CN106807416A - A kind of self-supporting nickel phosphide nanometer sheet material of electrocatalytic decomposition water hydrogen manufacturing and preparation method thereof - Google Patents
A kind of self-supporting nickel phosphide nanometer sheet material of electrocatalytic decomposition water hydrogen manufacturing and preparation method thereof Download PDFInfo
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- CN106807416A CN106807416A CN201710029811.8A CN201710029811A CN106807416A CN 106807416 A CN106807416 A CN 106807416A CN 201710029811 A CN201710029811 A CN 201710029811A CN 106807416 A CN106807416 A CN 106807416A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims abstract description 18
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 238000000354 decomposition reaction Methods 0.000 title abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 52
- 239000002120 nanofilm Substances 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract 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 abstract description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229960002163 hydrogen peroxide Drugs 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000010335 hydrothermal treatment Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 21
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 8
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 210000001367 artery Anatomy 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JTNHEIQTYTZTGU-UHFFFAOYSA-L [P].[Ni](O)O Chemical compound [P].[Ni](O)O JTNHEIQTYTZTGU-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- -1 sodium hypophosphites Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 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
-
- B01J35/33—
-
- 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
-
- 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
Abstract
The invention belongs to the preparation of porous nano catalysis material, metallic substrates direct growth porous nanometer structure material and its electro-catalysis application are particularly well-suited to.The material possesses multi-stage artery structure, and phosphatization nickel nano film is directly grown in nickel screen substrate skeleton, possess stronger mechanical stability, expose more avtive spot, solved to prepare the shortcomings of cumbersome, stability is poor, avtive spot is few in the presence of present preparation technology.The material is prepared using hydrogen peroxide hydrothermal oxidization etching growth nickel hydroxide nano piece is first passed through, afterwards using the synthetic method of sodium hypophosphite low temperature phosphor.This materials application greatly simplifies the preparation process of electrode in electrocatalytic decomposition aquatic products hydrogen, significantly improves the stability of catalyst, obtains preferably catalysis and produces hydrogen effect, with application value higher.The present invention uses equipment simple, and preparation condition is gentle, and raw material is easy to get inexpensively, is adapted to industrial mass production.
Description
Technical field
Phosphatization nickel nano film is loaded the present invention relates to a kind of nickel screen for possessing self supporting structure and greater activity specific surface area
The preparation method of catalysis material, and it is applied to electrocatalytic decomposition water hydrogen manufacturing, belong to inorganic nano catalysis material field.
Background technology
Being widely used in for fossil energy also results in serious environmental pollution etc. while being greatly facilitated progress of human society
Adverse consequences.To realize the sustainable development of modern society, find and develop reproducible green energy resource material and seem extremely have
It is necessary.Wherein, Hydrogen Energy is considered as future society most potential as the support future economy and the optimal clean energy resource of social development
Alternative energy source.Thus, the water electrolysis hydrogen production research involved by the production and utilization of hydrogen turns into grinding for current researcher
Study carefully emphasis.Although platinum based catalyst possesses excellent electrocatalytic hydrogen evolution performance, it is used as the high price of noble metal and rare
Property feature, significantly limit its extensive use in the industry.Meanwhile, in order to simplify electric decomposition water hydrogen production bioreactor, improve and produce
Hydrogen overall efficiency, reduces production cost, prepares the bifunctional catalyst for possessing liberation of hydrogen simultaneously and analysis oxygen and is also intended to the weight for considering
Point.Therefore, the bifunctional catalyst for possessing greater activity and stabilization is developed to be applied to water electrolysis hydrogen production and possess important showing
Sincere justice.
Transition metal material is subject to more and more because of its adjustable structure composition, active and relatively inexpensive price higher
Concern, the application in energy conversion and energy storage field is also more and more.Transient metal sulfide, oxide, carbide, nitridation
Thing and phosphide etc. show preferable electrocatalytic hydrogen evolution activity.Wherein, metal phosphide is urged relative to other nanometer of electricity
For agent, possesses more preferably activity and stability.In general, nanometer electrical catalyst is often prepared in the form of powder particle
Out.Thus, the use of binding agent in use is inevitable.Cumbersome coating procedure is unfavorable for large-scale business
Industry metaplasia is produced, while also improving production cost, reduces the competitive advantage of electrocatalytic hydrogen evolution.What is more important, activity is urged
Weaker bonding force has a strong impact on the stability of catalyst between agent and substrate.Recently, using hydro-thermal or the side of electro-deposition
Method obtains the elctro-catalyst of self-supporting, although ensure that bonding force higher between catalyst and substrate, alleviates catalyst and exists
The problem come off during desorbing gas, but its catalysis activity still has larger gap compared with precious metals pt base catalyst.Cause
This it is still necessary to, using more easily method, optimize the micro-nano structure of metal phosphide, further improve the work of its catalytic hydrogen evolution
Property.
