CN108176404A - A kind of chemical nickel plating composite catalyst, preparation method and nickel chemical plating technology - Google Patents
A kind of chemical nickel plating composite catalyst, preparation method and nickel chemical plating technology Download PDFInfo
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- CN108176404A CN108176404A CN201711449236.3A CN201711449236A CN108176404A CN 108176404 A CN108176404 A CN 108176404A CN 201711449236 A CN201711449236 A CN 201711449236A CN 108176404 A CN108176404 A CN 108176404A
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- Prior art keywords
- nickel
- chemical
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 289
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 130
- 238000007747 plating Methods 0.000 title claims abstract description 119
- 239000000126 substance Substances 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000005516 engineering process Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 71
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 239000000758 substrate Substances 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 28
- 229920000877 Melamine resin Polymers 0.000 claims description 27
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 26
- 239000003638 chemical reducing agent Substances 0.000 claims description 22
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000007598 dipping method Methods 0.000 claims description 17
- 150000002815 nickel Chemical class 0.000 claims description 17
- 238000005253 cladding Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 9
- 229940078494 nickel acetate Drugs 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- 229920000742 Cotton Polymers 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 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 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006197 hydroboration reaction Methods 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000004033 plastic Substances 0.000 claims 1
- 229920003023 plastic Polymers 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052763 palladium Inorganic materials 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 66
- 238000000034 method Methods 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 241000219146 Gossypium Species 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 4
- -1 Graphite alkene Chemical class 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- AYRVGWHSXIMRAB-UHFFFAOYSA-M sodium acetate trihydrate Chemical class O.O.O.[Na+].CC([O-])=O AYRVGWHSXIMRAB-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000005406 washing 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
-
- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
- Chemically Coating (AREA)
Abstract
The present invention provides a kind of chemical nickel plating composite catalysts, include the nano nickel particles of redox graphene load.The present invention starts with from traditional chemical nickel plating technology, and the palladium catalyst of high cost is substituted for the nano nickel catalyst of cheap redox graphene load, significantly reduces cost.Simultaneously because the synergistic effect between large stretch of graphene and the metallic nickel plated layer formed is so that the more traditional nickel plating mode of electric conductivity of the compound after chemical nickel plating significantly improves.The experimental results showed that the electric conductivity of coating that the catalyst that the present invention is prepared carries out chemical plating is up to 24390S m‑1。
Description
Technical field
The present invention relates to electroless plating technology field, more particularly, to a kind of chemical nickel plating composite catalyst, preparation method
And nickel chemical plating technology.
Background technology
The mode of traditional deposition nickel is electric deposition nickel, is to be restored the nickel ion in electroplate liquid in substrate using extrinsic current
Surface needs substrate to limit the application of nickel plating technology for conductive material, in order to solve this problem, developed chemical nickel plating
Technique can expand to substrate on nonconductive matrix bottom, so as to promote the industrialized development of nickel plating technology.
Chemical nickel plating is that the nickel ion reduction in chemical plating fluid is deposited on the surface with catalyst with reducing agent.It has
There is following advantage：(1) excellent corrosion resistance, the nickel alloy coating of the phosphorus doping particularly formed in acidic bath
In salt, alkali has extraordinary corrosion resistance in ammonia and seawater；(2) without external dc power supply, plated substrate can not led
Electric material；(3) heat treatment temperature is low, and the nickel coating of good hardness can be obtained after being heat-treated below 400 degrees Celsius；(4)
Chemical Ni-plating layer is fine and close, any surface finish；(5) high rigidity and high-wearing feature；(6) ingredient of chemical Ni-plating layer and thickness are uniform, no
Need processing of additionally polishing.Due to these advantages, so nickel chemical plating technology is widely studied.
However, current ripe nickel chemical plating technology needs precious metal palladium to substantially increase chemical plating as catalyst
Precious metals palladium catalyst in order to further reduce the cost, is substituted for the other materials with catalytic activity by the cost of nickel technique
It is crucial.Simultaneously because the coating of nickel chemical plating technology generation is made of nickel metallic particles, there is very strong connect between particle
Resistance get an electric shock so as to reduce the electric conductivity of coating.
