CN110067004A - Ni-W-P/CNTs/CC catalysis electrode and preparation method and application - Google Patents
Ni-W-P/CNTs/CC catalysis electrode and preparation method and application Download PDFInfo
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- CN110067004A CN110067004A CN201910483895.1A CN201910483895A CN110067004A CN 110067004 A CN110067004 A CN 110067004A CN 201910483895 A CN201910483895 A CN 201910483895A CN 110067004 A CN110067004 A CN 110067004A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 87
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 46
- 239000004744 fabric Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000011065 in-situ storage Methods 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000006722 reduction reaction Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000000853 adhesive Substances 0.000 abstract description 11
- 239000007772 electrode material Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000008367 deionised water Substances 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229960000935 dehydrated alcohol Drugs 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 230000029087 digestion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a kind of Ni-W-P/CNTs/CC catalysis electrodes comprising the Ni-W-P composite catalyzing material of complex carbon material substrate (CNTs/CC) and growth in situ on the complex carbon material substrate (CNTs/CC)；The complex carbon material substrate includes carbon cloth (CC) and the carbon nanotube (CNTs) being grown on the carbon cloth (CC).Above-mentioned Ni-W-P/CNTs/CC catalysis electrode, catalytic electrode material Ni-W-P growth in situ is on complex carbon material substrate (CNTs/CC), complex carbon material itself is highly stable, it is good conductive carrier, growth in situ Ni-W-P composite catalyzing material on it, firm self-supporting catalysis electrode can be formed, and then electrode catalyst activity and stability can be improved.Above-mentioned Ni-W-P/CNTs/CC catalysis electrode, does not use adhesive, so avoid the problem that apparent poor catalytic activity and poor work stability brought by adhesive.The present invention also provides the preparation method and applications of above-mentioned Ni-W-P catalysis electrode.
Description
Technical field
The invention belongs to catalysis material technical field, it is related to a kind of Ni-W-P/CNTs/CC catalysis electrode and preparation method thereof
And application.
Background technique
Energy and environment problem is two main problems that the current whole mankind faces.Due to hydrogen have high-energy density and
The characteristics of zero-emission (not discharging any greenhouse gases), it is considered to be most potential clean energy resource carrier, while hydrogen
Each class of electronic devices and power vehicle can be driven by modes such as hydrogen fuel cells.
Water electrolysis hydrogen production is one of optimal sustainable hydrogen manufacturing approach, but due to liberation of hydrogen and oxygen evolution reaction overpotential
Height will lead to the reduction of electrolysis water reaction energy conversion ratio, therefore, in order to reduce energy loss, improves energy conversion efficiency, needs
Efficient catalytic electrode material is researched and developed, electrolysis water reaction liberation of hydrogen is reduced and analyses the overpotential of oxygen process.
Currently, noble metal base catalysis material shows very high electro catalytic activity, wherein Pt race metal and Precious metal oxidation
Object is respectively provided with preferable liberation of hydrogen and analysis oxygen electro catalytic activity.But since it is expensive, reserves are rare, significantly limit it
Industrial application, therefore find and can substitute the lower cost materials of noble metal and have become a hot topic of research.
In addition, most of catalysis material is all in powdered, it is necessary to be coated on basal electrode with adhesive, due to viscous
The presence of knot agent will lead to electrode resistance increase, active site is reduced and the diffusion admittance of masking reaction ion, greatly reduce
The apparent catalytic activity of catalytic electrode material.Meanwhile the adhesive force of adhesive itself is difficult to ensure, in electrolytic process,
The cured film of formation is easy to fall off, so as to cause the poor work stability of catalysis electrode.
Summary of the invention
Based on this, it is necessary to provide a kind of new Ni-W-P/CNTs/CC catalysis electrode.
A kind of Ni-W-P/CNTs/CC catalysis electrode, comprising:
Complex carbon material substrate；The complex carbon material substrate includes carbon cloth and the carbon nanometer being attached on the carbon cloth
Pipe；
And Ni-W-P composite catalyzing material, growth in situ is in the complex carbon material substrate.
