CN110038603A - A kind of mixed metal phosphide base hollow out nanometer box and preparation method thereof, application - Google Patents
A kind of mixed metal phosphide base hollow out nanometer box and preparation method thereof, application Download PDFInfo
- Publication number
- CN110038603A CN110038603A CN201910446216.3A CN201910446216A CN110038603A CN 110038603 A CN110038603 A CN 110038603A CN 201910446216 A CN201910446216 A CN 201910446216A CN 110038603 A CN110038603 A CN 110038603A
- Authority
- CN
- China
- Prior art keywords
- hollow out
- metal phosphide
- mixed metal
- solution
- wraps
- 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 88
- 239000002184 metal Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 127
- 229910001868 water Inorganic materials 0.000 claims abstract description 83
- 239000011258 core-shell material Substances 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 130
- 239000008367 deionised water Substances 0.000 claims description 47
- 229910021641 deionized water Inorganic materials 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 46
- 230000015572 biosynthetic process Effects 0.000 claims description 41
- 238000003786 synthesis reaction Methods 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000012456 homogeneous solution Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- -1 potassium ferricyanide Chemical compound 0.000 claims description 13
- 230000036571 hydration Effects 0.000 claims description 11
- 238000006703 hydration reaction Methods 0.000 claims description 11
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 11
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 11
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 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 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- LGRDAQPMSDIUQJ-UHFFFAOYSA-N tripotassium;cobalt(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LGRDAQPMSDIUQJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 68
- 238000013019 agitation Methods 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 229910014572 C—O—P Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of mixed metal phosphide base hollow out nanometer box, include the following steps: to synthesize Ni3[Fe(CN)6]2·H2O nano cubic block；Synthesize Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure；Synthesize Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure；Synthesize mixed metal phosphide base hollow out nanometer box elctro-catalyst.Preparation process of the present invention is simple, and convenient for operation, and compared to the nanostructure of non-hollow out, products therefrom has shown excellent water oxygen electro catalytic activity, this and its unique engraved structure, advantageous mass transfer and load transfer channel, active site abundant are closely related.
Description
Technical field
The present invention relates to metal phosphide base hollow out nanometer box technical field more particularly to a kind of mixed metal phosphide bases
Hollow out nanometer box and preparation method thereof, application.
Background technique
With the tremendous expansion that today's society science and technology produces, also cumulative year after year, sustainable energy turn the demand to the energy
Changing and utilizing is the core topic for successfully managing current fossil energy exhaustion.Wherein, electro-catalysis water-splitting reaction is used as a kind of nothing
The Hydrogen Energy production ways that fossil fuel inputs, process cleans and environment are friendly, obtain extensive concern in recent years.It was reacting
Cheng Zhong, electro-catalysis water-splitting reaction can be divided into water reduction and two half-reactions of water oxygenization, and two are reacted while being occurred, and respective
Energy consumption has codetermined the efficiency of energy utilization of entire reaction.Compared to water reduction reaction, water oxidation reaction is due to being related to
To multistep electronics/proton coupling process, a variety of adsorbate groups are generated in reaction process, cause its kinetics increasingly complex
Slowly, bigger overpotential (i.e. more energy consumptions) is needed to overcome reaction energy barrier.Therefore, water oxidation reaction determines electricity
The final efficiency of water hydrogen producing technology is solved, and the water oxidation catalytic material that water oxygen reaction energy barrier is effectively reduced then becomes propulsion water crack
Solve the key of technological innovation.Although utilizing traditional noble metal electrocatalyst such as IrO2/RuO2, the mistake of water oxidation reaction can be reduced
Current potential；But precious metal material is often at high price, natural reserves are low and cyclical stability is poor, limits water electrolysis hydrogen production skill
The large-scale application of art.Therefore cheap, efficient, stable base metal water oxygen elctro-catalyst is designed and is developed, become current
The hot spot of chemistry and investigation of materials field.
Metal phosphide nanostructure due to having many advantages, such as that electro-chemical activity is high, at low cost, electro-catalysis, photocatalysis,
The storage of the electrochemical energies such as lithium ion battery and sodium-ion battery has obtained extensive research with conversion art.However, traditional
The active surface area of metal phosphide nanostructure is limited, limits the performance of its excellent potential.Hollow nanostructures are due to it
Unique structural advantage is expected to the electro-chemical activity of significant increase metal phosphide.But the electricity with hollow structure is urged
For agent, if duct is too small in its shell, electrolyte if, is difficult to be deep into lar nanometric cavities, therefore leads to elctro-catalyst
Active site it is under-utilized；On the other hand, even if there is partial electrolyte liquid to enter in lar nanometric cavities, then being produced in electrocatalytic reaction
Raw oxygen is also difficult quickly to be exported, and the bubble being trapped in lar nanometric cavities will certainly occupy amount of activated site, leads to electricity
Catalytic performance still has to be hoisted.So if advantageous mass transfer and load transfer channel are further constructed on the basis of hollow structure,
I.e. electrolyte can smoothly enter internal cavities participation electrocatalytic reaction, and the oxygen that electrocatalytic reaction generates also can be quick
Export, this will greatly enrich the active site of elctro-catalyst, can provide possibility for the further improvement of electro catalytic activity.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of mixed metal phosphide base hollow out nanometer boxes
And preparation method thereof, application, for the present invention compared to the nanostructure of non-hollow out, products therefrom shown excellent water oxygenization electricity
Catalytic activity, this and its unique engraved structure, advantageous mass transfer and load transfer channel, active site abundant are closely related.
