stability.
Electrolysis water catalysis material provided by the invention is flexible self-supporting structure, can be directly used as electrolysis water catalysis electrode,
It is carried on conductive carrier i.e. realization high-efficient electrolytic water hydrogen and oxygen production without binder, effectively avoids powder catalyst
In the defect of electro-catalysis application.
The present invention also provides application of the flexible electrolysis water catalysis material in water electrolysis hydrogen production oxygen.
The application are as follows: for the flexible electrolysis water catalysis material as catalysis electrode, platinum is auxiliary electrode, Ag/
AgCl is reference electrode；Electrolyte is alkalinity or acidic aqueous solution.
Preferably, electrolyte is 1M KOH aqueous solution.
It is that the present invention has the utility model has the advantages that
(1) present invention prepares Prussian blue similar object (Co-PBA) nanoparticle of cobalt-based by chemical synthesis, then with gather
Co-PBA/PAN composite nano-fiber membrane is made using electrostatic spinning in acrylonitrile (PAN) mixing, and self-supporting is made through high temperature cabonization
The electrolysis water catalysis material of cobalt-based carbon nano-composite fiber structure can be directly used as electrolysis water catalysis electrode, and production method is easy,
It is green safe, it can be achieved that large area continuous production.
(2) cobalt carbide is dispersed in porous carbon fiber in electrolysis water catalysis material prepared by the present invention, is increased
Catalytic site, while porous carbon fiber provides the carrier of catalytic site and enhances electric conductivity, improves conventional powder catalysis
The problem of material is easy to fall off, easy loss is suitable for the production of heavy industrialization electrolysis water, shows in electrolysis water field extremely wide
Wealthy application prospect.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of cobalt-based carbon nano-composite fiber, (b) is the size enlarged drawing of (a).
Fig. 2 is Co CNFs X-ray powder diffraction spectrogram.
The Co-PB/PAN nano fibrous membrane and the photo after carbonization treatment that Fig. 3 is preparation, wherein (a) obtains for electrostatic spinning
To Co-PB/PAN nano fibrous membrane, (b) it is the photo of carbon nano-fiber in the bent state, there is good flexibility, (c)
It is obtained after left-to-right respectively Co-PB/PAN nano fibrous membrane, pretreated Co-PB/PAN nano fibrous membrane and high temperature cabonization
Cobalt-based carbon nano-composite fiber.
Fig. 4 is that the carbon of doping different proportion (0%, 3%, 5% and 10%) cobalt-based prussian blue nano particle is nano combined
Fiber analyses oxygen performance as the electrocatalytic hydrogen evolution that catalysis electrode is tested in 1M KOH, wherein (a) is electrocatalytic hydrogen evolution HER figure,
(b) oxygen OER figure is analysed for electro-catalysis.
Fig. 5 is for cobalt-based carbon nano-composite fiber as catalysis electrode respectively in 1M KOH and 0.5M H2SO4The electricity of middle test
Catalytic hydrogen evolution analyses oxygen performance, wherein (a) is electrocatalytic hydrogen evolution HER figure, (b) analyses oxygen OER figure for electro-catalysis.
Specific embodiment
The present invention is specifically described and is described further combined with specific embodiments below, its object is to better
Understand technical connotation of the invention, but protection scope of the present invention practical range not limited to the following.
Agents useful for same is analytical reagents in embodiment, and experimental water is secondary deionized water.
Embodiment 1
1, the preparation of Co-PBA nano particle
The preparation of the Prussian blue analogue particle (Co-PBA) of cobalt includes synthesizing and purifying two steps.
It accurately weighs 0.15mmol cobalt acetate to be dissolved in 40ml water, obtains solution A.Six cyanogen of 0.08mmol is accurately weighed simultaneously
Base cobalt acid potassium is dissolved in 40ml water, and PVP is added while stirring, obtains B solution.Solution A is added slowly in B solution while stirring
(adding about 10min), solution gradually becomes pink by colourless, after all adding, continues to stir 10min.By above-mentioned mixed liquor
4h is stood, remaining impurity is removed for several times with water and ethyl alcohol centrifuge washing immediately, is then freeze-dried spare.
