CN108654656A - The preparation method and applications of phosphatization cobalt porous nano line/stainless steel composite electrocatalyst - Google Patents
The preparation method and applications of phosphatization cobalt porous nano line/stainless steel composite electrocatalyst Download PDFInfo
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- CN108654656A CN108654656A CN201810397314.8A CN201810397314A CN108654656A CN 108654656 A CN108654656 A CN 108654656A CN 201810397314 A CN201810397314 A CN 201810397314A CN 108654656 A CN108654656 A CN 108654656A
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 69
- 239000010935 stainless steel Substances 0.000 title claims abstract description 61
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 24
- 239000010941 cobalt Substances 0.000 title claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title abstract description 9
- 239000010411 electrocatalyst Substances 0.000 title abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 83
- 239000001257 hydrogen Substances 0.000 claims abstract description 83
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 230000000694 effects Effects 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 241000549556 Nanos Species 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- -1 washing Chemical compound 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000002688 persistence Effects 0.000 abstract 1
- 238000005554 pickling Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 235000012149 noodles Nutrition 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to elctro-catalyst technical fields, it is related to the preparation of Electrocatalytic Activity for Hydrogen Evolution Reaction agent, more particularly to a kind of preparation method of phosphatization cobalt porous nano line/stainless steel composite electrocatalyst, stainless steel is first cut into required size and pre-processes stainless steel substrate through pickling, then by urea, ammonium fluoride, CoCl2·6H2O is dissolved in deionized water, is put into substrate, and CoP/SS presomas, then high-temperature calcination is made in 120~160 DEG C of 6~10h of hydro-thermal reaction, finally by CoP/SS presomas with 350~450 DEG C of calcining 3~5h of phosphatization of ortho phosphorous acid hydrogen sodium to get.Prepared CoP porous nanos line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel is also applied to water electrolysis hydrogen production gas under acid condition by the present invention.The present invention introduces cheap stainless steel in electrocatalytic hydrogen evolution material, widens the source of liberation of hydrogen material.Method synthesis is simple, economical, is convenient for large-scale industrial production, and catalyst, which is made, has excellent electrocatalytic hydrogen evolution performance, good stability and persistence, has great importance solving future source of energy crisis.
Description
Technical field
The invention belongs to elctro-catalyst technical fields, are related to the preparation of Electrocatalytic Activity for Hydrogen Evolution Reaction agent, and in particular to a kind of phosphatization cobalt
The preparation method and applications of porous nano line/stainless steel composite electrocatalyst.
Background technology
Since the 21th century, the great difficult problem of facing mankind and challenge are no more than the energy and environment, and therefore, exploitation is new
, the clean energy resource that can be recycled will solve the problems, such as this.Under energy crisis and environmental pollution dual-pressure,
Hydrogen Energy is renewable because having many advantages, such as that fuel value is high, pollution-free, becomes the cleaning energy for being most hopeful to substitute existing fossil fuel
Source.Now there are many kinds of the methods of production hydrogen, such as：Fossil fuel produces hydrogen, and disadvantage is：Flow is complicated, energy consumption is big, pollution environment；
Photocatalyzed Hydrogen Production, disadvantage are：Transfer efficiency is low, not yet promotes practical.However electro-catalysis production hydrogen has simple and environmentally-friendly, feasibility
Height, the advantages that hydrogen of high-purity can be prepared.Therefore water electrolysis hydrogen production causes everybody extensive concern and research, the technology
Continuous popularization that will be slowly.But need to consume a large amount of electric energy during electrolysis water, it needs to find efficient elctro-catalyst
To reduce the overpotential of electrolysis water.
In current electrocatalytic hydrogen evolution material, the noble metals such as platinum have most excellent Hydrogen Evolution Performance, but because its is rare, high
It is expensive, limit the extensive use in electrocatalytic hydrogen evolution.Therefore a kind of cheap electrocatalytic hydrogen evolution material is developed your gold replaced
Belong to, has very important significance.