Here, we prepare the nickel phosphide nanometer being directly grown on nickel screen skeleton using simple synthetic method
Piece.The nickel phosphide nano material of the self-supporting for preparing maintains the loose structure of nickel screen, and phosphatization nickel nano film is intensive
Nickel screen skeleton is grown on, therefore ensure that its mechanical stability higher, and then ensure that its stability in use.Will
It is applied to alkaline electrolyte water electrolysis hydrogen production, obtains preferable catalytic effect.Because nickel phosphide is directly grown in porous nickel screen
On skeleton, unique combining structure assigns catalyst system electric conductivity higher and larger active area, these factors
It is greatly promoted the catalysis activity and stability of phosphatization nickel nano film.In view of the stronger oxidability of hydrogen peroxide, the party
Method provides possibility to synthesize other self-supporting metallic substrates nano catalytic materials, also indicates that the nickel phosphide nanometer of this self-supporting
Piece and its synthesis strategy have very big development and application prospect in energy conversion and energy storage field.
The content of the invention
The present invention is intended to provide a kind of phosphatization nickel nano film be directly grown in the self-supporting of nickel screen substrate surface material and
Its preparation method, tries hard to overcome existing poor catalyst stability, the few shortcoming of avtive spot.Preparation equipment of the present invention is simple, behaviour
Facilitate, save energy, raw material is simple and easy to get, it is with low cost.And synthesized nickel phosphide/nickel screen composite material exhibits go out compared with
Double-function catalyzing in alkaline electrolyte electrocatalytic hydrogen evolution and analysis oxygen high is active.
To achieve these goals, the present invention uses cheap nickel screen as substrate, using hydrogen peroxide in high temperature hydro-thermal
Under the conditions of stronger oxidability, obtain being directly grown in the nickel hydroxide nano piece on nickel screen skeleton, afterwards low temperature phosphor
Nickel hydroxide is converted into phosphatization nickel nano film；Whole process ensure that the phosphatization nickel nano film of resulting self-supporting possess compared with
Strong mechanical stability and more avtive spots expose, and then ensure to obtain the nickel phosphide electrocatalytic decomposition water of efficient stabilization
Catalyst for preparing hydrogen.
The present invention is to provide the preparation method that a kind of phosphatization nickel nano film is directly grown in metal nickel screen substrate, specific step
It is rapid as follows：
1. nickel screen is placed in hydrogen peroxide (10-20wt%) aqueous solution, hydro-thermal reaction 2-5 hours under the conditions of 100-150 DEG C；
2. after the nickel screen for being obtained after hydro-thermal process is washed through deionized water and ethanol, vacuum drying；
3. the nickel screen that will be obtained is placed in tube furnace middle part, and sodium hypophosphite is placed in tubular type furnace upper end；Under nitrogen protective condition,
Nitrogen flow rate is 50ml/min, and temperature programming is kept for 2-5 hour to 300-500 DEG C, and heating rate is 3-10 DEG C/min, and reaction is tied
Room temperature is naturally cooled to after beam；The usage amount of sodium hypophosphite is in parkerizing process：It is low when nickel screen size used is 1 × 3cm
The consumption of sodium hypophosphite is 300-1000mg in warm parkerizing process；Obtain nickel screen after phosphatization to be washed through deionized water and ethanol, very
Sky is dried；
4. above-mentioned product shows good electrochemistry liberation of hydrogen, oxygen evolution activity in the alkaline electrolyte, and has good stability；
As bifunctional catalyst, liberation of hydrogen, analysis oxygen are capable of achieving under the conditions of two electrode systems, under relatively low voltage conditions, and show
Go out preferable stability.