A kind of preparation method of mixed metal phosphide base hollow out nanometer box proposed by the present invention, includes the following steps:
S1, synthesis Ni3[Fe(CN)6]2·H2O nano cubic block
Six hydration nickel sulfate, two citric acid monohydrate trisodiums are dissolved in deionized water, homogeneous solution A is formed；By iron cyaniding
Potassium is dissolved in deionized water, stirs evenly to form solution B；Solution B is added in solution A while stirring, has been added
Continue to stir after finishing, stand aging, centrifuge washing is dry, obtains Ni3[Fe(CN)6]2·H2O nano cubic block；
S2, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure
Nickelous nitrate hexahydrate, two citric acid monohydrate trisodiums are dissolved in deionized water and form homogeneous solution, Ni is added3[Fe
(CN)6]2·H2O nano cubic block is ultrasonically formed homogeneous solution C；Potassium cobalticyanide is dissolved in deionized water and is stirred, is formed uniform
Solution D；Solution C is stirred, solution D is slowly dropped in solution C while stirring and continues to stir, stands aging,
Centrifuge washing, it is dry, obtain Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure；
S3, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure
By Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure is scattered in dehydrated alcohol, shape
At uniform dispersion E；Ammonium hydroxide is dissolved in deionized water, stirs evenly to form solution F；F solution is added dropwise under stirring
Into E solution, continue to stir, centrifuge washing, it is dry, obtain Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O
Hollow out core-shell structure；
S4, synthesis mixed metal phosphide base hollow out nanometer box elctro-catalyst
Ni prepared by S33[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure is put into porcelain boat
In, sample a is obtained, sodium hypophosphite is put into another porcelain boat, obtains sample b, sample b is put into tube furnace on air inlet
Trip, sample a are placed on opening downstream in tube furnace, in a nitrogen atmosphere, tube furnace are warming up to 300-450 DEG C, is calcined, cooling
To room temperature, wherein the parkerizing process of tube furnace is carried out in nitrogen atmosphere, until temperature is down to room temperature after reaction, is obtained
Mixed metal phosphide base hollow out nanometer box elctro-catalyst.
Preferably, in S1, six hydration nickel sulfate, two citric acid monohydrate trisodiums, the molar ratio of the potassium ferricyanide are 1-10:
1.25-12.5:0.67-6.7；
Preferably, six hydration nickel sulfate, two citric acid monohydrate trisodiums, the molar ratio of the potassium ferricyanide are 1.5:1.875:1.
Preferably, 3-6 is washed with deionized water in S1, S2, S3, during centrifuge washing to wash 2-5 times all over, dehydrated alcohol.
Preferably, in S2, Nickelous nitrate hexahydrate, two citric acid monohydrate trisodiums, the molar ratio of potassium cobalticyanide are 0.1-
0.4:0.12-0.48:0.07-0.28；
Preferably, Nickelous nitrate hexahydrate, Ni3[Fe(CN)6]2·H2The molal weight ratio of O nano cubic block is that mmol:g is
0.1-0.4:0.04-0.16.
Preferably, in S3, Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure, ammonium hydroxide
W/v g:ml is 0.05-0.3:5-35.
Preferably, in S4, Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2It is O hollow out core-shell structure, secondary
The weight ratio of sodium phosphate is 0.01-0.1:0.1-1；
Preferably, Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure: sodium hypophosphite
Weight ratio is 1:10.
Preferably, in S4, the heating rate of tube furnace is 1-10 DEG C/min.
Preferably, in S4, calcination time 1-6h.
The invention also provides a kind of mixed metal phosphide base hollow out nanometer boxes, according to the mixed metal phosphide
It is prepared by the preparation method of base hollow out nanometer box.
The invention also provides a kind of mixed metal phosphide base hollow out nanometer box answering in elctro-catalyst as mentioned
With.
The present invention is dexterously with Ni3[Fe(CN)6]2·H2O nano cubic block is template and kernel, further in its appearance
Bread covers layer of Ni3[Co(CN)6]2·12H2O shell, to form core-shell structure；Then ammonium hydroxide lithographic technique is used, it will be upper
It states resulting core-shell structure and is etched into hollow out nanometer box, and through high temperature phosphorization technology, to obtain a kind of mixed metal phosphide
Base hollow out nanometer box elctro-catalyst；Compared to the nanostructure of non-hollow out, products therefrom has shown excellent water oxygen electricity and has urged
Change activity, this and its unique engraved structure, advantageous mass transfer and load transfer channel, active site abundant are closely related.