Transition metal material includes transition metal carbide, sulfide, nitride and transition metal phosphide, is considered
It is optimal non-precious metal electrocatalytic hydrogen evolution material.Wherein, transition metal phosphide (TMPs), rich reserves, cheap, tool
There are certain mechanical strength, good conductivity, chemical stability and adsorbs Gibbs free energy (⊿ GH ≈ close to zero hydrogen
0), while when the introducing of the phosphorus atoms of electronegativity, the electronics of transition metal can be attracted and be conducive to hydrogen desorption.Therefore transition
Metal phosphide can be good at replacing precious metal material, have preferable Research Prospects in water electrolysis hydrogen production field.In these mistakes
It crosses in metal phosphide, phosphatization cobalt is demonstrated by excellent electrocatalytic hydrogen evolution performance.According to density functional theory（DFT）It calculates
Show that CoP has the Hydrogen Evolution Performance close to precious metals pt, CoP to show high electrocatalytic hydrogen evolution active sites in acid medium
Point and stability, cause the concern of practitioner.
CoP is in past research, by different synthetic methods, the phosphatization cobalt prepared, and pattern, Hydrogen Evolution Performance and steady
It is qualitative to have certain difference.Generally speaking, they are all the catalytic activity for increasing phosphatization cobalt, specific surface area and raising electrical conductance
Enhance catalytic performance, catalyst load on the carbon carrier can be remarkably reinforced to the electrocatalytic hydrogen evolution performance of integral material, but
Carbon carrier (graphene, carbon nanotube, carbon cloth etc.) price is all more expensive, and inventor selects cheap stainless steel as substrate.
Electrical conductance can be enhanced and increase catalytic activity specific surface area by not only containing carbon in stainless steel, but also be contained
The metallic elements such as iron, nickel, molybdenum, vanadium, by the synergistic effect between these metallic elements and cobalt element, Hydrogen Evolution Performance can be further
It is improved.
Invention content
In view of the above-mentioned deficiencies in the prior art, the invention discloses a kind of phosphatization cobalt porous nano line/stainless steels
Compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent preparation method.
Technical solution
A kind of preparation method of phosphatization cobalt porous nano line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel, is as follows：
Stainless steel substrates are cut into required size by the A, pretreatment of stainless steel, are put into 1~2h of ultrasound in dilute HCl solution, are taken out again
It is put into 1~2h of ultrasound in acetone, washing, alcohol are washed, dried, and obtain pretreated stainless steel substrate, for use；
B, hydro-thermal method synthesizes CoP/SS presomas, by urea, ammonium fluoride, CoCl2·6H2O dissolvings are ultrasonic in deionized water,
The solution for forming stable homogeneous, is transferred in polytetrafluoroethylene (PTFE) (PTFE) liner autoclave, is put into pretreated stainless steel substrate,
120~160 DEG C of 6~10h of hydro-thermal reaction, are cleaned with deionized water, are dried to obtain CoP/SS presomas, wherein the urea, fluorine
Change ammonia, CoCl2·6H2O and deionized water mole, volume ratio be 10~12 mmol：4~6 mmol：2~4 mmol：30~
40ml；
CoP/SS presomas are placed in Muffle furnace and calcine 2~4h in 300~400 DEG C, then by CoP/SS by C, high-temperature calcination
Presoma and ortho phosphorous acid hydrogen sodium, which are placed in two porcelain boats, to be put into tube furnace, and 350~450 DEG C of calcining 3~5h of phosphatization are obtained
The CoP porous nanos line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel, wherein the quality of the CoP/SS presomas and ortho phosphorous acid hydrogen sodium
Than for 240mg：300~500mg.
In the more excellent disclosed example of the present invention, stainless steel described in step A is 316 type, 1600 mesh, 316-SS；Required size
For 1.5 × 2 cm sizes.
In the more excellent disclosed example of the present invention, a concentration of 1~2 mol/l of HCl described in step A, drying temperature 60
℃。
In the more excellent disclosed example of the present invention, urea, ammonium fluoride, CoCl described in step B2·6H2O and deionized water are rubbed
You, volume ratio 10mmol：4mmol：2mmol：40ml.
In the more excellent disclosed example of the present invention, pretreated stainless steel is put into kettle described in step B, 120 DEG C of hydro-thermals are anti-
Answer 6h.
In the more excellent disclosed example of the present invention, drying temperature described in step B is 60 DEG C.
In the more excellent disclosed example of the present invention, CoP/SS presomas are calcined in Muffle furnace at 300 DEG C described in step C
2h。
In the more excellent disclosed example of the present invention, 350 DEG C of calcining phosphatization 3h described in step C.
