CN107447208A - A kind of method for preparing Pd Ni Fe P alloy films using chemical plating displacement - Google Patents
A kind of method for preparing Pd Ni Fe P alloy films using chemical plating displacement Download PDFInfo
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- CN107447208A CN107447208A CN201710486054.7A CN201710486054A CN107447208A CN 107447208 A CN107447208 A CN 107447208A CN 201710486054 A CN201710486054 A CN 201710486054A CN 107447208 A CN107447208 A CN 107447208A
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- alloy
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- chemical plating
- plating
- alloy films
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- 229910001096 P alloy Inorganic materials 0.000 title claims abstract description 26
- 238000007747 plating Methods 0.000 title claims abstract description 25
- 238000006073 displacement reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000126 substance Substances 0.000 title claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 27
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000004310 lactic acid Substances 0.000 claims abstract description 9
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 239000001509 sodium citrate Substances 0.000 claims abstract description 9
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- -1 methyl butyl Chemical group 0.000 claims abstract description 6
- 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 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004202 carbamide Substances 0.000 claims abstract description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000956 alloy Substances 0.000 abstract description 9
- 239000011790 ferrous sulphate Substances 0.000 abstract description 8
- 235000003891 ferrous sulphate Nutrition 0.000 abstract description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910000808 amorphous metal alloy Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052603 melanterite Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002669 PdNi Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical group [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on 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
- 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
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemically Coating (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method for preparing Pd Ni Fe P alloy films using chemical plating displacement, comprise the following steps：Using nickel sulfate, ferrous sulfate, sodium hypophosphite, lactic acid, trisodium citrate as chemical plating raw material, chemical plating is carried out on Cu sheet matrixes, obtains Ni Fe P alloy plating pieces；Ionic liquid methyl butyl imidazolitm chloride (molecular formula BMIMCl), ethylene glycol (EG), urea (mol ratio 1 are added in reaction vessel is replaced:1:1) anhydrous low melting point mixed solvent, containing palladium ionic liquids [BMIM]2PdCl4As displacement liquid, Ni Fe P alloy plating pieces are put into displacement liquid and soak a period of time, by replacing Pd Ni Fe P alloy films made from reaction, belong to amorphous alloy material, there is high surface energy, high catalytic activity is shown to evolving hydrogen reaction, technique is simple, and it is easy to prepare, cheap.
Description
Technical field
It is more particularly to a kind of to prepare Pd-Ni-Fe- using chemical plating-displacement the invention belongs to alloy catalyst preparation field
The method of P alloy films.
Background technology
The most abundant oxygen element in universe is the ideal fuels most cleaned.Hydrogen is called the fuel in future.Electrolytic aqueous solution is
A kind of method for preparing cleaning hydrogen energy source, although it is not cheap, there is provided high-purity hydrogen, and avoid and fired using fossil
Material, does not have greenhouse gases CO：Directly discharge.Therefore, the inexpensive hydrogen for preparing is so that the commercialized key factor of this technology.
In order to meet specialty, economic, environmental protection requirement, cheap hydrogen production is obtained, research obtains the coating material being properly electrolysed just very
It is necessary.Precious metals pt, Ru etc. have higher activity, and precious metal material is too expensive for commercial Application.Transition metal palladium,
Nickel, iron, cobalt etc. and its alloy have the double dominant of low liberation of hydrogen overpotential and low cost.To the Pd of nano shape (nano particle,
Nano wire or nanoporous etc.) to be doped be a kind of effective method.The focus addition base metal member studied at present
Element is Co, Ni, Cu and Fe etc..With dibit matching method, electro-deposition obtains Pd to such as Mustain on gold electrode at room temperature3Co is more
Brilliant catalyst, its oxygen reduction catalytic activity are sufficiently close to polycrystalline Pt under the same conditions, and are poisoned with preferable methanol tolerance
Ability.The PdNi made from electrodeposition process such as Du2Catalytic activity and stability to formic acid are superior to pure Pd catalyst.Some
Nonmetallic doping can also promote Pd catalytic performance.Addition such as P can make surface atom have high activity, and liberation of hydrogen exchanges
Current density increases, and liberation of hydrogen overpotential is reduced, and high catalytic activity and stability are shown to evolving hydrogen reaction.It is but tired due to preparing
Difficulty, it is also seldom on carrying out more than ternary or ternary composite mixed report in nano Pd particle at present.The main preparation of palladium base film
Method have traditional rolling, physical vapour deposition (PVD) (PVD), chemical vapor deposition (CVD), plating or electroforming, chemical plating (EP) and
Injection thermal decomposition etc..
The present invention is first with nickel sulfate (NiSO4·7H2O), ferrous sulfate (FeSO4·7H2O it is) metal precursor, with secondary
Sodium phosphite (NaH2PO2·H2O) metal ion is reduced for reducing agent, obtained alloy Ni-Fe-P is supported on matrix surface,
It is reducing agent by Pd using this alloy Ni-Fe-P2+Metal Pd particle is reduced to, forms Pd-Ni-Fe-P alloy films.