Detailed description of the invention
Fig. 1 is the flow chart for the mixed metal phosphide base hollow out nanometer box that the embodiment of the present invention 4 synthesizes；
Fig. 2 be the embodiment of the present invention 4 synthesize mixed metal phosphide base hollow out nanometer box X ray diffracting spectrum and
FeP、CoP、Ni2The XRD standard card of P；
Fig. 3 is the XPS high-resolution of Ni element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map；
Fig. 4 is the XPS high-resolution of Co element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map；
Fig. 5 is the XPS high-resolution of Fe element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map；
Fig. 6 is the XPS high-resolution of C element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map；
Fig. 7 is the XPS high-resolution of N element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map；
Fig. 8 is the XPS high-resolution of P element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map；
Fig. 9 is the Raman spectrum for the mixed metal phosphide base hollow out nanometer box that the embodiment of the present invention 4 synthesizes；
Figure 10 is the SEM photograph for the mixed metal phosphide base hollow out nanometer box that the embodiment of the present invention 4 synthesizes；
Figure 11 is the SEM photograph of the mixed metal phosphide base cubic block synthesized in comparative example of the present invention；
Figure 12 is the oxygen evolution reaction curve of mixed metal phosphide base hollow out nanometer box that the embodiment of the present invention 4 synthesizes and right
The oxygen evolution reaction curve of the mixed metal phosphide base cubic block synthesized in ratio；
Figure 13 is Tafel curve and the comparison for the mixed metal phosphide base hollow out nanometer box that the embodiment of the present invention 4 synthesizes
The Tafel curve of the mixed metal phosphide base cubic block synthesized in example.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of mixed metal phosphide base hollow out nanometer box, includes the following steps:
S1, synthesis Ni3[Fe(CN)6]2·H2O nano cubic block
Six hydration nickel sulfate, two citric acid monohydrate trisodiums are dissolved in deionized water, homogeneous solution A is formed；By iron cyaniding
Potassium is dissolved in deionized water, stirs evenly to form solution B；Solution B is added in solution A while stirring, has been added
Continue to stir after finishing, be stored at room temperature aging, centrifuge washing is dry, obtains Ni3[Fe(CN)6]2·H2O nano cubic block；
S2, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure
Nickelous nitrate hexahydrate, two citric acid monohydrate trisodiums are dissolved in deionized water and form homogeneous solution, Ni is added3[Fe
(CN)6]2·H2O nano cubic block is ultrasonically formed homogeneous solution C；Potassium cobalticyanide is dissolved in deionized water and is stirred, is formed uniform
Solution D；Solution C is stirred at room temperature, solution D is slowly dropped in solution C while stirring and continues to stir, room
Temperature stands aging, and centrifuge washing is dry, obtains Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure；
S3, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure
By Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure is scattered in dehydrated alcohol, shape
At uniform dispersion E；Ammonium hydroxide is dissolved in deionized water, stirs evenly to form solution F；F solution is added dropwise under stirring
Into E solution, continue to stir, centrifuge washing, it is dry, obtain Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O
Hollow out core-shell structure；
S4, synthesis mixed metal phosphide base hollow out nanometer box elctro-catalyst
Ni prepared by S33[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure is put into porcelain boat
In, sample a is obtained, sodium hypophosphite is put into another porcelain boat, obtains sample b, sample b is put into tube furnace on air inlet
Trip, sample a are placed on opening downstream in tube furnace, in a nitrogen atmosphere, tube furnace are warming up to 385 DEG C, calcining is cooled to room
Temperature, wherein the parkerizing process of tube furnace is carried out in nitrogen atmosphere, until temperature is down to room temperature after reaction, is mixed
Metal phosphide base hollow out nanometer box elctro-catalyst.
Embodiment 2
A kind of preparation method of mixed metal phosphide base hollow out nanometer box, includes the following steps:
S1, synthesis Ni3[Fe(CN)6]2·H2O nano cubic block
1mmol six hydration nickel sulfate, 1.25mmol two citric acid monohydrate trisodiums are dissolved in 100mL deionized water, are formed
Homogeneous solution A；
The 0.67mmol potassium ferricyanide is dissolved in 2mL deionized water, stirs evenly to form solution B；
B solution is added drop-wise in solution A while stirring, continues to stir 2min after being added dropwise, is stored at room temperature old
Change 6 days, centrifugation, be washed with deionized water in centrifugal process 3 times, dehydrated alcohol wash 2 times, finally place in air dry oven, in temperature
Dry 16h, drying obtain Ni at 60 DEG C of degree3[Fe(CN)6]2·H2O nano cubic block；
S2, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure
0.1mmol Nickelous nitrate hexahydrate, 0.12mmol two citric acid monohydrate trisodiums are dissolved in 3mL deionized water and are formed
0.04g Ni is added in even solution3[Fe(CN)6]2·H2O nano cubic block, ultrasound form homogeneous solution C；
0.07mmol potassium cobalticyanide is dissolved in 3mL deionized water, is stirred, homogeneous solution D is formed；
By solution C magnetic agitation 1h at room temperature, solution D is slowly dropped in solution C in the state of magnetic agitation
And continue to stir 5min, then magneton is taken out, stands aging 6 days at room temperature, is centrifuged, is washed with deionized water 3 in centrifugal process
It washes 1 time all over, dehydrated alcohol, finally places in air dry oven, dry 18h, drying obtain Ni under temperature 45 C3[Co
(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure；
S3, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure
By 0.05g Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2It is anhydrous that O core-shell structure is scattered in 25mL
In ethyl alcohol, uniform dispersion E is formed；
5mL ammonium hydroxide is dissolved in 50mL deionized water, stirs evenly to form solution F；
F solution is slowly dropped in E solution in the state of magnetic agitation, continues to stir 10min, centrifugation was centrifuged
Be washed with deionized water in journey 3 times, dehydrated alcohol wash 2 times, place the dry 12h of 50 DEG C of air dry ovens, obtain Ni3[Co(CN)6]2·
12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure；
S4, synthesis mixed metal phosphide base hollow out nanometer box elctro-catalyst
0.01g Ni prepared by S33[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure is put
Enter in porcelain boat, obtain sample a, 0.1g sodium hypophosphite is put into another porcelain boat, obtain sample b, sample b is put into tube furnace
Air inlet upstream, sample a are placed on opening downstream in tube furnace, in a nitrogen atmosphere, by tube furnace with the speed liter of 1 DEG C/min
Temperature is calcined 1h, is cooled to room temperature to 300 DEG C, and wherein the parkerizing process of tube furnace is carried out in nitrogen atmosphere, until reaction knot
Temperature is down to room temperature after beam, obtains mixed metal phosphide base hollow out nanometer box elctro-catalyst.