Above-mentioned Ni-W-P/CNTs/CC catalysis electrode, catalytic electrode material Ni-W-P growth in situ is in complex carbon material substrate
On, it is good conductive carrier that complex carbon material itself is highly stable, on it growth in situ Ni-W-P composite catalyzing material,
Firm self-supporting catalysis electrode can be formed, and then electrode catalyst activity and stability can be improved.Above-mentioned Ni-W-P/
CNTs/CC catalysis electrode, does not use adhesive, so avoid apparent poor catalytic activity and the operation is stable brought by adhesive
Property difference problem.
The present invention also provides the preparation methods of above-mentioned Ni-W-P/CNTs/CC catalysis electrode.
A kind of preparation method of Ni-W-P/CNTs/CC catalysis electrode, includes the following steps:
Complex carbon material substrate；The complex carbon material substrate includes carbon cloth and is grown on the carbon cloth (CC)
Carbon nanotube；
The growth in situ Ni-W-P composite catalyzing material on the complex carbon material substrate (CNTs/CC).
The preparation method of above-mentioned Ni-W-P/CNTs/CC catalysis electrode is urged by way of growth in situ by Ni-W-P is compound
Change material to be attached in complex carbon material substrate, to avoid using adhesive, and then avoids apparently being catalyzed brought by adhesive
The problem of poor activity and poor work stability.
Optionally, the Ni-W-P composite catalyzing material is by Hydrothermal Growth in the complex carbon material substrate.
Optionally, the growth in situ Ni-W-P composite catalyzing material in the complex carbon material substrate, includes the following steps:
Hydro-thermal reaction liquid is provided；The hydro-thermal reaction liquid obtains as follows: firstly, according to following meterings than preparing
Deionized water solution:
Then adjusting pH value is still aging to obtain hydro-thermal reaction liquid to 5.0~7.0；
Hydro-thermal reaction liquid and the complex carbon material substrate are transferred in autoclave, hydro-thermal reaction is carried out, reaction is completed
After be cooled to room temperature, it is rear to take out cleaning, dry at room temperature.
Optionally, the temperature of the hydro-thermal reaction is 150~250 DEG C, and the time is 6~10h.
Optionally, the complex carbon material substrate by carbon cloth chemical vapor carbon deposition nanotube obtain.
Optionally, the complex carbon material substrate obtains as follows:
S1, carbon cloth is put into dense H2SO4With dense HNO3In the mixed solution that volume ratio is 1: 1~3: 1,3h is impregnated, it is rear to clean
And it dries；
S2, the carbon cloth for obtaining S1 are put into 0.1molL-1Ni(NO3)2·6H2O, 0.5molL-1CH4N2The solution of O
In, hydro-thermal reaction is carried out, it is rear to take out drying；
S3, the carbon cloth for obtaining S2 are put into atmosphere tube type furnace, carry out heat preservation reduction reaction；Cool to room temperature with the furnace, it will
Melamine place carbon cloth upstream, then carry out chemical vapour deposition reaction, cool to room temperature with the furnace, obtain carbon nanotube with
The compound carbon material substrate of carbon cloth.
Optionally, in step s3, the temperature for keeping the temperature reduction reaction is 500~700 DEG C, and the time is 0.5~1.5h.
Optionally, in step s3, the temperature of chemical vapour deposition reaction is 800~1000 DEG C, and the time is 1~3h；It protects
The warm time is 1~2h.
The present invention also provides application of the above-mentioned Ni-W-P/CNTs/CC catalysis electrode in electrolysis water.
Preferably, above-mentioned Ni-W-P/CNTs/CC catalysis electrode is used as the catalysis of electrolysis water liberation of hydrogen and oxygen evolution reaction electric simultaneously
Pole.
Detailed description of the invention
Fig. 1 is the SEM photograph of complex carbon material substrate prepared by the present invention；
Fig. 2 is the SEM photograph of Ni-W-P/CNTs/CC catalysis electrode prepared by the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, right below in conjunction with specific embodiment
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are only used to explain the present invention,
It is not intended to limit the present invention.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more
Any and all combinations of relevant listed item.
A kind of Ni-W-P/CNTs/CC catalysis electrode, including complex carbon material substrate (CNTs/CC) and Ni-W-P it is compound
Catalysis material.
Wherein, the main function of complex carbon material substrate is the conductive carrier as Ni-W-P composite catalyzing material.Specifically
Ground, the complex carbon material substrate (CNTs/CC) include carbon cloth (CC) and the carbon nanotube that is attached on carbon cloth (CC)
(CNTs).Further, carbon nanotube is attached on carbon cloth (CC) by chemical vapor deposition manner.