The content of the invention
It is an object of the invention to provide a kind of method that Pd-Ni-Fe-P alloy films are prepared using chemical plating-displacement.With
Pd-Ni-Fe-P alloy films prepared by this method both have excellent catalytic activity, and its preparation method is simple, and cost is cheap, nothing
Need professional operation.
A kind of method that Pd-Ni-Fe-P alloy films are prepared using chemical plating-displacement proposed by the present invention, in electroless plating tank
In, add nickel sulfate (NiSO4·7H2O), ferrous sulfate (FeSO4·7H2O), sodium hypophosphite (NaH2PO2·H2O), lactic acid
And trisodium citrate is sufficiently stirred as chemical plating fluid, chemical plating is carried out on Cu pieces, obtain Ni-Fe-P alloy plating pieces；Putting
Change in reaction vessel add ionic liquid methyl butyl imidazolitm chloride (molecular formula BMIMCl), ethylene glycol (EG), urea (mole
Than 1:1:1) anhydrous low melting point mixed solvent, containing palladium ionic liquids [BMIM]2PdCl4As displacement liquid, Ni-Fe-P alloys
Plating piece, which is put into displacement liquid, soaks a period of time, and Pd-Ni-Fe-P alloy films are made.
Preferably, the plating solution optimization of C/C composites and process conditions of Ni-Fe-P alloys：Nickel sulfate 35g/L, sodium hypophosphite 40g/
L, ferrous sulfate 12g/L, trisodium citrate 30g/L, ammonium sulfate 20g/L, lactic acid 20mL/L, solution temperature is (90 ± 2) DEG C, molten
Liquid pH value is 9.0-10.0.
Preferably, palladium ionic liquids [BMIM] in displacement liquid2PdCl4Concentration is 5-10g/L, and alloy plating piece is in displacement liquid
8-12h is soaked, temperature is kept for 50~70 DEG C, and mixing speed is controlled in 200-300rm.
A kind of method that Pd-Ni-Fe-P alloy films are prepared using chemical plating-displacement, it is comprised the following steps that：
Step 1, with sand paper remove matrix Cu piece oxide-films, then rinsed well repeatedly with deionized water.Surface will be removed
The Cu pieces of oxide-film are in 3mol/L HNO330s is corroded in etchant, it is finally clean rear stand-by using deionized water rinsing；
Step 2, a certain amount of nickel sulfate (NiSO is weighed respectively4·7H2O), ferrous sulfate (FeSO4·7H2O), secondary phosphorous
Sour sodium (NaH2PO2·H2O), lactic acid, trisodium citrate, and dissolved respectively with distilled water, obtain settled solution.By what is dissolved
Nickel sulfate solution, ferrous sulfate, lactic acid, ortho phosphorous acid sodium solution are poured into sodium citrate solution in the case where being stirred continuously, and this is molten
Liquid adds distilled water to 200mL and stirred as chemical plating fluid, and drawing appropriate sodium hydroxide solution with suction pipe adjusts bath pH value.
Step 3, in inert-gas environment, taking a certain amount of ionic liquid methyl butyl imidazolitm chloride, (molecular formula is
BMIMCl), ethylene glycol (EG), urea (mol ratio 1:1:1) anhydrous low melting point mixed solvent is put into displacement reaction vessel, so
Backward low melting point in the mixed solvent is separately added into a certain amount of [BMIM] containing palladium ionic liquids2PdCl4, Alloy Plating that step 2 is obtained
Part, which is put into displacement liquid, soaks a period of time, and Pd-Ni-Fe-P alloy films are made by replacing to react.The change that replacement process occurs
It is as follows to learn reaction：
[PdCl4]-2+Fe→Pd+FeCl3 -
[PdCl4]-2+Ni→Pd+NiCl3 -
It is characteristic of the invention that：
(1) Pd-Ni-Fe-P alloy films prepared by the present invention belong to amorphous alloy material, have high surface energy, make surface
Atom has high activity, the increase of liberation of hydrogen exchange current density, and liberation of hydrogen overpotential is reduced, and high catalysis is shown to evolving hydrogen reaction
Activity.
(2) process of the present invention is simple, and reaction condition is gentle, and it is easy to prepare, cheap.
Brief description of the drawings
Accompanying drawing is the surface topography map of Pd-Ni-Fe-P alloy films in the present invention.
Embodiment
With reference to embodiment, the invention will be further described.