Embodiment 3
A kind of preparation method of mixed metal phosphide base hollow out nanometer box, includes the following steps:
S1, synthesis Ni3[Fe(CN)6]2·H2O nano cubic block
10mmol six hydration nickel sulfate, 12.5mmol two citric acid monohydrate trisodiums are dissolved in 1000mL deionized water, shape
At homogeneous solution A；
The 6.7mmol potassium ferricyanide is dissolved in 20mL deionized water, stirs evenly to form solution B；
B solution is added drop-wise in solution A while stirring, continues to stir 10min after being added dropwise, is stored at room temperature old
Change 10 days, centrifugation, be washed with deionized water in centrifugal process 6 times, dehydrated alcohol wash 5 times, finally place in air dry oven, in temperature
80 DEG C of dry 10h are spent, dries, obtains Ni3[Fe(CN)6]2·H2O nano cubic block；
S2, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure
0.4mmol Nickelous nitrate hexahydrate, 0.48mmol two citric acid monohydrate trisodiums are dissolved in 12mL deionized water and are formed
0.16g Ni is added in homogeneous solution3[Fe(CN)6]2·H2O nano cubic block, ultrasound form homogeneous solution C；
0.28mmol potassium cobalticyanide is dissolved in 12mL deionized water, is stirred, homogeneous solution D is formed；
By solution C magnetic agitation 5h at room temperature, solution D is slowly dropped in solution C in the state of magnetic agitation
And continue to stir 30min, then magneton is taken out, stands aging 10 days at room temperature, is centrifuged, is washed with deionized water in centrifugal process
6 times, dehydrated alcohol wash 4 times, finally place in air dry oven, in 80 DEG C of temperature dry 8h, dry, obtain Ni3[Co(CN)6]2·
12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure；
S3, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure
By 0.3g Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2It is anhydrous that O core-shell structure is scattered in 150mL
In ethyl alcohol, uniform dispersion E is formed；
35mL ammonium hydroxide is dissolved in 300mL deionized water, stirs evenly to form solution F；
F solution is slowly dropped in E solution in the state of magnetic agitation, continues to stir 60min, centrifugation was centrifuged
Be washed with deionized water in journey 6 times, dehydrated alcohol wash 4 times, place the dry 10h of 80 DEG C of air dry ovens, obtain Ni3[Co(CN)6]2·
12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure；
S4, synthesis mixed metal phosphide base hollow out nanometer box elctro-catalyst
0.1g Ni prepared by S33[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure is put
Enter in porcelain boat, obtain sample a, 1g sodium hypophosphite is put into another porcelain boat, obtain sample b, by sample b be put into tube furnace into
Port upstream, sample a are placed on opening downstream in tube furnace, in a nitrogen atmosphere, by tube furnace with the speed liter of 10 DEG C/min
Temperature is calcined 6h, is cooled to room temperature to 450 DEG C, and wherein the parkerizing process of tube furnace is carried out in nitrogen atmosphere, until reaction knot
Temperature is down to room temperature after beam, obtains mixed metal phosphide base hollow out nanometer box elctro-catalyst.
Embodiment 4
A kind of preparation method of mixed metal phosphide base hollow out nanometer box, includes the following steps:
S1, synthesis Ni3[Fe(CN)6]2·H2O nano cubic block
6mmol six hydration nickel sulfate, 7.5mmol two citric acid monohydrate trisodiums are dissolved in 590mL deionized water, are formed equal
Even solution A；
The 4mmol potassium ferricyanide is dissolved in 10mL deionized water, stirs evenly to form solution B；
B solution is added drop-wise in solution A while stirring, continues to stir 5min after being added dropwise, is stored at room temperature old
Change 7 days, centrifugation, be washed with deionized water in centrifugal process 5 times, dehydrated alcohol wash 3 times, finally place in air dry oven, in temperature
It spends 50 DEG C of dryings for 24 hours, dries, obtain Ni3[Fe(CN)6]2·H2O nano cubic block；
S2, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure
0.25mmol Nickelous nitrate hexahydrate, 0.31mmol two citric acid monohydrate trisodiums are dissolved in 8mL deionized water and are formed
0.1g Ni is added in homogeneous solution3[Fe(CN)6]2·H2O nano cubic block, ultrasound form homogeneous solution C；
0.16mmol potassium cobalticyanide is dissolved in 8mL deionized water, is stirred, homogeneous solution D is formed；
By solution C magnetic agitation 2h at room temperature, solution D is slowly dropped in solution C in the state of magnetic agitation
And continue to stir 10min, then magneton is taken out, stands aging 7 days at room temperature, is centrifuged, is washed with deionized water 5 in centrifugal process
It washes 2 times all over, dehydrated alcohol, finally places in air dry oven, dry for 24 hours in temperature 50 C, drying obtains Ni3[Co(CN)6]2·
12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure；
S3, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure
By 0.1g Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2It is anhydrous that O core-shell structure is scattered in 50mL
In ethyl alcohol, uniform dispersion E is formed；
15mL ammonium hydroxide is dissolved in 100mL deionized water, stirs evenly to form solution F；
F solution is slowly dropped in E solution in the state of magnetic agitation, continues to stir 20min, centrifugation was centrifuged
Be washed with deionized water in journey 5 times, dehydrated alcohol wash 2 times, it is dry for 24 hours to place 60 DEG C of air dry ovens, obtains Ni3[Co(CN)6]2·
12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure；
S4, synthesis mixed metal phosphide base hollow out nanometer box elctro-catalyst
0.02g Ni prepared by S33[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure is put
Enter in porcelain boat, obtain sample a, 0.2g sodium hypophosphite is put into another porcelain boat, obtain sample b, sample b is put into tube furnace
Air inlet upstream, sample a are placed on opening downstream in tube furnace, in a nitrogen atmosphere, by tube furnace with the speed liter of 5 DEG C/min
Temperature is calcined 3h, is cooled to room temperature to 400 DEG C, and wherein the parkerizing process of tube furnace is carried out in nitrogen atmosphere, until reaction knot
Temperature is down to room temperature after beam, obtains mixed metal phosphide base hollow out nanometer box elctro-catalyst.
