CN109797404A - The binary metal phosphide and preparation method and application of molybdenum trioxide (tungsten) regulation - Google Patents
The binary metal phosphide and preparation method and application of molybdenum trioxide (tungsten) regulation Download PDFInfo
- Publication number
- CN109797404A CN109797404A CN201910076389.0A CN201910076389A CN109797404A CN 109797404 A CN109797404 A CN 109797404A CN 201910076389 A CN201910076389 A CN 201910076389A CN 109797404 A CN109797404 A CN 109797404A
- Authority
- CN
- China
- Prior art keywords
- regulation
- electrode
- moo
- test
- cop
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- RYFIDLXZHPNUFF-UHFFFAOYSA-N [Mo].O=[W](=O)=O Chemical compound [Mo].O=[W](=O)=O RYFIDLXZHPNUFF-UHFFFAOYSA-N 0.000 title abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 137
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- 239000006260 foam Substances 0.000 claims abstract description 46
- 229910015675 MoO3−x Inorganic materials 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000003491 array Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000012360 testing method Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 30
- 230000007812 deficiency Effects 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- 238000000840 electrochemical analysis Methods 0.000 claims description 7
- 229940101209 mercuric oxide Drugs 0.000 claims description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 7
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004364 calculation method Methods 0.000 claims description 6
- 230000005518 electrochemistry Effects 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 230000002441 reversible effect Effects 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000008595 infiltration Effects 0.000 abstract description 2
- 238000001764 infiltration Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 description 7
- 239000010949 copper Substances 0.000 description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 2
- KBNUQQRKODIBRW-UHFFFAOYSA-N [Cu].[W].[Co] Chemical compound [Cu].[W].[Co] KBNUQQRKODIBRW-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ICPIKPGERJWARK-UHFFFAOYSA-N cobalt copper molybdenum Chemical compound [Co][Cu][Mo] ICPIKPGERJWARK-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 229910018864 CoMoO4 Inorganic materials 0.000 description 1
- 229910005809 NiMoO4 Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- Catalysts (AREA)
Abstract
The present invention relates to the binary metal phosphides and preparation method and application of a kind of molybdenum trioxide (tungsten) regulation.It is matrix that adopt the present invention, which be by nickel foam, prepares column presoma by hydro-thermal method first, then passes through the method for low temperature phosphor formation MoO3‑xThe columnar arrays structure of the porous surface of regulation.There are amorphous MoO in the structure3‑xAnd CoP/Ni5P4Hetero-junctions is conducive to the activation of hydrone and the precipitation of hydrogen.In addition, vertical porous cylindrical array structure can speed up the infiltration of electrolyte, exposes more electrochemical surface areas and gas is facilitated to be desorbed from catalyst surface.This structure has very big potential using value in electro-catalysis field.
Description
Technical field
The present invention relates to the binary metal phosphides and preparation method and application of a kind of molybdenum trioxide (tungsten) regulation, specifically
Take function as the function nano design of material and modification technique of guiding, grows molybdenum cobalt nickel on nickel foam substrate using hydro-thermal method
Column presoma and low temperature phosphor technology prepare porous columnar arrays structure.
Background technique
Because preparation process is simple with equipment, and free of contamination advantage, electrochemistry total moisture solution be considered as prepare it is high-purity
The promising approach of hydrogen.Theoretical calculation with the experimental results showed that binary transition metal phosphide have good electrolysis water performance,
This is mainly due to the adsorption energy of alloy effect and suitable hydrogen between its good electric conductivity, binary metal.But in alkali
Under the conditions of property, due to its poor hydrophily, water activates that form hydrionic process slower.Amorphous metal oxide has
Good hydrophily can speed up the activation of water, generate more hydrogen ions.In addition, electrocatalytic reaction also requires material to have
The desorption performance of good mass transfer and gas.Porous columnar arrays structure is capable of providing more specific surface areas, Ke Yibao
Reveal the active site of more electrochemical reactions.Simultaneously as its porous structure, the process of osmosis of electrolyte are accelerated,
It can speed up electrochemical reaction.In addition, porous structure is conducive to desorption of the gas molecule from electrode surface, and then enhances electricity and urge
Change performance.Hydro-thermal method prepares CoMoO4/NiMoO4Columnar arrays structure uses the column structure prepared to continue to repair as presoma
Porous columnar arrays structure is adornd into not realize also.
Summary of the invention
The object of the present invention is to provide a kind of molybdenum trioxide (tungsten) to regulate and control binary metal phosphide and preparation method and application,
Realization uses the column structure prepared to continue to be modified into porous columnar arrays structure as presoma.