2, the preparation of Co-PB/PAN nano fibrous membrane
It accurately weighs above-mentioned nano particle 0.584g to be dispersed in 52mL DMF, 5.84g PAN (Co- is added while stirring
PBA nano particle: PAN=10% continues to stir 12h, after PAN is completely dissolved, obtains the opaque thick solution of blue, i.e.,
For spinning solution.
It takes the above-mentioned spinning solution of 50ml to be put into five threading 10ml syringes respectively, chooses the metal that internal diameter is 0.6mm
Syringe needle, fltting speed are 1.0mL h-1It is used to prepare nanofiber.The distance between needle point and receiver board are 15cm, and voltage is
25.0kV, environment temperature are 23~30 DEG C, and ambient humidity is 30~40%.Then by the spinning film being prepared in 80 DEG C of vacuum
It dries and saves in baking oven.
3, the preparation of Co base carbon nanofiber membrane
Be placed on being sandwiched in graphite flake after above-mentioned nano fibrous membrane cut-parts in corundum boat, first in air with 5 DEG C/
Min, which is warming up in 280 DEG C, pre-oxidizes 2h, then is heat-treated 1000 DEG C in the tube furnace of nitrogen atmosphere with identical heating rate, protects
Warm 3h, is finally cooled to room temperature under nitrogen protection, obtains flexible self-supporting cobalt-based carbon nano-composite fiber structure electrolysis water system
Hydrogen oxygen electrocatalysis material.
4, Co base carbon nano-fiber is used for electrolysis water
Directly using self-supporting cobalt-based carbon nano-composite fiber as catalyst operation electrode, platinum is to electrode, and Ag/AgCl is ginseng
Than electrode, 1M KOH solution is that electrolyte carries out three electrode electro-catalysis test.
It is Co nanometers one-dimensional in cobalt-based carbon nano-composite fiber (appearance structure is as shown in attached drawing 1,2) manufactured in the present embodiment
Particle is doped in carbon backbone tertiary conductive network, promotes electron transmission and mass transfer, increases catalytic site, while porous carbon
Fiber provides the carrier of catalytic site and enhances electric conductivity.And production method is easy, green safe, the tunica fibrosa of preparation is soft
Property bent (such as attached drawing 3 (b) shown in), it can be achieved that large area continuous production (such as shown in attached drawing 3 (a)), is suitable for extensive
Electrolysis water production is industrialized, extremely wide application prospect is shown in electrolysis water field.
Electrochemical results show: under alkaline condition, the initiation site that electro-catalysis produces hydrogen (HER) is 70~100mV,
Current density is 10mAcm-2When current potential be 290~300mV (as shown in Fig. 4)；Electro-catalysis produces oxygen (OER) initiation site
1.24~1.30V, current density 10mAcm-2When current potential be 1.52~1.60V.
Embodiment 2
Referring to the method for embodiment 1, change the ratio (ratio of Co-PB and the PAN difference that Co-PB is adulterated in nanofiber
It is 0%, 3% and 5%), other conditions are constant.
The experimental results showed that in nanofiber the Prussian blue analog nanoparticle of cation doping base promote electron transmission and
Mass transfer increases catalytic site, is conducive to improve electrocatalysis characteristic, experimental result is as shown in Fig. 4.
Embodiment 3
Referring to the method for embodiment 1, using above-mentioned Co base carbon nano-composite fiber as catalyst operation electrode, platinum is to electricity
Pole, Ag/AgCl are reference electrode, and 0.5M sulfuric acid solution is that electrolyte carries out three electrode electro-catalysis test.
The experimental results showed that this catalyst all has good electrolysis water catalytic performance under acid and alkaline condition, and
Electro-catalysis H2-producing capacity under alkaline condition is better than under acid condition, and the electro-catalysis under acid condition produces oxygen performance and is better than acid
Under the conditions of property, experimental result is as shown in Fig. 5.