The present invention has following features：
1. material is prepared using cheap, nontoxic raw material, be conducive to environmental protection；
2. preparation process is simple to operate, without large-scale, complicated equipment, reduces preparation cost；
3. the material for preparing has heat endurance and chemical stability higher；
4. the material for preparing has loose structure, in lamella, with specific surface area active higher；And it is directly grown in nickel
Net surface, it is difficult for drop-off, it is ensured that catalyst stability in use；
5. method preparation technology and equipment are simple, there is preferable large-scale industrial production prospect.
Sodium hypophosphite can also be replaced with sulphur powder or selenium powder in preparation process belonging to of the invention, be used to prepare metal vulcanization
Thing or selenides；Metal nickel screen can also be replaced with other metal materials such as iron net, copper mesh, molybdenum foil, be used to prepare corresponding
The metal phosphide of self-supporting etc..
Brief description of the drawings
The wide-angle XRD spectrum of sample Ni/NF and NiP/NF in Fig. 1 examples 1, shows that the material for preparing is nickel phosphide
With the composite of metallic nickel；
ESEM (SEM) photo (a) of sample NiP/NF and transmission electron microscope (TEM) photo (b), table in Fig. 2 examples 1
The bright nickel phosphide for preparing is in lamellar structure, and dense growth is on nickel screen skeleton, and phosphatization nickel nano film is piled up by little particle
Form, leave more micropore on lamella；
Electrocatalytic hydrogen evolution (HER) in Fig. 3 examples 2 under the alkaline electrolyte environment (1.0M KOH) of sample NiP/NF
Linear scan polarization curve and corresponding Tafel curves, showing phosphatization nickel nano film to be directly grown on nickel screen skeleton can show
Write ground and improve electro-catalysis HER reactivities and kinetics；
Oxygen (OER) is analysed in electro-catalysis in Fig. 4 examples 2 under the alkaline electrolyte environment (1.0M KOH) of sample NiP/NF
Linear scan polarization curve and corresponding Tafel curves, showing phosphatization nickel nano film to be directly grown on nickel screen skeleton can show
Write ground and improve electro-catalysis OER reactivities and kinetics；
Sample NiP/NF is used as bifunctional catalyst, the linear scan pole under the conditions of two electrode systems in Fig. 5 examples 3
Change curve, show that NiP/NF can at lower voltages realize the electro-catalysis aquatic products hydrogen under the conditions of alkaline environment.
Specific embodiment
Embodiment 1：
After business nickel screen (1 × 3cm of size) is washed successively through ethanol, acetone, deionized water, 100 DEG C of dryings 12 are small
When.The clean nickel screen that will be obtained is placed in 50mL reactors, includes 30mL hydrogen peroxide (10wt%) solution.By the reaction of good seal
Kettle reacts 2 hours under being placed in 120 DEG C of environment, and natural cooling is cooled to room temperature after question response terminates, and after product is scrubbed, enters
One step in 100 DEG C of dryings, labeled as Ni/NF.The Ni/NF for obtaining is characterized through XRD and SEM and is turned out to be nickel hydroxide nano piece, and
It is directly grown in nickel screen surface.Nickel screen after the oxide etch that will be obtained is placed in tube furnace middle part, and 300mg sodium hypophosphites are put
In tube furnace top, under nitrogen protection, nitrogen flow rate is 50mL/ minute, and temperature programming is kept for 2 hours to 350 DEG C, is heated up fast
Rate is 3 DEG C/min, room temperature is naturally cooled to after terminating, after product is washed through deionized water and ethanol, further at 100 DEG C
Dry, labeled as NiP/NF.Sample is characterized through XRD, SEM, TEM and XPS etc. and turns out to be the nickel phosphide with lamellar structure, and
And be directly grown on metallic nickel network framework.Wherein XRD spectra shows that the sample for obtaining is nickel phosphide；SEM and TEM show
To phosphatization nickel nano film be made up of nanometer little particle, and there are a large amount of micropores；XPS high-resolution spectrogram confirms the product for obtaining
Really it is nickel phosphide.