Wherein, Ni-W-P composite catalyzing material is the main active catalytic part of catalysis electrode, and growth in situ is compound
In carbon material substrate (CNTs/CC).
Above-mentioned Ni-W-P/CNTs/CC catalysis electrode, catalytic electrode material Ni-W-P growth in situ is in complex carbon material substrate
(CNTs/CC) on, it is good conductive carrier that complex carbon material (CNTs/CC) itself is highly stable, on it growth in situ
Ni-W-P composite catalyzing material can form firm self-supporting catalysis electrode, and then electrode catalyst activity and steady can be improved
It is qualitative.Above-mentioned Ni-W-P/CNTs/CC catalysis electrode, does not use adhesive, so avoid apparently catalysis work brought by adhesive
Property difference and the problem of poor work stability.
The present invention also provides the preparation methods of above-mentioned Ni-W-P/CNTs/CC catalysis electrode.
A kind of preparation method of Ni-W-P/CNTs/CC catalysis electrode, includes the following steps:
It provides complex carbon material substrate (CNTs/CC)；The complex carbon material substrate includes carbon cloth (CC) and is attached to described
Carbon nanotube (CNTs) on carbon cloth；
The growth in situ Ni-W-P composite catalyzing material in the complex carbon material substrate.
Wherein, in a preferred embodiment, complex carbon material substrate (CNTs/CC) passes through chemical on carbon cloth (CC)
Be vapor-deposited carbon nanotube (CNTs) acquisition.That is, carbon nanotube (CNTs) is grown in by chemical vapor deposition manner
On carbon cloth (CC).
Further, complex carbon material substrate (CNTs/CC) obtains as follows:
S1, carbon cloth (CC) is put into dense H2SO4With dense HNO3In the mixed solution that volume ratio is 1: 1~3: 1,3h is impregnated, after
It cleans and dries；
S2, the carbon cloth (CC) that S1 is obtained is put into 0.1molL-1Ni(NO3)2·6H2O, 0.5molL-1CH4N2O's is molten
In liquid, hydro-thermal reaction is carried out, it is rear to take out drying；
S3, the carbon cloth (CC) that S2 is obtained is put into atmosphere tube type furnace, carries out heat preservation reduction reaction；Cool to room with the furnace
Melamine is placed the upstream of carbon cloth (CC), then carries out chemical vapour deposition reaction, cool to room temperature with the furnace, obtain by temperature
Carbon nanotube (CNTs) and carbon cloth (CC) compound carbon material substrate.
In step sl, in a preferred embodiment, the cleaning agent for cleaning use can be dehydrated alcohol, also or third
Ketone.
In step sl, in a preferred embodiment, the temperature of drying is 60 DEG C.It is, of course, understood that of the invention
Drying temperature be not limited thereto.
In step s 2, in a preferred embodiment, the solvent of solution is the mixture of ethylene glycol and deionized water, wherein
The volume ratio of ethylene glycol and deionized water is 1: 1.
In step s 2, in a preferred embodiment, the temperature of hydro-thermal reaction is 120~160 DEG C, and the time is 6~12h.
In step s 2, in a preferred embodiment, the temperature of drying is also 60 DEG C.It is, of course, understood that this hair
Bright drying temperature is not limited thereto.
In step s3, in a preferred embodiment, the temperature for keeping the temperature reduction reaction is 500~700 DEG C, the time 0.5
~1.5h.
In step s3, in a preferred embodiment, atmosphere is H in atmosphere tube type furnace2With the mixed atmosphere of Ar.More into one
Step ground, it is preferred that H2With H in the mixed atmosphere of Ar2Volume ratio be 5~10%.
In step s3, in a preferred embodiment, the temperature of chemical vapour deposition reaction is 800~1000 DEG C, the time
For 1~3h；Soaking time is 1~2h.
In a preferred embodiment, Ni-W-P composite catalyzing material is by Hydrothermal Growth in the complex carbon material substrate
(CNTs/CC) on.
In a particular embodiment, hydro-thermal method includes the following steps: hydro-thermal reaction liquid and the complex carbon material substrate
(CNTs/CC) it is transferred in autoclave, carries out hydro-thermal reaction, be cooled to room temperature after the reaction was completed, it is rear to take out cleaning, it does at room temperature
It is dry.