Claims (10)
1. a kind of preparation method of flexibility electrolysis water catalysis material, which comprises the following steps:
(1) the Prussian blue similar object nanoparticle of cobalt-based is prepared；
(2) it disperses the Prussian blue similar object nanoparticle of cobalt-based in organic solvent, adds polyacrylonitrile and spinning solution is made,
Co-PBA/PAN composite nano-fiber membrane is made in electrostatic spinning；
(3) pre-oxidation treatment is carried out to Co-PBA/PAN composite nano-fiber membrane, then carries out carbonization treatment in an inert atmosphere, made
Obtain the flexible electrolysis water catalysis material.
2. preparation method as described in claim 1, which is characterized in that in step (1), it is general to prepare cobalt-based using chemical synthesis
Shandong scholar's indigo plant analog nanoparticle, preparation method, comprising: first by cobalt acetate obtained solution A soluble in water, six cyano cobalt acid
Potassium, polyvinylpyrrolidone or neopelex is soluble in water obtains B solution, then solution A is added while stirring
Into B solution, reaction generates the Prussian blue similar object nanoparticle of cobalt-based.
3. preparation method as described in claim 1, which is characterized in that in step (2), the Prussian blue similar object nanoparticle of cobalt-based
The mass ratio of son and polyacrylonitrile is 0.1~1.5:10, and the mass percent of polyacrylonitrile is 6~12% in spinning solution.
4. preparation method as described in claim 1, which is characterized in that the condition of the electrostatic spinning are as follows: metal needle
Internal diameter is 0.6~0.7mm, and fltting speed is 0.8~1.5mL h-1, the distance between needle point and receiver board are 15~18cm, electricity
Pressure is 25~30kV, and environment temperature is 23~30 DEG C, and ambient humidity is 30~40%.
5. preparation method as described in claim 1, which is characterized in that in step (3), the condition of pre-oxidation treatment are as follows: air
260~280 DEG C of 0.5~2h of processing under atmosphere.
6. preparation method as described in claim 1, which is characterized in that in step (3), the condition of carbonization treatment are as follows: with 5~10
DEG C/min is warming up to 700~1100 DEG C, keep the temperature 1~6h.
7. preparation method as described in claim 1, which is characterized in that in step (3), the inert atmosphere is nitrogen or argon
Gas, gas flow rate 100sccm.
8. a kind of flexibility electrolysis water catalysis material as made from claim 1-7 described in any item preparation methods.
9. application of the flexibility electrolysis water catalysis material as claimed in claim 8 in water electrolysis hydrogen production oxygen.
10. application as claimed in claim 9, which is characterized in that the flexible electrolysis water catalysis material as catalysis electrode,
Platinum is auxiliary electrode, and Ag/AgCl is reference electrode；Electrolyte is alkalinity or acidic aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810804162.9A CN108940285A (en) | 2018-07-20 | 2018-07-20 | A kind of preparation method and application of flexibility electrolysis water catalysis material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810804162.9A CN108940285A (en) | 2018-07-20 | 2018-07-20 | A kind of preparation method and application of flexibility electrolysis water catalysis material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108940285A true CN108940285A (en) | 2018-12-07 |
Family
ID=64497956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810804162.9A Pending CN108940285A (en) | 2018-07-20 | 2018-07-20 | A kind of preparation method and application of flexibility electrolysis water catalysis material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108940285A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621969A (en) * | 2018-12-25 | 2019-04-16 | 江南大学 | A kind of self-supporting bimetallic nickel tungsten carbide complete solution water material and preparation method thereof |