Embodiment 2：
Sample NiP/NF in embodiment 1 is directly as working electrode.The electrochemistry work that electro-chemical test is controlled in computer
Carried out on standing, using three electrode test systems, used as to electrode, Pt lines are used as working electrode, and 1.0M KOH for Ag/AgCl
The aqueous solution is used as alkaline electrolyte.The test scope of polarization curve, is 0 to -0.6V (vs reversible hydrogen electrodes) to HER, is to OER
1.2 to 1.7V (vs reversible hydrogen electrodes).The linear polarisation curves and Tafel curves difference of the catalyst of Fig. 3 and Fig. 4 display synthesis
To HER and OER processes.
Embodiment 3：
Sample NiP/NF in embodiment 2 is direct respectively as negative electrode and anode, under two electrode test system conditions, with
The 1.0M KOH aqueous solution is used as alkaline electrolyte.Electro-chemical test is carried out on the electrochemical workstation that computer is controlled.Electrode
Sweep limits is 1.1 to 2.0V.Fig. 5 shows the linear scan polarization curve of synthesized catalyst.Be can see by figure
When voltage is 1.62V, the catalyst system and catalyzing just can reach 10mA/cm2Current density, show the catalyst it is excellent electro-catalysis analysis
Hydrogen, oxygen evolution activity.
Above to the detailed description of one embodiment of the present of invention process, but the content is only obtaining for present invention preparation
Embodiment of the catalyst under preferable preparation condition, it is impossible to be considered as limiting practical range of the invention.Therefore Yi Benfa
Variation and improvement for being done in bright application range etc., all should still belong within patent covering scope of the invention.
Claims (3)
1. a kind of phosphatization nickel nano film is directly grown in the material of porous-metal nickel network framework, it is characterised in that many with self-supporting
Pore structure, phosphatization nickel nano film is equably grown on nickel screen skeleton；Phosphatization nickel nano film/the nickel screen of the self-supporting for preparing is multiple
Condensation material, activity higher is shown to alkaline electrolysis plastidome electrocatalytic hydrogen evolution and oxygen evolution reaction；Its preparation method include with
Lower step：
A) metal nickel screen is placed in aqueous hydrogen peroxide solution, hydro-thermal process is for a period of time at a certain temperature；
B) nickel screen that will be obtained after hydro-thermal process is washed through deionized water and ethanol, vacuum drying；
C) under nitrogen protection, nitrogen flow rate is 50mL/min, and nickel screen after hydro-thermal is placed in into tube furnace middle part, and sodium hypophosphite is placed in
Tube furnace top, temperature programming to uniform temperature is kept for a period of time, and heating rate is 3-10 DEG C/min, is then naturally cooled to
Room temperature；
D) gained nickel phosphide is washed through deionized water, vacuum drying.
2. phosphatization nickel nano film according to claim 1 is directly grown in the preparation method of nickel screen skeleton, it is characterised in that：
The first diluted hydrogenperoxide steam generator hydro-thermal process of nickel screen, afterwards again through low temperature phosphor process；In hydrothermal treatment process, use
The solubility of hydrogen peroxide is 10-20wt%, and hydrothermal temperature is 100-150 DEG C.The hydro-thermal reaction time is 2-5 hours.
3. phosphatization nickel nano film according to claim 1 is directly grown in the preparation method of nickel screen skeleton, it is characterised in that：
When nickel screen size used is 1x3cm, the consumption of sodium hypophosphite is 300-1000mg during low temperature phosphor；Low temperature phosphor temperature
It it is 300-500 DEG C, the reaction time is 2-5 hours.
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| CN201710029811.8A CN106807416A (en) | 2017-01-12 | 2017-01-12 | A kind of self-supporting nickel phosphide nanometer sheet material of electrocatalytic decomposition water hydrogen manufacturing and preparation method thereof |
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| CN201710029811.8A CN106807416A (en) | 2017-01-12 | 2017-01-12 | A kind of self-supporting nickel phosphide nanometer sheet material of electrocatalytic decomposition water hydrogen manufacturing and preparation method thereof |
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| CN107694584A (en) * | 2017-10-15 | 2018-02-16 | 华东师范大学 | A kind of self-supporting catalyst of phosphatizing nickel and its preparation method and application |
| CN107876071A (en) * | 2017-10-23 | 2018-04-06 | 曲阜师范大学 | Fe2P nano-array surface modification Ni (OH)2Liberation of hydrogen catalyst and its preparation method and application |
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