Wherein, hydro-thermal reaction liquid obtains as follows:
Firstly, according to following meterings than preparing deionized water solution:
Then adjusting pH value is still aging to obtain hydro-thermal reaction liquid to 5.0~7.0；
It is highly preferred that adjusting pH value by ammonium hydroxide or hydrochloric acid.It can avoid doing to avoid other foreign ions are introduced in this way
It disturbs.
It is highly preferred that digestion time is more than or equal to 12h, that is to say, that the solution left standstill after adjusting pH value is aged 12
Hour or more.
Optionally, the temperature of above-mentioned hydro-thermal reaction is 150~250 DEG C, and the time is 6~10h.
The preparation method of above-mentioned Ni-W-P/CNTs/CC catalysis electrode is urged by way of growth in situ by Ni-W-P is compound
Change material to be attached on complex carbon material substrate (CNTs/CC), to avoid using adhesive, and then avoid brought by adhesive
The problem of apparent poor catalytic activity and poor work stability.
The present invention also provides application of the above-mentioned Ni-W-P/CNTs/CC catalysis electrode in electrolysis water.
Preferably, above-mentioned Ni-W-P/CNTs/CC catalysis electrode is used as the catalysis of electrolysis water liberation of hydrogen and oxygen evolution reaction electric simultaneously
Pole.
It is, of course, understood that can also only make the catalyst of electrolysis water evolving hydrogen reaction, it can also only make electrolysis elutriation
The catalysis electrode of oxygen reaction.
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1
The preparation of complex carbon material substrate (CNTs/CC):
The carbon cloth (CC) of 1.0 × 1.0mm is put into dense H2SO4With dense HNO33h is impregnated in the mixed solution that volume ratio is 3: 1
After clean, after dehydrated alcohol, acetone successively clean, 60 DEG C of dryings.
Carbon cloth (CC) after drying is put into the molten of 0.1molL-1Ni (NO3) 26H2O, 0.5molL-1CH4N2O
In liquid (solvent is the ethylene glycol of volume ratio 1: 1 and the mixture of deionized water), taken out after hydro-thermal reaction 6h at 120 DEG C, 60
DEG C drying with water bath.
Carbon cloth (CC) after drying with water bath is put into atmosphere tube type furnace, heat preservation reduction reaction 0.5h is carried out at 500 DEG C,
It cools to room temperature with the furnace, then melamine is placed to the upstream of carbon cloth (CC), in 800 DEG C of progress chemical vapour deposition reaction 1h,
Soaking time is 1h, cools to room temperature with the furnace, obtains complex carbon material substrate (CNTs/CC).
Hydro-thermal reaction liquid, solution composition are prepared using deionized water are as follows: Ni (NO3) 26H2O 0.1molL-1,
Na2WO42H2O 0.1molL-1, NaH2PO2H2O 0.06molL-1, NH4Cl 0.01molL-1,
Na3C6H5O7·2H2O 0.2mol·L-1.Solution ph is adjusted to 5.5, is then allowed to stand ageing 12h.
The above-mentioned complex carbon material substrate (CNTs/CC) prepared and hydro-thermal reaction liquid are transferred together equipped with polytetrafluoro
In the autoclave of ethylene liner, the hydro-thermal reaction 8h at 150 DEG C takes out after being cooled to room temperature, through deionized water, dehydrated alcohol according to
After secondary ultrasonic cleaning, dry at room temperature.
Obtained Ni-W-P/CNTs/CC catalysis electrode, is denoted as A1.
Embodiment 2
The preparation of complex carbon material substrate (CNTs/CC):
The carbon cloth (CC) of 1.0 × 1.0mm is put into dense H2SO4 and dense HNO3 volume ratio to impregnate in 3: 1 mixed solution
It is cleaned after 3h, after dehydrated alcohol, acetone successively clean, 60 DEG C of dryings.
Carbon cloth (CC) after drying is put into 0.1molL-1Ni (NO3) 26H2O, 0.5molL-1 CH4N2O's
In solution (solvent is the ethylene glycol of volume ratio 1: 1 and the mixture of deionized water), taken out after hydro-thermal reaction 6h at 150 DEG C,
60 DEG C of drying with water baths.
Carbon cloth (CC) after drying with water bath is put into atmosphere tube type furnace, heat preservation reduction reaction 1h is carried out at 600 DEG C, with
Furnace is cooled to room temperature, then melamine is placed to the upstream of carbon cloth (CC), in 1000 DEG C of progress chemical vapour deposition reaction 2h, is protected
The warm time is 2h, cools to room temperature with the furnace, obtains complex carbon material substrate (CNTs/CC).