A kind of binary metal phosphide of molybdenum trioxide regulation provided by the invention is the porous cylindrical array structure of hydridization,
The molybdenum trioxide (tungsten) is generated in-situ amorphous structure, and column volume array is meso-hole structure, pore diameter range 5-
10 nanometers, the length of column is 15-30 microns, and diameter is 3-5 microns;There are amorphous MoO in its structure3-xAnd
CoP/Ni5P4Hetero-junctions, wherein x is the quantity of Lacking oxygen, 0 < X < 1;
Preparation method includes the column presoma and low temperature phosphor for growing molybdenum cobalt nickel on nickel foam substrate using hydro-thermal method.
In the binary metal phosphide of the molybdenum trioxide regulation provided by the invention, three oxygen of the molybdenum trioxide
Change tungsten to replace;The CoP/Ni5P4Hetero-junctions can use CoP/CuP or Ni5P4/ CuP or CuP/Ni5P4Instead of.
The preparation method of the binary metal phosphide of molybdenum trioxide provided by the invention regulation the following steps are included:
1) foam nickel surface is cleaned;Nickel foam is immersed in 0.01-1 M dilute hydrochloric acid, the ultrasound in ultrasonic cleaning instrument
Concussion 5-50 minutes, removes the NiO film of surface compact;Ultrasonic cleaning is clean in deionized water again, then ultrasonic in acetone
Cleaning;It is finally cleaned in dehydrated alcohol, the nickel foam cleaned up is placed in 20-80 DEG C of vacuum oven dry 3-20
h;
2) hydro-thermal method grows the column presoma of molybdenum cobalt nickel on nickel foam substrate;By 0.002-0.5 M Ni (NO3)3·5H2O、
0.002-0.5 M Co(NO3)2、0.004-1 M Na2MoO4、0.002-0.8 M NH4F is added in reaction kettle, magnetic agitation
10-60 min obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, is 100-180 DEG C in temperature
Baking oven in keep the temperature 5-10 hours;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;It is placed in 30-
Dry 2-10 h in 80 DEG C of vacuum oven;
3) low temperature phosphor prepares porous columnar arrays structure, and obtained molybdenum cobalt nickel column shape presoma is placed in pipe reaction furnace
Downstream, sodium hypophosphite are placed in the upstream of pipe reaction furnace, first by pipe reaction stove evacuation, are passed through argon gas, flow velocity 10-
100 cc min-1;Select heating rate for 2-20 DEG C/min, in 200-600 DEG C of heat preservation 1-6 h;After natural cooling, deionized water
The impurity for rinsing surface, obtains amorphous state deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure.
Further, the application of the binary metal phosphide regulated and controled the present invention provides molybdenum trioxide or tungstic acid, including
(molybdenum trioxide described in detail below is answered for application in terms of for electrocatalytic hydrogen evolution, Electrochemical oxygen evolution and electrochemistry total moisture solution
With).
The binary metal phosphide of molybdenum trioxide regulation for the application in terms of electrocatalytic hydrogen evolution the following steps are included:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is straight
It connecing and is used as working electrode, tested in three-electrode system, be respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode,
1 M KOH is electrolyte, is first carried out processing 30 minutes of logical argon gas to electrolyte before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., in the potential region of -1.232 V of V to -0.832
The CV circulation for carrying out 100 circles, LSV test is then carried out in the potential region of -1.232 V of V to -0.832, is come with this to non-
Crystalline defects type MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The Hydrogen Evolution Performance of array structure is assessed;
3) the iR compensation and conversion of current potential:
In this during, all current potentials all pass through 90% iR compensation, in addition, the current potential in this experiment will be converted into it is reversible
Hydrogen potential, specific calculation formula are as follows: ERHE=EHg/HgO+0.098+0.059pH。
It is 10 mA cm that experimental result, which is shown in current density,-2When, overpotential is only 90 mV, shows good electricity
Catalytic hydrogen evolution performance.
The binary metal phosphide of molybdenum trioxide regulation for the application in terms of Electrochemical oxygen evolution the following steps are included:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is straight
It connecing and is used as working electrode, tested in three-electrode system, be respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode,
1 M KOH is electrolyte, is first carried out processing 30 minutes of logical argon gas to electrolyte before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., in the potential region of 0.268 V to 0.768 V into
The CV circulation that row 100 encloses, the test of LSV is then carried out in the potential region of 0.268 V to 0.768 V, is come with this to amorphous
State deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The analysis oxygen performance of array structure is assessed;
3) the iR compensation and conversion of current potential:
In this during, all current potentials all pass through 90% iR compensation, in addition, the current potential in this experiment will be converted into it is reversible
Hydrogen potential, specific calculation formula are as follows: ERHE=EHg/HgO+0.098+0.059pH。
The experimental results showed that porous cylindrical array has catalytic efficiency more higher than business iridium dioxide, it is in current density
50 mA cm-2When, overpotential has dropped close to 100 mV, it is shown that its higher practical application value.