According to phosphatization cobalt porous nano line made from the method for the invention/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel, by being permitted
Donna rice grain forms, and has gap, about 40~60 nm of nanowire diameter between nano particle.
Another object of the present invention is, by prepared CoP porous nanos line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction of stainless steel
Agent is applied to water electrolysis hydrogen production gas under acid condition.
Porous CoP nano wires shorten the distance of electron-transport during liberation of hydrogen, to accelerate electron-transport, into
And electrocatalytic hydrogen evolution reaction rate is improved, reduce the overpotential of reaction.
The electrocatalytic hydrogen evolution performance test of CoP porous nanos line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent material of stainless steel
Evolving hydrogen reaction is carried out with CHI760e electrochemical workstations（HER）Electro-chemical test, using three electrodes, size is 0.5 ×
0.5cm CoP/SS, saturated calomel electrode and carbon-point are respectively as working electrode, reference electrode and to electrode.Polarization curve with
Sweep speed is sulfuric acid of 5 mV/s in 0.5 M（pH=0.40）Middle test.
Advantageous effect
CoP porous nanos particle/stainless steel composite electrocatalyst composite material prepared by the present invention, synthetic method is simple, more
Economy is convenient for large-scale industrial production, the composite material to have excellent electrocatalytic hydrogen evolution performance, good stability and hold
Long property has great importance solving future source of energy crisis.Cheap stainless steel is introduced into electrocatalytic hydrogen evolution material,
The source of liberation of hydrogen material is widened.
Description of the drawings
The XRD diffraction spectrograms of Fig. 1, CoP porous nano line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel.
The microscopic appearance of Fig. 2, CoP porous nano line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel, wherein（a-b）For CoP/
The scanning electron microscope (SEM) photograph of SS（FESEM）；（b-d）For CoP/SS transmission electron microscope pictures（TEM）.
Fig. 3, CoP porous nano line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel are in acidity (0.5 M H2SO4) in liberation of hydrogen live
Property, wherein（a）It is CoP porous nanos line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel in 0.5 M H2SO4In polarization curve；（b）
For（a）Corresponding Tafel slopes.
Specific implementation mode
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited in following embodiments.
Embodiment 1
A kind of preparation method of phosphatization cobalt porous nano line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel, is as follows：
A, the pretreatment of stainless steel, by 316 type stainless steels（316-SS）It is 1.5 × 2 cm to be cut into size, is put into the 1M of preparation
It is ultrasonically treated 1h in HCl solution, places into and is ultrasonically treated 1h in acetone, finally washing, alcohol are washed, dried, and are obtained pretreated
316 type stainless steels,
Base material is compared with carbon cloth, carbon cloth is also cut into 1.5 × 2cm, acetone, ethyl alcohol, water is used to process drying, obtain respectively
To pretreated carbon cloth；
B, the presoma of hydro-thermal method synthesis CoP/SS, weighs the urea of 10mmol, the ammonium fluoride of 4mmol, the CoCl of 2mmol2·
6H2O is dissolved in the deionized water of 40ml volumes, and then ultrasound 15min forms the solution of stable homogeneous, is transferred into 50ml
Polytetrafluoroethylene (PTFE) (PTFE) liner autoclave in, the stainless steel handled well is put into kettle, the hydro-thermal reaction 6h at 120 DEG C,
It is cleaned with deionized water, is dried to obtain CoP/SS presomas,
Base material is compared with carbon cloth, step is same as above, dry CoP/CC presomas；
CoP/SS presomas are calcined 2h by C, high-temperature calcination at 300 DEG C in Muffle furnace, finally by 240mg CoP/SS forerunners
Body, 500mg ortho phosphorous acid hydrogen sodium are placed in two porcelain boats and are put into tube furnace, and 350 DEG C of calcining phosphatization 3h obtain that CoP is porous to be received
The compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of rice noodles/stainless steel,
Base material is compared with carbon cloth, CoP/CC presoma steps are same as above, and obtain the compound liberation of hydrogen electricity of CoP porous nanos line/CC
Catalyst.
The phenetic analysis of CoP porous nanos line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent material of stainless steel
As shown in Figure 1, as can be seen from the figure Co3O4With the diffraction maximum of the X-ray of CoP, corresponding standard card is
PDF#73-1701 and PDF#29-0491.