Comparative example
A kind of preparation method of mixed metal phosphide base cubic block, includes the following steps:
S1, synthesis Ni3[Fe(CN)6]2·H2O nano cubic block
6mmol six hydration nickel sulfate, 7.5mmol two citric acid monohydrate trisodiums are dissolved in 590mL deionized water, are formed equal
Even solution A；
The 4mmol potassium ferricyanide is dissolved in 10mL deionized water, stirs evenly to form solution B；
B solution is added drop-wise in solution A while stirring, continues to stir 5min after being added dropwise, is stored at room temperature old
Change 7 days, centrifugation, be washed with deionized water in centrifugal process 5 times, dehydrated alcohol wash 3 times, finally place in air dry oven, in temperature
It spends 50 DEG C of dryings for 24 hours, dries, obtain Ni3[Fe(CN)6]2·H2O nano cubic block；
S2, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure
0.25mmol Nickelous nitrate hexahydrate, 0.31mmol two citric acid monohydrate trisodiums are dissolved in 8mL deionized water and are formed
0.1g Ni is added in homogeneous solution3[Fe(CN)6]2·H2O nano cubic block, ultrasound form homogeneous solution C；
0.16mmol potassium cobalticyanide is dissolved in 8mL deionized water, is stirred, homogeneous solution D is formed；
By solution C magnetic agitation 2h at room temperature, solution D is slowly dropped in solution C in the state of magnetic agitation
And continue to stir 10min, then magneton is taken out, stands aging 7 days at room temperature, is centrifuged, is washed with deionized water 5 in centrifugal process
It washes 2 times all over, dehydrated alcohol, finally places in air dry oven, dry for 24 hours in temperature 50 C, drying obtains Ni3[Co(CN)6]2·
12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure；
S3, synthesis mixed metal phosphide base cubic block
0.02g Ni prepared by S23[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure is put into porcelain
In boat, sample a is obtained, 0.2g sodium hypophosphite is put into another porcelain boat, obtains sample b, sample b is put into air inlet in tube furnace
Mouth upstream, sample a are placed on opening downstream in tube furnace, in a nitrogen atmosphere, tube furnace are warming up to the speed of 5 DEG C/min
400 DEG C, 3h is calcined, is cooled to room temperature, wherein the parkerizing process of tube furnace is carried out in nitrogen atmosphere, until after reaction
Temperature is down to room temperature, obtains mixed metal phosphide base cubic block.
Performance test:
Fig. 1 is the flow chart for the mixed metal phosphide base hollow out nanometer box that the embodiment of the present invention 4 synthesizes.As seen from the figure,
We prepare a kind of Ni first3[Fe(CN)6]2·H2O nano cubic block, then with Ni3[Fe(CN)6]2·H2O nano cubic block
For template and kernel, layer of Ni further is coated in its outer surface3[Co(CN)6]2·12H2O shell, to form nucleocapsid knot
Structure；Then ammonium hydroxide lithographic technique is used, above-mentioned resulting core-shell structure is etched into hollow out nanometer box, and be aided with subsequent high temperature
Parkerizing process finally obtains a kind of mixed metal phosphide base hollow out nanometer box elctro-catalyst.
Fig. 2 be the embodiment of the present invention 4 synthesize mixed metal phosphide base hollow out nanometer box X ray diffracting spectrum and
FeP, CoP and Ni2The XRD standard card of P.The XRD standard card of FeP is ICDD 00-003-1066, the XRD standard card of CoP
Piece is ICDD 01-089-4862, Ni2The XRD standard card of P is ICDD 03-065-1989.Wherein, ICDD 00-003-
1066 characteristic peak is used ● is indicated, the characteristic peak of ICDD 01-089-4862 is indicated with ■, the feature of ICDD 03-065-1989
Peak is indicated with *.As shown in Figure 2, comprising there are three types of the object phases of metal phosphide, i.e. FeP, CoP and Ni in products therefrom2P, it was demonstrated that
The elctro-catalyst that the embodiment of the present invention 4 synthesizes is mixed metal phosphide base hollow out nanometer box.
Fig. 3 is the XPS high-resolution of Ni element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map.As shown in figure 3, can be wherein the metallic state for belonging to nickel phosphide in metal phosphide for the peak at 853.1eV in combination
Niδ+Peak；Corresponding position in conjunction with where can be 856.6eV is Ni 2p3/2Acromion；It is in conjunction with the peak that can be 860.8eV
The characteristic peak of oxidation state nickel, this is because caused by the oxidation of sample surfaces nickel element.