The binary metal phosphide of molybdenum trioxide regulation includes following for the application in terms of electrochemistry total moisture solution field
Step:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is straight
It connecing and is used as working electrode, tested in three-electrode system, be respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode,
1 M KOH is electrolyte.First electrolyte is carried out processing 30 minutes of logical argon gas before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., carries out 100 circles in the potential region of 0 V to 1.7 V
CV circulation.Then LSV test is carried out in the potential region of 0 V to 1.7 V, is come with this to amorphous state deficiency MoO3-xIt adjusts
The porous cylindrical CoP/Ni of control5P4The total moisture solution performance of array structure is assessed;
3) the iR compensation of current potential: in this during, all current potentials all pass through 90% iR compensation.
By the hybridization porous columnar arrays assembling of amorphous state oxygen defect molybdenum trioxide (tungsten) in situ regulation binary metal phosphide
Complete solution water electrode system show good complete solution it is aqueous can, current density be 10 mA cm-2When, overpotential is only 279
MV shows the electrode system formed than business platinum carbon and iridium dioxide more preferably catalytic performance.
The present invention provides a kind of molybdenum trioxide (tungsten) regulation binary metal phosphide and preparation method and application, realize and use
The column structure prepared continues to be modified into porous columnar arrays structure as presoma.The present invention can not only prepare amorphous
State deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure, and the ratio of change cobalt source and nickel source can be passed through
To regulate and control the electronic structure of hetero-junctions.This porous orthogonal array structure can increase the contact area with electrolyte, exposure
More electrochemical reaction sites, accelerate the gas generated to remove from the surface of material.It is expected to prepare other using this technology
Amorphous state MoO3-xThe porous cylindrical array structure of regulation, and it is used as the catalyst of electrocatalytic decomposition water.
The present invention solves the problems, such as that water activates slow in alkaline environment.Meanwhile porous columnar arrays structure can
The active site of the more electrochemical reactions of exposure, accelerates the infiltration of electrolyte, is conducive to gas molecule from the de- of electrode surface
It is attached, and then accelerate electrocatalysis characteristic.The reason of its performance of high spot reviews increases, long-time stability and method it is pervasive
Property.Main difficult point is how to be accurately controlled condition, prepares porous columnar arrays structure.
Detailed description of the invention
Fig. 1 is amorphous state deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The flow chart of array structure;Wherein (a)
The washing of nickel foam, (b) hydro-thermal method prepares molybdenum cobalt nickel column shape presoma, and (c) low temperature phosphor prepares amorphous state deficiency
MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure;
Fig. 2 is the stereoscan photograph (a) and power spectrum test result (b-b5) of molybdenum cobalt nickel column shape presoma;(a) and Fig. 2 in Fig. 2
In (b) be molybdenum cobalt nickel column shape presoma stereoscan photograph, (b1-b4) is the energy stave of molybdenum cobalt nickel column shape presoma in Fig. 2
Sign is as a result, column presoma contains tetra- kinds of elements of Mo, Co, Ni and O as we can see from the figure, and is evenly distributed in column forerunner
In body;
Fig. 3 is MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Scanning electron microscope (SEM) the observation result and power spectrum of array structure are surveyed
Test result: (a) low power large area porous cylindrical CoP/Ni5P4Array structure, (b) the porous knot of the damaged surface of high power small area
Structure, (c) single MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure and corresponding power spectrum test result;
Fig. 4 is MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The transmission electron microscope (TEM) of array structure: (a) porous under low power
Column structure, (b) high-resolution transmission electron microscope, amorphous substance MoO3-x, two kinds of corresponding substances of obvious crystal structure are respectively
CoP(0.245 nm) and Ni5P4(0.197 nm);
Fig. 5 is MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The electrochemistry liberation of hydrogen (a) of array structure (Mo-CoNiP), electrification
Learn analysis oxygen (b) and total moisture solution (c) the performance test results.
Specific embodiment
Combined with specific embodiments below, it is further elaborated on the present invention.The experiment of actual conditions is not specified in embodiment
Method, usually according to normal condition and condition described in handbook, or according to the normal condition proposed by manufacturer;Used is logical
With equipment, material, reagent etc., it is commercially available unless otherwise specified.
Embodiment 1
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes, remove surface compact in supersonic cleaning machine
NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaning in dehydrated alcohol will
The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares molybdenum cobalt nickel column shape presoma:
By 0.002 M Ni (NO3)3·5H2O、0.002 M Co(NO3)2、0.004 M Na2MoO4、0.1 M NH4F is added to
In reaction kettle, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, in temperature
10 hours are kept the temperature in the baking oven that degree is 160 DEG C;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;
Dry 6 h are placed in 60 DEG C of vacuum oven.