| CN109913887A (en) * | 2019-03-15 | 2019-06-21 | 浙江工业大学 | A kind of flexible electrode catalyst and its preparation method and application of the nitrogen-doped carbon cladding Pt nanoparticle based on electrostatic spinning technique |
| CN110459740A (en) * | 2019-07-16 | 2019-11-15 | 五邑大学 | A kind of carbon nanotube cladding cobalt oxide material and its preparation method and application |
| CN110665533A (en) * | 2019-10-29 | 2020-01-10 | 深圳大学 | Non-noble metal doped carbon fiber membrane for purifying formaldehyde at room temperature and preparation method and application thereof |
| CN111229276A (en) * | 2020-01-16 | 2020-06-05 | 大连理工大学 | Double-layer composite electrolytic water anode catalyst and preparation method thereof |
| CN111974453A (en) * | 2020-05-28 | 2020-11-24 | 武汉工程大学 | Cobalt iron prussian blue derivative/carbon nanofiber composite material and preparation method and application thereof |
| CN112430898A (en) * | 2020-11-11 | 2021-03-02 | 山东大学 | Thermal or solvent dual-stimulus color-change response nanofiber membrane and preparation method and application thereof |
| CN112479179A (en) * | 2020-12-11 | 2021-03-12 | 南昌航空大学 | Preparation method of composite wave absorbing agent based on biomass material |
| CN112619649A (en) * | 2019-09-24 | 2021-04-09 | 中国石油大学(华东) | Nickel-cobalt-iron ternary oxide electrolytic water composite material and preparation method and application thereof |
| CN113106559A (en) * | 2021-03-02 | 2021-07-13 | 湖北工程学院 | Prussian blue-like derived metal oxide carbon nitrogen nanofiber flexible electrode material and preparation method and application thereof |
| CN113351259A (en) * | 2021-07-16 | 2021-09-07 | 河南科技大学 | Method for synthesizing disulfide by catalyzing mercapto compound oxidation with cobalt nanoparticle/carbon fiber composite mesoporous material |
| CN113969413A (en) * | 2021-10-29 | 2022-01-25 | 中国海洋大学 | Preparation method and application of cobalt phosphide-loaded porous carbon nanofiber electrocatalyst |
| CN114990884A (en) * | 2022-04-15 | 2022-09-02 | 山东大学 | Composite nanofiber membrane for degrading antibiotic pollutants through photo-thermal enhancement and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101874131A (en) * | 2007-11-30 | 2010-10-27 | 丰田自动车株式会社 | Process for production of carbon nanofiber carrying metal microparticles |
| CN105862174A (en) * | 2016-04-08 | 2016-08-17 | 合肥工业大学 | Preparation method of novel metal organic complex fibers and derivative porous carbon fibers thereof |
| CN105958073A (en) * | 2016-06-28 | 2016-09-21 | 王行柱 | Preparation method of flexible carbon nanofiber film for flexible positive electrode of foldable lithium battery |
| JP2017124393A (en) * | 2015-07-31 | 2017-07-20 | Toto株式会社 | Photocatalytic material and manufacturing method therefor |
| CN107715899A (en) * | 2017-10-26 | 2018-02-23 | 复旦大学 | A kind of nanometer phosphatization cobalt porous carbon nanofiber flexible membrane and preparation method thereof |
| CN109119649A (en) * | 2018-08-31 | 2019-01-01 | 广东工业大学 | A kind of cobalt atom is anchored on monatomic catalyst of the cobalt on carbon nano-fiber and its preparation method and application |
-
2018
- 2018-07-20 CN CN201810804162.9A patent/CN108940285A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101874131A (en) * | 2007-11-30 | 2010-10-27 | 丰田自动车株式会社 | Process for production of carbon nanofiber carrying metal microparticles |
| JP2017124393A (en) * | 2015-07-31 | 2017-07-20 | Toto株式会社 | Photocatalytic material and manufacturing method therefor |
| CN105862174A (en) * | 2016-04-08 | 2016-08-17 | 合肥工业大学 | Preparation method of novel metal organic complex fibers and derivative porous carbon fibers thereof |