Therefore, how to develop the chemical nickel plating catalyst of other low costs, and improve the electric conductivity of coating, have become
For forward position scientific research personnel numerous in the field widely one of focus of attention.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of chemical nickel plating composite catalyst, the present invention
The chemical nickel plating composite catalyst being prepared conducts electricity very well.
The present invention provides a kind of chemical nickel plating composite catalyst, including graphene oxide-loaded nano nickel particles.
Preferably, the grain size of the nano nickel particles is 5~100nm.
The present invention provides a kind of preparation method of chemical nickel plating composite catalyst, including：
A) graphene oxide is dispersed in the first solvent, obtains the first solution；
Nickel salt is dispersed in the second solvent, obtains the second solution；
B) substrate is immersed in the first solution, obtains the substrate of graphene oxide cladding；
C) substrate of graphene oxide cladding is impregnated in the second solution, drying obtains catalyst precursor；
D) catalyst precursor is restored in the presence of a reducing agent, obtains chemical nickel plating composite catalyst.
Preferably, a concentration of 1wt%~30wt% of the graphene oxide in the first solution；The first solution choosing
From one or more of water, methanol, ethyl alcohol, propyl alcohol and dimethylformamide；The nickel salt is dispersed in dense in the second solution
It spends for 0.1wt%~60wt%；One kind in water, methanol, ethyl alcohol, propyl alcohol and dimethylformamide of second solution or
It is several.
Preferably, the nickel salt is one or more in nickel sulfate, nickel chloride, nickel nitrate, nickel acetate and nickel oxalate；
The one kind or several of the substrate in melamine sponge, polyurethane sponge, cotton, engineering plastics, timber and metal product
Kind.
Preferably, step B) time of the dipping is 30~60min；Step C) dipping time for 10~
20min；Drying is further included after the dipping；The temperature of the drying is 80 DEG C~100 DEG C；The time of drying is 10~20min.
Preferably, the step D is specially and the catalyst precursor is immersed in the solution of reducing agent, is washed, is dried
It is dry, obtain chemical nickel plating composite catalyst；The time of the dipping is 10~20min；The temperature of the drying is 80~100
℃；The time of the drying is 30~40min.
Preferably, the reducing agent is sodium borohydride or potassium borohydride；A concentration of 0.1wt% of the reducing agent solution
~20wt%；Solvent in the reducing agent solution is selected from one or more of water, methanol, ethyl alcohol and propyl alcohol.
The present invention provides a kind of nickel chemical plating technology, including：
The chemical nickel plating composite catalyst described in above-mentioned technical proposal, 70~100 DEG C of guarantors are added in chemical nickel-plating solution
50~70min is held, obtains nickel coating.
Preferably, in the chemical nickel-plating solution：Nickel source is selected from nickel sulfate, nickel chloride, nickel nitrate, nickel acetate and nickel oxalate
In it is one or more；Reducing agent is selected from one or more of sodium hypophosphite, sodium borohydride, borine and hydrazine；Complexing agent is selected from
Sodium acetate or sodium citrate；Inhibitor is thiocarbamide.