(3) low temperature phosphor prepares porous columar structure:
Obtained molybdenum cobalt nickel column shape presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace
Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min,
450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency MoO3-xWhat is regulated and controled is more
Hole column CoP/Ni5P4Array structure.
Embodiment 2
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes, remove surface compact in supersonic cleaning machine
NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaning in dehydrated alcohol will
The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares tungsten-cobalt nickel column shape presoma:
By 0.002 M Ni (NO3)3·5H2O、0.002 M Co(NO3)2、0.004 M Na2WO4、0.1 M NH4F is added to instead
It answers in kettle, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, in temperature
To keep the temperature 10 hours in 160 DEG C of baking ovens;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;It sets
Dry 6 h in 60 DEG C of vacuum oven.
(3) low temperature phosphor prepares porous columar structure:
Obtained tungsten-cobalt nickel column shape presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace
Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min,
450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency WO3-xWhat is regulated and controled is porous
Column CoP/Ni5P4Array structure.
Embodiment 3
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes, remove surface compact in supersonic cleaning machine
NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaning in dehydrated alcohol will
The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares molybdenum cupro-nickel column presoma:
By 0.002 M Ni (NO3)3·5H2O、0.002 M Cu(NO3)2、0.004 M Na2MoO4、0.1 M NH4F is added to
In reaction kettle, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, in temperature
10 hours are kept the temperature in the baking oven that degree is 160 DEG C;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;
Dry 6 h are placed in 60 DEG C of vacuum oven.
(3) low temperature phosphor prepares porous columar structure:
Obtained molybdenum cupro-nickel column presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace
Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min,
450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency MoO3-xWhat is regulated and controled is more
Hole column CuP/Ni5P4Array structure.
Embodiment 4
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes, remove surface compact in supersonic cleaning machine
NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaning in dehydrated alcohol will
The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares molybdenum cobalt copper post shape presoma:
By 0.002 M Cu (NO3)2、0.002 M Co(NO3)2、0.004 M Na2MoO4、0.1 M NH4F is added to reaction kettle
In, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, is in temperature
10 hours are kept the temperature in 160 DEG C of baking oven;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;It is placed in
Dry 6 h in 60 DEG C of vacuum oven.
(3) low temperature phosphor prepares porous columar structure:
Obtained molybdenum cobalt copper post shape presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace
Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min,
450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency MoO3-xWhat is regulated and controled is more
Hole column CoP/CuP array structure.
Embodiment 5
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes, remove surface compact in supersonic cleaning machine
NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaning in dehydrated alcohol will
The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares tungsten-cobalt copper post shape presoma:
By 0.002 M Cu (NO3)2、0.002 M Co(NO3) 2、0.004 M Na2WO4、0.1 M NH4F is added to reaction kettle
In, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, is in temperature
10 hours are kept the temperature in 160 DEG C of baking oven;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;It is placed in
Dry 6 h in 60 DEG C of vacuum oven.
(3) low temperature phosphor prepares porous columar structure:
Obtained tungsten-cobalt copper post shape presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace
Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min,
450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency WO3-xWhat is regulated and controled is porous
Column CoP/CuP array structure.
Embodiment 6
(1) nickel foam surface clean:
Nickel foam is immersed in 0.1 M dilute hydrochloric acid, ultrasonic vibration 30 minutes in ultrasonic cleaning instrument, removes surface compact
NiO film;Ultrasonic cleaning is clean in deionized water again.Then it is cleaned by ultrasonic in acetone;Finally cleaned in dehydrated alcohol, it will
The nickel foam cleaned up is placed in 60 DEG C of vacuum oven dry 6 h.
(2) hydro-thermal method prepares tungsten ambrose alloy column presoma:
By 0.002 M Ni (NO3)3·5H2O、0.002 M Cu(NO3)2、0.004 M Na2WO4、0.1 M NH4F is added to instead
It answers in kettle, 30 min of magnetic agitation obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, in temperature
To keep the temperature 10 hours in 160 DEG C of baking ovens;Surface residue is rinsed out with a large amount of deionized water after natural cooling;It is placed in 60
DEG C vacuum oven in dry 6 h.
(3) low temperature phosphor prepares porous columar structure:
Obtained tungsten ambrose alloy column presoma is placed in the downstream of pipe reaction furnace, sodium hypophosphite is placed in the upper of pipe reaction furnace
Trip is passed through argon gas first by pipe reaction stove evacuation, and flow velocity is 20 cc min-1;Select heating rate for 10 DEG C/min,
450 DEG C of 2 h of heat preservation;After natural cooling, deionized water rinses the impurity on surface, obtains amorphous state deficiency WO3-xWhat is regulated and controled is porous
Column Ni5P4/ CuP array structure.