Step 1, with sand paper remove matrix Cu piece oxide-films, then rinsed well repeatedly with deionized water.Surface will be removed
The Cu pieces of oxide-film are in 3mol/L HNO330s is corroded in etchant, it is finally clean rear stand-by using deionized water rinsing；
Step 2, a certain amount of nickel sulfate (NiSO is weighed respectively4·7H2O), ferrous sulfate (FeSO4·7H2O), secondary phosphorous
Sour sodium (NaH2PO2·H2O), lactic acid, trisodium citrate, and dissolved respectively with distilled water, obtain settled solution.By what is dissolved
Nickel sulfate solution, ferrous sulfate, lactic acid, ortho phosphorous acid sodium solution are poured into sodium citrate solution in the case where being stirred continuously, and this is molten
Liquid adds distilled water to 200mL and stirred as chemical plating fluid, and drawing appropriate sodium hydroxide solution with suction pipe adjusts bath pH value.Change
Learn the plating solution optimization of C/C composites and process conditions of plating Ni-Fe-P alloy films：Nickel sulfate 35g/L, sodium hypophosphite 40g/L, sulfuric acid are sub-
Iron 12g/L, trisodium citrate 30g/L, ammonium sulfate 20g/L, lactic acid 20mL/L, solution temperature are (90 ± 2) DEG C, and solution ph is
10.0。
Step 3, in inert-gas environment, take 400mL ionic liquid methyl butyl imidazolitm chloride (molecular formula BMIMCl),
Ethylene glycol (EG), urea (mol ratio 1:1:1) anhydrous low melting point mixed solvent is put into displacement reaction vessel, then to low molten
Point in the mixed solvent is separately added into 3g [BMIM] containing palladium ionic liquids2PdCl4, the alloy plating piece that step 2 obtains is put into displacement liquid
Middle immersion 10h, temperature are kept for 60 DEG C, and mixing speed control is in 250rm, obtained Pd-Ni-Fe-P alloy films.Using energy disperse spectroscopy
(EDX) surface composition is carried out to analyze to obtain its atom composition：Pd, 25.5% (atomic fraction, similarly hereinafter), Ni, 28%, Fe,
26.5%th, P, 20%.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (2)
- A kind of 1. method that Pd-Ni-Fe-P alloy films are prepared using chemical plating-displacement, it is characterised in that：With nickel sulfate, sulfuric acid Ferrous iron, sodium hypophosphite, lactic acid, trisodium citrate are chemical plating raw material, and chemical plating is carried out on Cu sheet matrixes, obtains Ni-Fe-P Alloy plating piece；Ionic liquid methyl butyl imidazolitm chloride (molecular formula BMIMCl), ethylene glycol are added in reaction vessel is replaced (EG), urea (mol ratio 1:1:1) anhydrous low melting point mixed solvent, containing palladium ionic liquids [BMIM]2PdCl4As displacement liquid, Ni-Fe-P alloy plating pieces are put into displacement liquid and soak a period of time, Pd-Ni-Fe-P alloy films are made by replacing to react.
- 2. the method according to claim 1 that Pd-Ni-Fe-P alloy films are prepared using chemical plating-displacement, its feature are existed In：[BMIM] containing palladium ionic liquids in displacement liquid2PdCl4For 8-15g/L, Ni-Fe-P alloy plating pieces soak 8- in displacement liquid 12h, temperature are kept for 50-70 DEG C, and mixing speed is controlled in 200-300rm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710486054.7A CN107447208B (en) | 2017-06-23 | 2017-06-23 | Method for preparing Pd-Ni-Fe-P alloy film by chemical plating-displacement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710486054.7A CN107447208B (en) | 2017-06-23 | 2017-06-23 | Method for preparing Pd-Ni-Fe-P alloy film by chemical plating-displacement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107447208A true CN107447208A (en) | 2017-12-08 |
| CN107447208B CN107447208B (en) | 2020-04-10 |
Family
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| CN201710486054.7A Active CN107447208B (en) | 2017-06-23 | 2017-06-23 | Method for preparing Pd-Ni-Fe-P alloy film by chemical plating-displacement |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786853A (en) * | 2018-06-13 | 2018-11-13 | 天津大学 | Nano-porous catalyst method, nanoporous PdCuNi-S catalyst and purposes are prepared using crystal alloy |
| CN110292942A (en) * | 2019-06-11 | 2019-10-01 | 广东国鸿氢能科技有限公司 | A kind of preparing hydrogen by sodium borohydride hydrolysis catalyst and preparation method thereof |
| CN110548527A (en) * | 2019-07-26 | 2019-12-10 | 青岛科技大学 | method for preparing supported Ni-Fe-P-MnFeO 3 electrocatalyst by chemical plating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108786853A (en) * | 2018-06-13 | 2018-11-13 | 天津大学 | Nano-porous catalyst method, nanoporous PdCuNi-S catalyst and purposes are prepared using crystal alloy |
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| CN110548527A (en) * | 2019-07-26 | 2019-12-10 | 青岛科技大学 | method for preparing supported Ni-Fe-P-MnFeO 3 electrocatalyst by chemical plating |
| CN110548527B (en) * | 2019-07-26 | 2022-08-09 | 青岛科技大学 | Preparation of load type Ni-Fe-P-MnFeO by chemical plating 3 Method of electrocatalyst |
| CN111013621A (en) * | 2019-11-14 | 2020-04-17 | 河南城建学院 | Method for producing transition metal carbonitrides |
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