As shown in Fig. 2, it can be seen that CoP catalyst is nano thread structure from figure a.Scheme b, can be seen that nano wire in c
Diameter about 40~60 nm, from d figures it can be seen that nano wire is made of many nano particles, have between particle it is certain between
Away from.
As shown in figure 3, there is excellent electro-catalysis analysis in acidity from CoP/SS elctro-catalysts are apparent that in figure
Hydrogen performance, Hydrogen Evolution Performance are better than CoP/CC Hydrogen Evolution Performance close to Pt/C.
The electrocatalytic hydrogen evolution the performance test results such as Fig. 3 of composite electro catalytic liberation of hydrogen material in acidity obtained by the present invention
It is shown, when current density is 10 mA/cm2When, the overpotential of Pt/C, CoP/SS and CoP/CC composite materials are followed successively by 49,62
With 118 mV, tower phenanthrene slope is followed successively by 33.7,45.6 and 59.5 mV/decade.
Embodiment 2
A kind of preparation method of phosphatization cobalt porous nano line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel, is as follows：
A, the pretreatment of stainless steel, by 316 type stainless steels（316-SS）It is 1.5 × 2 cm to be cut into size, is put into preparation
It is ultrasonically treated 1.5h in 1.5M HCl solutions, places into and is ultrasonically treated 1.5h in acetone, finally washing, alcohol are washed, dried, and are obtained pre-
Processed 316 type stainless steel；
B, the presoma of hydro-thermal method synthesis CoP/SS, weighs the urea of 11mmol, the ammonium fluoride of 5mmol, the CoCl of 3mmol2·
6H2O is dissolved in the deionized water of 42ml volumes, and then ultrasound 15min forms the solution of stable homogeneous, is transferred into 50ml
Polytetrafluoroethylene (PTFE) (PTFE) liner autoclave in, the stainless steel handled well is put into kettle, the hydro-thermal reaction 8h at 140 DEG C,
It is cleaned with deionized water, is dried to obtain CoP/SS presomas；
CoP/SS presomas are calcined 2h by C, high-temperature calcination at 350 DEG C in Muffle furnace, finally by 260g CoP/SS forerunners
Body, 300mg ortho phosphorous acid hydrogen sodium are placed in two porcelain boats and are put into tube furnace, and 400 DEG C of calcining phosphatization 4h obtain that CoP is porous to be received
The compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of rice noodles/stainless steel.
Embodiment 3
A kind of preparation method of phosphatization cobalt porous nano line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel, is as follows：
A, the pretreatment of stainless steel, by 316 type stainless steels（316-SS）It is 1.5 × 2 cm to be cut into size, is put into the 2M of preparation
It is ultrasonically treated 2h in HCl solution, places into and is ultrasonically treated 2h in acetone, finally washing, alcohol are washed, dried, and are obtained pretreated
316 type stainless steels；
B, the presoma of hydro-thermal method synthesis CoP/SS, weighs the urea of 12mmol, the ammonium fluoride of 6mmol, the CoCl of 4mmol2·
6H2O is dissolved in the deionized water of 45ml volumes, and then ultrasound 15min forms the solution of stable homogeneous, is transferred into 50ml
Polytetrafluoroethylene (PTFE) (PTFE) liner autoclave in, the stainless steel handled well is put into kettle, the hydro-thermal reaction 10h at 150 DEG C,
It is cleaned with deionized water, is dried to obtain CoP/SS presomas；
CoP/SS presomas are calcined 2h by C, high-temperature calcination at 400 DEG C in Muffle furnace, finally by 250g CoP/SS forerunners
Body, 400mg ortho phosphorous acid hydrogen sodium are placed in two porcelain boats and are put into tube furnace, and 450 DEG C of calcining phosphatization 5h obtain that CoP is porous to be received
The compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of rice noodles/stainless steel.