Embodiment 7
(1) composition of test macro:
The amorphous MoO that will be grown on nickel foam substrate3-x(WO3-x) regulation binary metal phosphide heterojunction structure it is straight
It connects and is used as working electrode, tested in three-electrode system.It is respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode,
1 M KOH is electrolyte.First lead to argon gas to electrolyte before test to handle 30 minutes.
(2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., in the potential region of -1.232 V of V to -0.832
Carry out the CV circulation of 100 circles.Then LSV test is carried out in the potential region of -1.232 V of V to -0.832, is come with this to non-
Crystalline defects type MoO3-x(WO3-x) the HER performance of binary metal phosphide heterojunction array structure of regulation assessed.?
The test that LSV curve is carried out in the potential region of 0.268 V to 0.768 V, is come with this to amorphous state deficiency MoO3-x
(WO3-x) the OER performance of binary metal phosphide heterojunction array structure of regulation assessed.It is tested in two electrode systems
Amorphous state deficiency MoO3-x(WO3-x) regulation binary metal phosphide heterojunction array structure total moisture solution performance.
(3) the iR compensation and conversion of current potential:
In this during, all current potentials all pass through 90% iR compensation, in addition, the current potential in this experiment will be converted into it is reversible
Hydrogen potential, specific calculation formula are as follows: ERHE=EHg/HgO+0.098+0.059pH。
Claims (8)
1. a kind of binary metal phosphide of molybdenum trioxide regulation, it is characterised in that: the binary metal phosphorus of molybdenum trioxide regulation
Compound is the porous cylindrical array structure of hydridization, and the molybdenum trioxide is generated in-situ amorphous structure, columnar arrays
For meso-hole structure, pore diameter range is 5-10 nanometers, and the length of column is 15-30 microns, and diameter is 3-5 microns;In its structure
There are amorphous MoO3-xAnd CoP/Ni5P4Hetero-junctions, wherein x is the quantity of Lacking oxygen, 0 < X < 1;Preparation method includes
The column presoma and low temperature phosphor of molybdenum cobalt nickel are grown on nickel foam substrate using hydro-thermal method.
2. the binary metal phosphide of molybdenum trioxide regulation described in accordance with the claim 1, it is characterised in that: three oxidations
Molybdenum is replaced with tungstic acid.
3. the binary metal phosphide of molybdenum trioxide regulation according to claim 1 or 2, it is characterised in that: CoP/Ni5P4
Hetero-junctions CoP/CuP or Ni5P4/ CuP or CuP/Ni5P4Instead of.
4. the preparation method of the binary metal phosphide of molybdenum trioxide described in claim 1 regulation, it is characterised in that including with
Lower step:
1) foam nickel surface is cleaned;Nickel foam is immersed in 0.01-1 M dilute hydrochloric acid, the ultrasound in ultrasonic cleaning instrument
Concussion 5-50 minutes, removes the NiO film of surface compact;Ultrasonic cleaning is clean in deionized water again, then ultrasonic in acetone
Cleaning;It is finally cleaned in dehydrated alcohol, the nickel foam cleaned up is placed in 20-80 DEG C of vacuum oven dry 3-20
h;
2) hydro-thermal method grows the column presoma of molybdenum cobalt nickel on nickel foam substrate;By 0.002-0.5 M Ni (NO3)3·5H2O、
0.002-0.5 M Co(NO3)2、0.004-1 M Na2MoO4、0.002-0.8 M NH4F is added in reaction kettle, magnetic agitation
10-60 min obtains uniform solution;Then the nickel foam cleaned up is added in reaction kettle, is 100-180 DEG C in temperature
Baking oven in keep the temperature 5-10 hours;Substance remained on surface is rinsed out with a large amount of deionized water after natural cooling;It is placed in 30-
Dry 2-10 h in 80 DEG C of vacuum oven;
3) low temperature phosphor prepares the columnar arrays structure of porous surface, and obtained molybdenum cobalt nickel column shape presoma is placed in pipe reaction
The downstream of furnace, sodium hypophosphite are placed in the upstream of pipe reaction furnace, first by pipe reaction stove evacuation, are passed through argon gas, flow velocity
For 10-100 cc min-1;Select heating rate for 2-20 DEG C/min, in 200-600 DEG C of heat preservation 1-6 h;After natural cooling, go
Ionized water rinses the impurity on surface, obtains amorphous state deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure.