Fig. 4 is the XPS high-resolution of Co element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map.In Fig. 4, wherein combination can belong to the Co 2p of Co species in Co-P for the peak of 778.3eV3/2；Can be in combination
Peak at 781.4eV and 782.4eV is the satellites of oxidation state cobalt and oxidation state cobalt, this is because sample and air contact process
Caused by surface oxidation occurs for middle cobalt element.
Fig. 5 is the XPS high-resolution of Fe element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map.For the high-resolution XPS spectrum of Fe 2p shown in fig. 5, through over-fitting, three peaks are high-visible.Peak pair at 706.8eV
Should be in the Fe element in iron phosphide, and the peak at 710.5eV is the characteristic peak of oxidation state iron, this is because sample is exposed to air
Caused by surface oxidation occurs for middle ferro element, satellite peak value is then located at 713.8eV.
Fig. 6 is the XPS high-resolution of C element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map.As shown in fig. 6, the peak that wherein combination can be located at appearance at 284.5eV can belong to graphitic carbon C=C/C-C, 285.5eV
C-P/C-O-P and C-N key is corresponded respectively to the peak at 286.4eV.The appearance of C species mostlys come from cyanogen in precursors
The carbonization of base shows not only to contain metal phosphide in resulting elctro-catalyst, also contains a large amount of carbon, this can be elctro-catalyst
The promotion of electric conductivity and electro catalytic activity provide safeguard.
Fig. 7 is the XPS high-resolution of N element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map.Wherein combination can positioned at the peak at 397.7eV, 399.9eV, 401.7eV, can be attributed to respectively pyridine nitrogen, pyrroles's nitrogen and
Quaternary nitrogen.Cyano of the appearance at nitrogen peak in precursors shows that the carbon component in elctro-catalyst contains a large amount of nitrogen member
Element, the i.e. formation of nitrogen-doped carbon.
Fig. 8 is the XPS high-resolution of P element in the mixed metal phosphide base hollow out nanometer box of the synthesis of the embodiment of the present invention 4
Map.The high-resolution XPS spectrum of P 2p can be to have a peak respectively at 129.3eV and 134.4eV in combination；Wherein combination can be located at
Peak at 129.3eV corresponds to the P in metal phosphideδ-, relative to elemental phosphorous (130eV), negative displacement is had occurred in this peak, therefore
With negative electrical charge；And combining can then be attributed to expose P elements oxygen in aerial metal phosphide at the peak at 134.4eV
Change the oxidation phosphate species formed.
Fig. 9 is the Raman spectrum for the mixed metal phosphide base hollow out nanometer box that the embodiment of the present invention 4 synthesizes；It can by Fig. 9
Can be clearly seen in 1350cm-1And 1580cm-1There are two apparent peaks at place, respectively correspond the D band and G band of carbon material.It is logical
Often, the peak D represents the lattice defect of carbon atom, and the peak G represents carbon atom sp2Stretching vibration in the face of hydridization.Wherein, the peak D and the peak G peak
Strong ratio (ID/IG) it is the important parameter for characterizing carbon material degree of graphitization, ratio is smaller, illustrates that carbon material has higher stone
Blackization degree.According to calculating it is found that the I of the mixed metal phosphide base hollow out nanometer box of synthesisD/IGAbout 0.95, illustrate that this is urged
Carbon degree of graphitization with higher in agent.
Figure 10 is the SEM photograph for the mixed metal phosphide base hollow out nanometer box that the embodiment of the present invention 4 synthesizes.It can from figure
With find out the sample pattern be cube block structure, and examine it can be found that cubic block face by hollow out, i.e., it is hollow
The formation of nanometer box, therefore advantageous mass transfer can be provided for the active site inside nanometer box for this engraved structure and load transfer is logical
Road, to promote its electro catalytic activity.
Figure 11 is the SEM photograph of the mixed metal phosphide base cubic block synthesized in comparative example of the present invention.As seen from the figure, when
When carrying out high temperature phosphorization as presoma using the core-shell structure that does not etch, products therefrom although also showing the pattern of cubic block,
Be cubic block face not by hollow out, that is, lacked advantageous mass transfer and load transfer channel.
Figure 12 is the oxygen evolution reaction curve of mixed metal phosphide base hollow out nanometer box that the embodiment of the present invention 4 synthesizes and right
The oxygen evolution reaction curve of the mixed metal phosphide base cubic block synthesized in ratio.According to calculating it is known that when to mix gold
Category phosphide base cubic block is catalyst, and current density reaches 10mA/cm2When required overpotential be 271mV；And when with mixed
Conjunction metal phosphide base hollow out nanometer box is catalyst, reaches 10mA/cm in current density2When, it is thus only necessary to 243mV's is excessively electric
Position shows that prepared mixed metal phosphide base hollow out nanometer box has excellent oxygen evolution activity, this and its unique hollow out
Structure, advantageous mass transfer and load transfer channel, active site abundant are closely related.