| CN105958073A (en) * | 2016-06-28 | 2016-09-21 | 王行柱 | Preparation method of flexible carbon nanofiber film for flexible positive electrode of foldable lithium battery |
| CN107715899A (en) * | 2017-10-26 | 2018-02-23 | 复旦大学 | A kind of nanometer phosphatization cobalt porous carbon nanofiber flexible membrane and preparation method thereof |
| CN109119649A (en) * | 2018-08-31 | 2019-01-01 | 广东工业大学 | A kind of cobalt atom is anchored on monatomic catalyst of the cobalt on carbon nano-fiber and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 钱江华等: "普鲁士蓝衍生物Cd2[Fe(CN)6]•2H2O纳米棒的合成与表征", 《上海第二工业大学学报》 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621969B (en) * | 2018-12-25 | 2020-08-04 | 江南大学 | Self-supporting bimetal nickel-tungsten carbide fully-hydrolyzed material and preparation method thereof |
| CN109621969A (en) * | 2018-12-25 | 2019-04-16 | 江南大学 | A kind of self-supporting bimetallic nickel tungsten carbide complete solution water material and preparation method thereof |
| CN109913887A (en) * | 2019-03-15 | 2019-06-21 | 浙江工业大学 | A kind of flexible electrode catalyst and its preparation method and application of the nitrogen-doped carbon cladding Pt nanoparticle based on electrostatic spinning technique |
| CN110459740A (en) * | 2019-07-16 | 2019-11-15 | 五邑大学 | A kind of carbon nanotube cladding cobalt oxide material and its preparation method and application |
| CN110459740B (en) * | 2019-07-16 | 2022-06-24 | 五邑大学 | Carbon nanotube coated cobalt oxide material and preparation method and application thereof |
| CN112619649B (en) * | 2019-09-24 | 2022-08-16 | 中国石油大学(华东) | Nickel-cobalt-iron ternary oxide electrolytic water composite material and preparation method and application thereof |
| CN112619649A (en) * | 2019-09-24 | 2021-04-09 | 中国石油大学(华东) | Nickel-cobalt-iron ternary oxide electrolytic water composite material and preparation method and application thereof |
| CN110665533A (en) * | 2019-10-29 | 2020-01-10 | 深圳大学 | Non-noble metal doped carbon fiber membrane for purifying formaldehyde at room temperature and preparation method and application thereof |
| CN111229276A (en) * | 2020-01-16 | 2020-06-05 | 大连理工大学 | Double-layer composite electrolytic water anode catalyst and preparation method thereof |
| CN111229276B (en) * | 2020-01-16 | 2022-09-06 | 大连理工大学 | Double-layer composite type water electrolysis anode catalyst and preparation method thereof |
| CN111974453B (en) * | 2020-05-28 | 2023-04-07 | 武汉工程大学 | Cobalt iron prussian blue derivative/carbon nanofiber composite material and preparation method and application thereof |
| CN111974453A (en) * | 2020-05-28 | 2020-11-24 | 武汉工程大学 | Cobalt iron prussian blue derivative/carbon nanofiber composite material and preparation method and application thereof |
| CN112430898B (en) * | 2020-11-11 | 2022-06-07 | 山东大学 | Thermal or solvent dual-stimulus color-change response nanofiber membrane and preparation method and application thereof |
| CN112430898A (en) * | 2020-11-11 | 2021-03-02 | 山东大学 | Thermal or solvent dual-stimulus color-change response nanofiber membrane and preparation method and application thereof |
| CN112479179A (en) * | 2020-12-11 | 2021-03-12 | 南昌航空大学 | Preparation method of composite wave absorbing agent based on biomass material |
| CN112479179B (en) * | 2020-12-11 | 2023-09-29 | 南昌航空大学 | Preparation method of composite wave absorber based on biomass material |
| CN113106559A (en) * | 2021-03-02 | 2021-07-13 | 湖北工程学院 | Prussian blue-like derived metal oxide carbon nitrogen nanofiber flexible electrode material and preparation method and application thereof |
| CN113351259A (en) * | 2021-07-16 | 2021-09-07 | 河南科技大学 | Method for synthesizing disulfide by catalyzing mercapto compound oxidation with cobalt nanoparticle/carbon fiber composite mesoporous material |