5. the application of binary metal phosphide described in claim 1,2 or 3, it is characterised in that it is used for electrocatalytic hydrogen evolution, electricity
The application of chemistry analysis oxygen and electrochemistry total moisture solution.
6. the application of binary metal phosphide according to claim 5, it is characterised in that described is used for electrocatalytic hydrogen evolution
Application the following steps are included:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is direct
It as working electrode, is tested in three-electrode system, is respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode, 1
M KOH is electrolyte, is first carried out processing 30 minutes of logical argon gas to electrolyte before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., in the potential region of -1.232 V of V to -0.832
The CV circulation for carrying out 100 circles, LSV test is then carried out in the potential region of -1.232 V of V to -0.832, is come with this to non-
Crystalline defects type MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The Hydrogen Evolution Performance of array structure is assessed;
3) the iR compensation and conversion of current potential:
In this during, all current potentials all pass through 90% iR compensation, in addition, the current potential in this experiment will be converted into it is reversible
Hydrogen potential, specific calculation formula are as follows: ERHE=EHg/HgO+0.098+0.059pH。
7. the application of binary metal phosphide according to claim 5, it is characterised in that described is used for Electrochemical oxygen evolution
Application the following steps are included:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is direct
It as working electrode, is tested in three-electrode system, is respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode, 1
M KOH is electrolyte, is first carried out processing 30 minutes of logical argon gas to electrolyte before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., in the potential region of 0.268 V to 0.768 V into
The CV circulation that row 100 encloses, the test of LSV is then carried out in the potential region of 0.268 V to 0.768 V, is come with this to amorphous
State deficiency MoO3-xThe porous cylindrical CoP/Ni of regulation5P4The analysis oxygen performance of array structure is assessed;
3) the iR compensation and conversion of current potential:
In this during, all current potentials all pass through 90% iR compensation, in addition, the current potential in this experiment will be converted into it is reversible
Hydrogen potential, specific calculation formula are as follows: ERHE=EHg/HgO+0.098+0.059pH。
8. the application of binary metal phosphide according to claim 5, it is characterised in that described is used for the full water of electrochemistry
Decomposition application the following steps are included:
1) composition of test macro:
The amorphous state deficiency MoO that will be grown on nickel foam substrate3-xThe porous cylindrical CoP/Ni of regulation5P4Array structure is direct
It as working electrode, is tested in three-electrode system, is respectively to electrode with carbon-point, mercury/mercuric oxide electrode is reference electrode, 1
M KOH is electrolyte, is first carried out processing 30 minutes of logical argon gas to electrolyte before test;
2) Electrochemical Test Procedure:
First electrode is activated before formal test, i.e., carries out 100 circles in the potential region of 0 V to 1.7 V
CV circulation, then in the potential region of 0 V to 1.7 V carry out LSV test, come with this to amorphous state deficiency MoO3-xIt adjusts
The porous cylindrical CoP/Ni of control5P4The total moisture solution performance of array structure is assessed;
3) the iR compensation of current potential: in this during, all current potentials all pass through 90% iR compensation.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910076389.0A CN109797404B (en) | 2019-01-26 | 2019-01-26 | Molybdenum trioxide (tungsten) regulated binary metal phosphide, preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910076389.0A CN109797404B (en) | 2019-01-26 | 2019-01-26 | Molybdenum trioxide (tungsten) regulated binary metal phosphide, preparation method and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109797404A true CN109797404A (en) | 2019-05-24 |
CN109797404B CN109797404B (en) | 2020-08-21 |
Family
ID=66559009
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910076389.0A Active CN109797404B (en) | 2019-01-26 | 2019-01-26 | Molybdenum trioxide (tungsten) regulated binary metal phosphide, preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109797404B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110433833A (en) * | 2019-08-14 | 2019-11-12 | 华南理工大学 | A kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent and preparation method thereof based on modified synergic |