Hydro-thermal reaction liquid, solution composition are as follows: Ni (NO are prepared using deionized water3)2·6H2O 0.2mol·L-1,
Na2WO4·2H2O 0.1mol·L-1, NaH2PO2·H2O 0.06mol·L-1, NH4Cl 0.01mol·L-1, Na3C6H5O7·
2H2O 0.2mol·L-1, adjusting solution ph is 6.5, is then allowed to stand ageing 12h.
The above-mentioned complex carbon material substrate (CNTs/CC) prepared and hydro-thermal reaction liquid are transferred together equipped with polytetrafluoro
In the autoclave of ethylene liner, the hydro-thermal reaction 8h at 200 DEG C takes out after being cooled to room temperature, through deionized water, dehydrated alcohol according to
After secondary ultrasonic cleaning, dry at room temperature.
Obtained Ni-W-P/CNTs/CC catalysis electrode, is denoted as A2.
Embodiment 3
Complex carbon material substrate (CNTs/CC) is prepared according to the method in embodiment 1.
Hydro-thermal reaction liquid is prepared using deionized water, solution composition is the same as embodiment 1.Adjusting solution ph is 6.5, then quiet
Set ageing 12h.
The above-mentioned complex carbon material substrate (CNTs/CC) prepared and hydro-thermal reaction liquid are transferred together equipped with polytetrafluoro
In the autoclave of ethylene liner, the hydro-thermal reaction 8h at 180 DEG C takes out after being cooled to room temperature, through deionized water, dehydrated alcohol according to
After secondary ultrasonic cleaning, dry at room temperature.
Obtained Ni-W-P/CNTs/CC catalysis electrode, is denoted as A3.
Embodiment 4
Complex carbon material substrate (CNTs/CC) is prepared according to the method for embodiment 2.
Hydro-thermal reaction liquid is prepared using deionized water, solution composition is the same as embodiment 1.Adjusting solution ph is 6.5, then quiet
Set ageing 12h.
The above-mentioned complex carbon material substrate (CNTs/CC) prepared and hydro-thermal reaction liquid are transferred together equipped with polytetrafluoro
In the autoclave of ethylene liner, the hydro-thermal reaction 8h at 180 DEG C takes out after being cooled to room temperature, through deionized water, dehydrated alcohol according to
After secondary ultrasonic cleaning, dry at room temperature.
Obtained Ni-W-P/CNTs/CC catalysis electrode, is denoted as A4.
Embodiment 5
Complex carbon material substrate (CNTs/CC) is prepared according to the method for embodiment 1.
Solution is prepared using deionized water, solution composition is the same as embodiment 2.Adjusting solution ph is 7, is then allowed to stand ageing
12h。
The above-mentioned complex carbon material substrate (CNTs/CC) prepared and hydro-thermal reaction liquid are transferred together equipped with polytetrafluoro
In the autoclave of ethylene liner, the hydro-thermal reaction 8h at 200 DEG C takes out after being cooled to room temperature, through deionized water, dehydrated alcohol according to
After secondary ultrasonic cleaning, dry at room temperature.
Obtained Ni-W-P/CNTs/CC catalysis electrode, is denoted as A5.
Performance test
Object mutually detects:
Obtain the object phase of Ni-W-P/CNTs/CC catalysis electrode respectively by X-ray diffractometer, test result is shown in Table 1.
Overpotential detection:
In three-electrode system, in 1molL-1It is 10mA in current density in electrolysis water reaction in KOH solution
cm-2Under, respectively using Ni-W-P/CNTs/CC catalysis electrode A1-A5 as cathode, measure overpotential of hydrogen evolution；Ni-W-P is urged respectively
Polarizing electrode A1-A5 measures overpotential for oxygen evolution as anode.Test result is shown in Table 1.