Figure 13 is Tafel curve and the comparison for the mixed metal phosphide base hollow out nanometer box that the embodiment of the present invention 4 synthesizes
The Tafel curve of the mixed metal phosphide base cubic block synthesized in example.As seen from the figure, vertical compared to mixed metal phosphide base
Square (47mV/Dec), mixed metal phosphide base hollow out nanometer box have the smallest Tafel slope (31mV/Dec), this explanation
With the increase of overpotential, mixed metal phosphide base hollow out nanometer box is capable of providing the electro-catalysis oxygen evolution reaction of higher efficiency.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of mixed metal phosphide base hollow out nanometer box, which comprises the steps of:
S1, synthesis Ni3[Fe(CN)6]2·H2O nano cubic block
Six hydration nickel sulfate, two citric acid monohydrate trisodiums are dissolved in deionized water, homogeneous solution A is formed；The potassium ferricyanide is molten
In deionized water, stir evenly to form solution B；Solution B is added in solution A while stirring, after addition
Continue to stir, stand aging, centrifuge washing is dry, obtains Ni3[Fe(CN)6]2·H2O nano cubic block；
S2, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure
Nickelous nitrate hexahydrate, two citric acid monohydrate trisodiums are dissolved in deionized water and form homogeneous solution, Ni is added3[Fe
(CN)6]2·H2O nano cubic block is ultrasonically formed homogeneous solution C；Potassium cobalticyanide is dissolved in deionized water, is stirred, is formed equal
Even solution D；Solution C is stirred, solution D is slowly dropped in solution C while stirring and continues to stir, is stood old
Change, centrifuge washing, it is dry, obtain Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure；
S3, synthesis Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure
By Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure is scattered in dehydrated alcohol, is formed equal
Even dispersion liquid E；Ammonium hydroxide is dissolved in deionized water, stirs evenly to form solution F；It is molten that F solution is added drop-wise to E under stirring
In liquid, continue to stir, centrifuge washing, it is dry, obtain Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core
Shell structure；
S4, synthesis mixed metal phosphide base hollow out nanometer box elctro-catalyst
Ni prepared by S33[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure is put into porcelain boat,
Sample a is obtained, sodium hypophosphite is put into another porcelain boat, obtains sample b, sample b is put into air inlet upstream in tube furnace, sample
Product a is placed on opening downstream in tube furnace, in a nitrogen atmosphere, tube furnace is warming up to 300-450 DEG C, calcining is cooled to room
Temperature, wherein the parkerizing process of tube furnace is carried out in nitrogen atmosphere, until temperature is down to room temperature after reaction, is mixed
Metal phosphide base hollow out nanometer box elctro-catalyst.
2. the preparation method of mixed metal phosphide base hollow out nanometer box according to claim 1, which is characterized in that in S1
In, six hydration nickel sulfate, two citric acid monohydrate trisodiums, the molar ratio of the potassium ferricyanide are 1-10:1.25-12.5:0.67-6.7；
Preferably, six hydration nickel sulfate, two citric acid monohydrate trisodiums, the molar ratio of the potassium ferricyanide are 1.5:1.875:1.
3. the preparation method of mixed metal phosphide base hollow out nanometer box according to claim 1, which is characterized in that
3-6 is washed with deionized water in S1, S2, S3, during centrifuge washing to wash 2-5 times all over, dehydrated alcohol.
4. the preparation method of mixed metal phosphide base hollow out nanometer box according to claim 1, which is characterized in that in S2
In, Nickelous nitrate hexahydrate, two citric acid monohydrate trisodiums, the molar ratio of potassium cobalticyanide are 0.1-0.4:0.12-0.48:0.07-
0.28；
Preferably, Nickelous nitrate hexahydrate, Ni3[Fe(CN)6]2·H2It is 0.1- that the molal weight ratio of O nano cubic block, which is mmol:g,
0.4:0.04-0.16.
5. the preparation method of mixed metal phosphide base hollow out nanometer box according to claim 1, which is characterized in that in S3
In, Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O core-shell structure, ammonium hydroxide w/v g:ml be
0.05-0.3:5-35.
6. the preparation method of mixed metal phosphide base hollow out nanometer box according to claim 1, which is characterized in that in S4
In, Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure, sodium hypophosphite weight ratio be
0.01-0.1:0.1-1；
Preferably, Ni3[Co(CN)6]2·12H2O wraps up Ni3[Fe(CN)6]2·H2O hollow out core-shell structure: the weight of sodium hypophosphite
Than for 1:10.
7. the preparation method of mixed metal phosphide base hollow out nanometer box according to claim 1, which is characterized in that in S4
In, the heating rate of tube furnace is 1-10 DEG C/min.
8. the preparation method of mixed metal phosphide base hollow out nanometer box according to claim 1, which is characterized in that in S4
In, calcination time 1-6h.
9. a kind of mixed metal phosphide base hollow out nanometer box, which is characterized in that according to claim 1-8 mixed
Close the preparation method preparation of metal phosphide base hollow out nanometer box.