| CN113351259B (en) * | 2021-07-16 | 2023-08-25 | 河南科技大学 | Method for synthesizing disulfide by catalyzing oxidization of sulfhydryl compound by cobalt nanoparticle/carbon fiber composite mesoporous material |
| CN113969413A (en) * | 2021-10-29 | 2022-01-25 | 中国海洋大学 | Preparation method and application of cobalt phosphide-loaded porous carbon nanofiber electrocatalyst |
| CN114990884A (en) * | 2022-04-15 | 2022-09-02 | 山东大学 | Composite nanofiber membrane for degrading antibiotic pollutants through photo-thermal enhancement and preparation method and application thereof |
| CN114990884B (en) * | 2022-04-15 | 2023-11-07 | 山东大学 | Composite nanofiber membrane for photo-thermal enhanced degradation of antibiotic pollutants and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108940285A (en) | A kind of preparation method and application of flexibility electrolysis water catalysis material | |
| CN108736031B (en) | Self-supporting PtCo alloy nanoparticle catalyst and preparation method and application thereof | |
| Barakat et al. | Cobalt/copper-decorated carbon nanofibers as novel non-precious electrocatalyst for methanol electrooxidation | |
| CN107587161B (en) | A kind of preparation method of rodlike NiFeSe/C electrolysis water catalyst | |
| CN108823600B (en) | Nickel-molybdenum carbide nanoparticle/carbon fiber composite nanomaterial, and preparation method and application thereof | |
| CN112941669B (en) | Metal-nitrogen co-doped carbon nanofiber material and preparation method and application thereof | |
| CN105642326B (en) | A kind of porous carbon carried metal composite material and preparation method and application | |
| CN109319753B (en) | Three-dimensional ordered macroporous ferronickel phosphide material and preparation and application thereof | |
| CN109908938A (en) | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT | |
| CN112194818B (en) | Copper/silver-based electrode with conductive bacterial cellulose composite membrane as substrate | |
| CN112968185B (en) | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure | |
| CN113061937B (en) | FeCoNiIrRu high-entropy nanoparticle catalytic material applied to acidic oxygen evolution reaction and preparation method thereof | |
| CN109950560A (en) | A kind of preparation method and applications of the carbon fiber loaded nitrogen-doped carbon nanocomposite based on biomass | |
| CN109621969B (en) | Self-supporting bimetal nickel-tungsten carbide fully-hydrolyzed material and preparation method thereof | |
| CN111841588A (en) | Preparation method and application of phosphide/carbon composite porous fiber | |
| CN112877812B (en) | Bimetal-doped metal phosphide nanofiber and preparation method thereof | |
| CN106362767A (en) | Nanometer platinum-copper alloy catalytic material for electrolysis of water | |
| CN110492083A (en) | A kind of preparation method of molybdenum disulfide/graphene/carbon multistage hole composite material | |
| CN110504456A (en) | It is a kind of based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode and its preparation method and application | |
| CN110921641B (en) | Transition metal phosphide nano material and preparation method and application thereof | |
| CN114784303B (en) | Preparation and application of rare earth-based organic framework anode material modified by copper polyphenol supermolecular network interface | |
| CN113604830B (en) | NiSe with micro-nano double-stage holes and high structural stability 2 -CoSe 2 /CFs composite material and preparation thereof | |
| CN113083272A (en) | FeNxPreparation method of nano-particle doped bamboo-like carbon nano-tube | |
| CN107694586B (en) | It a kind of graphene winding molybdenum carbide/carbosphere elctro-catalyst and preparation method thereof and applies in water electrolysis hydrogen production in acid condition | |
| CN111346658A (en) | Electrolytic water catalytic material of platinum-doped carbide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181207 |