Tank voltage detection:
In two electrode systems, use Ni-W-P/CNTs/CC catalysis electrode A1-A5 simultaneously as 1molL-1 KOH respectively
The cathode and anode in electrolysis water reaction in solution, measurement current density is 10mAcm-2Tank voltage.Test result is shown in Table
1。
1 Ni-W-P catalysis electrode of table is analyzed and characterized and the performance test results
From table 1 it follows that embodiment 1-5's is smaller in overpotential of hydrogen evolution, overpotential for oxygen evolution and tank voltage,
The process of liberation of hydrogen and oxygen evolution reaction can obviously be accelerated, improve the efficiency of electrolysis water reaction；And then it proves provided by the present invention
Ni-W-P/CNTs/CC catalysis electrode, the anode and cathode that can not only react simultaneously as electrolysis water, accelerates liberation of hydrogen and analysis
The process of oxygen reaction, improves the efficiency of electrolysis water reaction.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of Ni-W-P/CNTs/CC catalysis electrode characterized by comprising
Complex carbon material substrate；The complex carbon material substrate includes carbon cloth and the carbon nanotube that is grown on the carbon cloth；
And Ni-W-P composite catalyzing material, growth in situ is in the complex carbon material substrate.
2. a kind of preparation method of Ni-W-P/CNTs/CC catalysis electrode, which comprises the steps of:
Complex carbon material substrate is provided；The complex carbon material substrate includes that carbon cloth and the carbon being grown on the carbon cloth are received
Mitron；
The growth in situ Ni-W-P composite catalyzing material in the complex carbon material substrate.
3. the preparation method of Ni-W-P/CNTs/CC catalysis electrode according to claim 2, which is characterized in that the Ni-
W-P composite catalyzing material is by Hydrothermal Growth in the complex carbon material substrate.
4. the preparation method of Ni-W-P/CNTs/CC catalysis electrode according to claim 3, which is characterized in that described multiple
Growth in situ Ni-W-P composite catalyzing material in carbon material substrate is closed, is included the following steps:
Hydro-thermal reaction liquid is provided；The hydro-thermal reaction liquid obtains as follows: firstly, according to following meterings than prepare go from
Sub- aqueous solution:
Then adjusting pH value is still aging to obtain hydro-thermal reaction liquid to 5.0~7.0；
Hydro-thermal reaction liquid and the complex carbon material substrate are transferred in autoclave, hydro-thermal reaction is carried out, it is cold after the reaction was completed
But rear to take out cleaning to room temperature, it dries at room temperature.
5. the preparation method of Ni-W-P/CNTs/CC catalysis electrode according to claim 4, which is characterized in that the hydro-thermal
The temperature of reaction is 150~250 DEG C, and the time is 6~10h.
6. the preparation method of Ni-W-P/CNTs/CC catalysis electrode according to claim 2, which is characterized in that described compound
Carbon material substrate by carbon cloth chemical vapor carbon deposition nanotube obtain.
7. the preparation method of Ni-W-P/CNTs/CC catalysis electrode according to claim 6, which is characterized in that described compound
Carbon material substrate obtains as follows:
S1, carbon cloth is put into dense H2SO4With dense HNO3In the mixed solution that volume ratio is 1: 1~3: 1,3h is impregnated, cleans and dries afterwards
It is dry；
S2, the carbon cloth for obtaining S1 are put into 0.1molL-1 Ni(NO3)2·6H2O, 0.5molL-1 CH4N2In the solution of O,
Hydro-thermal reaction is carried out, it is rear to take out drying；
S3, the carbon cloth for obtaining S2 are put into atmosphere tube type furnace, carry out heat preservation reduction reaction；Room temperature is cooled to the furnace, by trimerization
Cyanamide places the upstream of carbon cloth, then carries out chemical vapour deposition reaction, cools to room temperature with the furnace, obtains carbon nanotube and carbon cloth
Compound carbon material substrate.
8. the preparation method of Ni-W-P/CNTs/CC catalysis electrode according to claim 7, which is characterized in that in step S3
In, the temperature for keeping the temperature reduction reaction is 500~700 DEG C, and the time is 0.5~1.5h.
9. the preparation method of Ni-W-P/CNTs/CC catalysis electrode according to claim 7, which is characterized in that in step S3
In, the temperature of chemical vapour deposition reaction is 800~1000 DEG C, and the time is 1~3h；Soaking time is 1~2h.
10. application of the Ni-W-P/CNTs/CC catalysis electrode of claim 1 in electrolysis water.
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