Embodiment 4
A kind of preparation method of phosphatization cobalt porous nano line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel, is as follows：
A, the pretreatment of stainless steel, by 316 type stainless steels（316-SS）It is 1.5 × 2 cm to be cut into size, is put into preparation
It is ultrasonically treated 1h in 1.8M HCl solutions, places into and is ultrasonically treated 2h in acetone, finally washing, alcohol are washed, dried, and are pre-processed
The 316 type stainless steels crossed；
B, the presoma of hydro-thermal method synthesis CoP/SS, weighs the urea of 11mmol, the ammonium fluoride of 5mmol, the CoCl of 4mmol2·
6H2O is dissolved in the deionized water of 44ml volumes, and then ultrasound 15min forms the solution of stable homogeneous, is transferred into 50ml
Polytetrafluoroethylene (PTFE) (PTFE) liner autoclave in, the stainless steel handled well is put into kettle, the hydro-thermal reaction 7h at 140 DEG C,
It is cleaned with deionized water, is dried to obtain CoP/SS presomas；
CoP/SS presomas are calcined 2h by C, high-temperature calcination at 380 DEG C in Muffle furnace, finally by 245mg CoP/SS forerunners
Body, 450mg ortho phosphorous acid hydrogen sodium are placed in two porcelain boats and are put into tube furnace, and 450 DEG C of calcining phosphatization 4h obtain that CoP is porous to be received
The compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of rice noodles/stainless steel.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of phosphatization cobalt porous nano line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel, which is characterized in that including such as
Lower step：
Stainless steel substrates are cut into required size by the A, pretreatment of stainless steel, are put into 1~2h of ultrasound in dilute HCl solution, are taken out again
It is put into 1~2h of ultrasound in acetone, washing, alcohol are washed, dried, and obtain pretreated stainless steel substrate, for use；
B, hydro-thermal method synthesizes CoP/SS presomas, by urea, ammonium fluoride, CoCl2·6H2O dissolvings are ultrasonic in deionized water, shape
At the solution of stable homogeneous, it is transferred in polytetrafluoroethylene (PTFE) (PTFE) liner autoclave, is put into pretreated stainless steel substrate,
120~160 DEG C of 6~10h of hydro-thermal reaction, are cleaned with deionized water, are dried to obtain CoP/SS presomas, wherein the urea, fluorine
Change ammonia, CoCl2·6H2O and deionized water mole, volume ratio be 10~12 mmol：4~6 mmol：2~4 mmol：30~
40ml；
CoP/SS presomas are placed in Muffle furnace and calcine 2~4h in 300~400 DEG C, then by CoP/SS by C, high-temperature calcination
Presoma and ortho phosphorous acid hydrogen sodium, which are placed in two porcelain boats, to be put into tube furnace, and 350~450 DEG C of calcining 3~5h of phosphatization are obtained
The CoP porous nanos line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of stainless steel, wherein the quality of the CoP/SS presomas and ortho phosphorous acid hydrogen sodium
Than for 240mg：300~500mg.
2. the preparation method of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of phosphatization cobalt porous nano line/stainless steel according to claim 1, special
Sign is：Stainless steel described in step A is 316 type, 1600 mesh, 316-SS；Required size is 1.5 × 2 cm sizes.
3. the preparation method of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of phosphatization cobalt porous nano line/stainless steel according to claim 1, special
Sign is：A concentration of 1~2 mol/l of HCl described in step A, drying temperature are 60 DEG C.
4. the preparation method of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of phosphatization cobalt porous nano line/stainless steel according to claim 1, special
Sign is：Urea, ammonium fluoride, CoCl described in step B2·6H2O and deionized water mole, volume ratio 10mmol：
4mmol：2mmol：40ml.
5. the preparation method of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of phosphatization cobalt porous nano line/stainless steel according to claim 1, special
Sign is：Pretreated stainless steel is put into kettle described in step B, 120 DEG C of hydro-thermal reaction 6h, the drying temperature is 60
℃。
6. the preparation method of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of phosphatization cobalt porous nano line/stainless steel according to claim 1, special
Sign is：CoP/SS presomas are calcined into 2h in Muffle furnace at 300 DEG C described in step C.
7. the preparation method of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of phosphatization cobalt porous nano line/stainless steel according to claim 1, special
Sign is：Phosphatization 3h is calcined described in step C at 350 DEG C.
8. according to phosphatization cobalt porous nano line/compound Electrocatalytic Activity for Hydrogen Evolution Reaction of stainless steel made from any the methods of claim 1-7
Agent.
9. the compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of phosphatization cobalt porous nano line/stainless steel according to claim 8, it is characterised in that：Institute
It states catalyst to be made of many nano particles, there is gap, about 40~60 nm of nanowire diameter between nano particle.
10. a kind of application of catalyst as claimed in claim 8, it is characterised in that：By prepared CoP porous nanos line/no
The compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of steel of becoming rusty is applied to water electrolysis hydrogen production gas under acid condition.
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