10. a kind of application of mixed metal phosphide base hollow out nanometer box as claimed in claim 9 in elctro-catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910446216.3A CN110038603B (en) | 2019-05-27 | 2019-05-27 | Mixed metal phosphide-based hollow nano-box and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910446216.3A CN110038603B (en) | 2019-05-27 | 2019-05-27 | Mixed metal phosphide-based hollow nano-box and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110038603A true CN110038603A (en) | 2019-07-23 |
| CN110038603B CN110038603B (en) | 2021-10-08 |
Family
ID=67283616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910446216.3A Active CN110038603B (en) | 2019-05-27 | 2019-05-27 | Mixed metal phosphide-based hollow nano-box and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110038603B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114784300A (en) * | 2022-05-30 | 2022-07-22 | 安徽理工大学 | Fe-Ni based or Fe-Co based mott-Schottky electrocatalyst, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170044679A1 (en) * | 2015-08-11 | 2017-02-16 | Wisconsin Alumni Research Foundation | High performance earth-abundant electrocatalysts for hydrogen evolution reaction and other reactions |
| CN109301267A (en) * | 2018-10-29 | 2019-02-01 | 广东工业大学 | A kind of phosphide nanocatalyst and preparation method thereof |
| US20190048482A1 (en) * | 2017-08-10 | 2019-02-14 | Board Of Trustees Of The University Of Arkansas | 3d reduced graphene oxide foams embedded with nanocatalysts, synthesizing methods and applications of same |
| CN109437338A (en) * | 2018-11-30 | 2019-03-08 | 福州大学 | The preparation method of one type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material |
| CN109518216A (en) * | 2018-11-15 | 2019-03-26 | 同济大学 | A kind of phosphatization cobalt nanometer frame and its preparation and application |
| CN109647458A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | The method that self-template methods synthesis has the double-metal phosphide elctro-catalyst of hollow structure |
-
2019
- 2019-05-27 CN CN201910446216.3A patent/CN110038603B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170044679A1 (en) * | 2015-08-11 | 2017-02-16 | Wisconsin Alumni Research Foundation | High performance earth-abundant electrocatalysts for hydrogen evolution reaction and other reactions |
| US20190048482A1 (en) * | 2017-08-10 | 2019-02-14 | Board Of Trustees Of The University Of Arkansas | 3d reduced graphene oxide foams embedded with nanocatalysts, synthesizing methods and applications of same |
| CN109301267A (en) * | 2018-10-29 | 2019-02-01 | 广东工业大学 | A kind of phosphide nanocatalyst and preparation method thereof |
| CN109518216A (en) * | 2018-11-15 | 2019-03-26 | 同济大学 | A kind of phosphatization cobalt nanometer frame and its preparation and application |
| CN109437338A (en) * | 2018-11-30 | 2019-03-08 | 福州大学 | The preparation method of one type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material |
| CN109647458A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | The method that self-template methods synthesis has the double-metal phosphide elctro-catalyst of hollow structure |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114784300A (en) * | 2022-05-30 | 2022-07-22 | 安徽理工大学 | Fe-Ni based or Fe-Co based mott-Schottky electrocatalyst, preparation method and application thereof |
| CN114784300B (en) * | 2022-05-30 | 2023-09-15 | 安徽理工大学 | Fe-Ni-based or Fe-Co-based Mort-Schottky electro-catalyst, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110038603B (en) | 2021-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111229232B (en) | Foam nickel-based porous NiFe hydrotalcite nano-sheet and preparation and application thereof | |
| WO2020073398A1 (en) | Ultrathin ni-fe-mof nanosheet, preparation method therefor and application thereof | |
| Hao et al. | Unraveling the synergistic effect of defects and interfacial electronic structure modulation of pealike CoFe@ Fe3N to achieve superior oxygen reduction performance | |
| Hao et al. | Highly efficient overall-water splitting enabled via grafting boron-inserted Fe-Ni solid solution nanosheets onto unconventional skeleton | |
| CN110813350B (en) | Carbon-based composite electrocatalyst and preparation method and application thereof | |
| CN106025302A (en) | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material | |
| CN110838588B (en) | Rechargeable zinc-air battery bifunctional catalyst and preparation method and application thereof | |
| CN105107536A (en) | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis | |
| Guo et al. | Synthesis of Cobalt–Glycerate hierarchical structure and their conversion into hierarchical CoP nanospheres for the hydrogen evolution reaction | |
| Li et al. | Ultrathin 2D nanosheet based 3D hierarchical hollow polyhedral CoM/C (M= Ni, Cu, Mn) phosphide nanocages as superior electrocatalysts toward oxygen evolution reaction | |
| CN109248703A (en) | A kind of load Ni3The preparation method and its resulting materials of the nitrogen-doped carbon nanocomposite of Fe and application | |
| WO2021232751A1 (en) | Porous coo/cop nanotubes, preparation method therefor and use thereof | |
| CN109731586B (en) | Preparation method and application of copper-containing metal organic framework-derived hierarchical porous copper phosphide/carbohydrate electrolysis electrocatalyst | |
| CN106252674A (en) | A kind of N doping charcoal carries non noble metal oxygen reduction/oxygen and separates out bifunctional catalyst | |
| CN112844427A (en) | Co-B-P-O nanoparticle loaded reduced graphene oxide composite material and preparation method and application thereof | |
| CN104868094A (en) | Porous ruthenium dioxide and manganese dioxide combined electrode and preparation method and application thereof | |
| CN110965076A (en) | Preparation method of electrolytic water electrode with double-function three-dimensional layered core-shell structure | |
| CN106960730A (en) | A kind of high stability nickel cobalt double-hydroxide electrode material and preparation method thereof | |
| Li et al. | Integration of heterointerface and porosity engineering to achieve efficient hydrogen evolution of 2D porous NiMoN nanobelts coupled with Ni particles | |
| Ren et al. | Multifunctional metal-phosphide-based electrocatalysts for highly efficient solar hydrogen production integrated devices | |
| CN110474059B (en) | Method for solid-phase macro synthesis of non-noble metal oxygen reduction catalyst, catalyst and application thereof | |
| CN110038603A (en) | A kind of mixed metal phosphide base hollow out nanometer box and preparation method thereof, application | |
| Yang et al. | Fast acid-leaching strategy treated hollow cobalt–carbon materials as highly efficient electrochemical catalysts for Zn–air batteries | |
| CN117187856A (en) | Preparation method of bifunctional phosphide catalyst and full water decomposition application thereof | |
| Han et al. | Flocculent VS nanoparticle aggregate-modified NiCo 2 S 4 nanograss arrays for electrocatalytic water splitting |
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 |