CN111558387A (en) * | 2020-05-18 | 2020-08-21 | 湖南大学 | Molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution |
CN112593248A (en) * | 2020-12-15 | 2021-04-02 | 苏州大学张家港工业技术研究院 | Ruthenium and iron co-doped tungsten oxide and preparation method and application thereof |
CN112680748A (en) * | 2020-12-01 | 2021-04-20 | 江南大学 | A/B/Si ternary composite silicon-based photoelectrode with bionic structure and preparation method thereof |
CN112978815A (en) * | 2021-03-14 | 2021-06-18 | 北京工业大学 | Preparation method of nickel-tungsten phosphide-nickel-tungsten oxide with heterostructure |
CN113699552A (en) * | 2021-08-26 | 2021-11-26 | 中南大学 | Cobalt phosphate-molybdenum trioxide composite nanorod array three-dimensional electrode material and preparation method and application thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002317289A (en) * | 2001-04-19 | 2002-10-31 | Asahi Kasei Corp | Hydrogen generating electrode |
CN101717948A (en) * | 2009-12-25 | 2010-06-02 | 天津大学 | Nano-structure nickel-tungsten-phosphorus (Ni-W-P) activated cathode used in the chlor-alkali industry and method for producing same |
CN104988536A (en) * | 2015-08-04 | 2015-10-21 | 重庆大学 | Method for preparing high-performance molybdenum-based hydrogen evolution electrode by phosphatizing molybdate precursor |
KR101729888B1 (en) * | 2016-01-28 | 2017-04-24 | 서강대학교산학협력단 | Photoelectrochemical Water Splitting System Using Porous Transition Metal Oxide Semiconductor |
CN108411322A (en) * | 2018-03-09 | 2018-08-17 | 三峡大学 | A kind of preparation method of the cobalt sulfide with molybdenum disulfide In-situ reaction electrode and its application on water electrolysis hydrogen producing |
CN108448117A (en) * | 2018-03-07 | 2018-08-24 | 中国科学院上海高等研究院 | Ultra-thin nickel cobalt oxide nanometer sheet electrod-array rich in oxygen defect and preparation method |
CN108560017A (en) * | 2017-12-07 | 2018-09-21 | 华东理工大学 | A kind of amorphous cobalt tungsten modifying foam nickel catalysis electrode, preparation method and applications |
CN108588750A (en) * | 2018-03-16 | 2018-09-28 | 江苏大学 | A kind of double-metal phosphide elctro-catalyst and preparation method thereof and its application |
CN108970625A (en) * | 2018-07-23 | 2018-12-11 | 成都新柯力化工科技有限公司 | A kind of amorphous phase catalyst being used to prepare fuel cell hydrogen and preparation method |
-
2019
- 2019-01-26 CN CN201910076389.0A patent/CN109797404B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002317289A (en) * | 2001-04-19 | 2002-10-31 | Asahi Kasei Corp | Hydrogen generating electrode |
CN101717948A (en) * | 2009-12-25 | 2010-06-02 | 天津大学 | Nano-structure nickel-tungsten-phosphorus (Ni-W-P) activated cathode used in the chlor-alkali industry and method for producing same |
CN104988536A (en) * | 2015-08-04 | 2015-10-21 | 重庆大学 | Method for preparing high-performance molybdenum-based hydrogen evolution electrode by phosphatizing molybdate precursor |
KR101729888B1 (en) * | 2016-01-28 | 2017-04-24 | 서강대학교산학협력단 | Photoelectrochemical Water Splitting System Using Porous Transition Metal Oxide Semiconductor |
CN108560017A (en) * | 2017-12-07 | 2018-09-21 | 华东理工大学 | A kind of amorphous cobalt tungsten modifying foam nickel catalysis electrode, preparation method and applications |
CN108448117A (en) * | 2018-03-07 | 2018-08-24 | 中国科学院上海高等研究院 | Ultra-thin nickel cobalt oxide nanometer sheet electrod-array rich in oxygen defect and preparation method |
CN108411322A (en) * | 2018-03-09 | 2018-08-17 | 三峡大学 | A kind of preparation method of the cobalt sulfide with molybdenum disulfide In-situ reaction electrode and its application on water electrolysis hydrogen producing |
CN108588750A (en) * | 2018-03-16 | 2018-09-28 | 江苏大学 | A kind of double-metal phosphide elctro-catalyst and preparation method thereof and its application |
CN108970625A (en) * | 2018-07-23 | 2018-12-11 | 成都新柯力化工科技有限公司 | A kind of amorphous phase catalyst being used to prepare fuel cell hydrogen and preparation method |
Non-Patent Citations (4)
Title |
---|
CHENG DU ET AL.: "Nest-like NiCoP for Highly Efficient Overall Water Splitting", 《ACS CATALYSIS》 * |
JINGQI TIAN ET AL.: "Self-Supported Nanoporous Cobalt Phosphide Nanowire Arrays: An Efficient 3D Hydrogen-Evolving Cathode over the Wide Range of pH 0−14", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY COMMUNICATION》 * |
R. SIVAKUMAR ET AL.: "Characterization on electron beam evaporated a-MoO3 thin films by the influence of substrate temperature", 《CURRENT APPLIED PHYSICS》 * |
XIN-YAO YU ET AL.: "Formation of Ni–Co–MoS2 Nanoboxes with Enhanced Electrocatalytic Activity for Hydrogen Evolution", 《ADV. MATER.》 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110433833A (en) * | 2019-08-14 | 2019-11-12 | 华南理工大学 | A kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent and preparation method thereof based on modified synergic |
CN110433833B (en) * | 2019-08-14 | 2022-03-25 | 华南理工大学 | Non-noble metal hydrogen evolution electrocatalyst based on synergistic modification and preparation method thereof |
CN111558387A (en) * | 2020-05-18 | 2020-08-21 | 湖南大学 | Molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution |
CN112680748A (en) * | 2020-12-01 | 2021-04-20 | 江南大学 | A/B/Si ternary composite silicon-based photoelectrode with bionic structure and preparation method thereof |
CN112593248A (en) * | 2020-12-15 | 2021-04-02 | 苏州大学张家港工业技术研究院 | Ruthenium and iron co-doped tungsten oxide and preparation method and application thereof |
CN112593248B (en) * | 2020-12-15 | 2021-09-03 | 苏州大学张家港工业技术研究院 | Ruthenium and iron co-doped tungsten oxide and preparation method and application thereof |
CN112978815A (en) * | 2021-03-14 | 2021-06-18 | 北京工业大学 | Preparation method of nickel-tungsten phosphide-nickel-tungsten oxide with heterostructure |
CN112978815B (en) * | 2021-03-14 | 2022-11-15 | 北京工业大学 | Preparation method of nickel-tungsten phosphide-nickel-tungsten oxide with heterostructure |
CN113699552A (en) * | 2021-08-26 | 2021-11-26 | 中南大学 | Cobalt phosphate-molybdenum trioxide composite nanorod array three-dimensional electrode material and preparation method and application thereof |
CN113699552B (en) * | 2021-08-26 | 2022-07-29 | 中南大学 | Cobalt phosphate-molybdenum trioxide composite nanorod array three-dimensional electrode material and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN109797404B (en) | 2020-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109797404A (en) | The binary metal phosphide and preparation method and application of molybdenum trioxide (tungsten) regulation | |
Xiao et al. | Synthesizing nanoparticles of Co-P-Se compounds as electrocatalysts for the hydrogen evolution reaction | |
US11859296B2 (en) | Method for producing 2,5-furandicarboxylic acid (FDCA) by electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) and simultaneously generating hydrogen by water electrolysis | |
CN108083242A (en) | The purposes of ternary phosphatization ferronickel nanometer sheet, its preparation method and electrolysis water | |
CN110479328B (en) | Fe-doped cobalt hydroxyphosphite nanosheet array structure material and preparation method and application thereof | |
CN109585862B (en) | Preparation method of dual-functional cobalt and nitrogen and oxygen doped carbon in-situ composite electrode | |
JP7162300B2 (en) | Electrocatalyst and method for producing the same | |
CN111889128A (en) | Preparation method of cage-shaped ferronickel bimetallic phosphide loaded nitrogen-doped porous carbon material | |
CN110479329A (en) | A kind of preparation and application of phosphorus doping cobaltous telluride nano material | |
CN111663152B (en) | Preparation method and application of foam nickel-loaded amorphous phosphorus-doped nickel molybdate bifunctional electrocatalytic electrode | |
CN108823597A (en) | Annealing method prepares the method and its application of the nickel sulfide liberation of hydrogen catalyst of N doping | |
Guo et al. | Surface self-reconstruction of telluride induced by in-situ cathodic electrochemical activation for enhanced water oxidation performance | |
CN107805826A (en) | Possess ferro-phosphorus modified electrode and preparation method that electrocatalytic oxidation separates out performance | |
CN109136982A (en) | By sacrificing the method to electrode synthesizing nano compound material and its application in electrolysis water catalyst | |
Li et al. | Integration of heterointerface and porosity engineering to achieve efficient hydrogen evolution of 2D porous NiMoN nanobelts coupled with Ni particles | |
CN114744224B (en) | Preparation and application of nitrogen-doped carbon nanotube-loaded nickel-cobalt composite nanowire | |
CN114875442A (en) | Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof | |
CN113512738B (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
CN106935869A (en) | Three-dimensional manometer cobaltosic oxide, preparation method and application | |
CN206127438U (en) | Liberation of hydrogen electrode | |
CN116525846A (en) | Nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co for fuel cell 9 S 8 Nanoparticle composite catalyst and preparation method thereof | |
CN110607532A (en) | Preparation method of Co-Ni-P/fs-Si material for hydrogen evolution by water electrolysis | |
CN110368961A (en) | A kind of preparation method of lamella self assembly starfish shape richness nickel telluride Raney nickel | |
CN113463131B (en) | Copper monatomic catalyst and preparation method and application thereof | |
CN108325546A (en) | A kind of difunctional electrochemical catalyst |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
OL01 | Intention to license declared | ||
OL01 | Intention to license declared |