Compared with prior art, the present invention provides a kind of chemical nickel plating composite catalyst, including redox graphene
The nano nickel particles of load.The present invention starts with from traditional chemical nickel plating technology, the palladium catalyst of high cost is substituted for cheap
The nano nickel catalyst of redox graphene load, significantly reduces cost.Simultaneously because large stretch of graphene and institute's shape
Into metallic nickel plated layer between synergistic effect so that chemical nickel plating after compound the more traditional nickel plating mode of electric conductivity it is notable
It improves.The experimental results showed that the electric conductivity of coating that the catalyst that the present invention is prepared carries out chemical plating is up to 24390S m-1。
Description of the drawings
Fig. 1 is that the nano nickel particles loaded using redox graphene described in the one of technical solution of the present invention are made
It is catalyst without palladium chemical nickel plating workflow schematic diagram；
Fig. 2 is the schematic diagram provided by the invention that can improve chemical Ni-plating layer electric conductivity；
The optical photograph of melamine sponge after (a) chemical nickel plating that Fig. 3 is prepared for the embodiment of the present invention 1；(b) it is chemical
Melamine sponge SEM photograph after nickel plating, insertion figure show section structure；(c) the melamine sponge after chemical nickel plating
Amplified SEM photograph；
Fig. 4 is the XRD spectrum that the embodiment of the present invention 1 prepares the sponge after chemical nickel plating；
Fig. 5 is the TEM figures that the embodiment of the present invention 1 prepares (a) coating；(b) the details in a play not acted out on stage, but told through dialogues phase of coating；(c) in Fig. 5 b white edges area
The P elements scanning figure in domain；(d) in the nickel element scanning figure in Fig. 5 b white edges region；(e) carbon in Fig. 5 b white edges region is swept
Tracing；(f) the XPS spectrum figure of nickel；(g) the XPS spectrum figure of phosphorus；
Fig. 6 is the material conductivity and comparative example of the present invention 1 that the embodiment of the present invention 1 prepares nickel chemical plating technology preparation
In traditional chemical nickel plating technology prepare material conductivity compare figure.
Specific embodiment
The present invention provides a kind of chemical nickel plating composite catalyst, preparation method and nickel chemical plating technology, this field skills
Art personnel can use for reference present disclosure, be suitably modified technological parameter realization.In particular, it should be pointed out that all similar replacements and
Change apparent to those skilled in the art, they shall fall within the protection scope of the present invention.The method of the present invention
And application is described by preferred embodiment, related personnel can significantly not depart from the content of present invention, spirit and model
Enclose it is interior methods herein and application are modified or suitably changed with combining, to realize and using the technology of the present invention.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to people in the art
Known to member prepared by conventional method.
All raw materials of the present invention, are not particularly limited its purity, present invention preferably employs analytically pure purity.
The definition of the no palladium chemical nickel plating is not particularly limited in the present invention, with no palladium well known to those skilled in the art
The definition of chemical nickel plating.
The present invention provides a kind of chemical nickel plating composite catalysts, include the nickel nanometer of redox graphene load
Grain.
First, chemical nickel plating composite catalyst provided by the invention includes redox graphene.
The specific choice of the graphene oxide is not particularly limited in the present invention, with oxygen well known to those skilled in the art
Graphite alkene, those skilled in the art can carry out according to the requirement of practical situations, raw material situation and product
Selection and adjustment, performance of the present invention to ensure and improving nickel coating, graphene oxide composite material of the present invention is preferably function
The graphene oxide of change；More preferably carboxylated or hydroxylated graphene oxide.
Redox graphene of the present invention is formed in situ in substrate；The thickness of the redox graphene layer
Degree is preferably 10nm~1 μm.The present invention for the carboxylated or hydroxylated graphene oxide concrete mode without limit
It is fixed, it is well known to those skilled in the art.
Chemical nickel plating composite catalyst provided by the invention includes nano nickel particles；The grain size of the nano nickel particles is preferred
For 5~100nm.
Nano nickel particles of the present invention are the nano nickel particles prepared by reducing process.The present invention is for specific
Preparation process is following to be clearly described, and details are not described herein.
Catalyst of the present invention is can form the material of nickel coating with chemical plating fluid chemically reactive.
The present invention provides a kind of preparation method of chemical nickel plating composite catalyst, including：
A) graphene oxide is dispersed in the first solvent, obtains the first solution；
Nickel salt is dispersed in the second solvent, obtains the second solution；
B) substrate is immersed in the first solution, obtains the substrate of graphene oxide cladding；
C) substrate of graphene oxide cladding is impregnated in the second solution, drying obtains catalyst precursor；
D) catalyst precursor is restored in the presence of a reducing agent, obtains chemical nickel plating composite catalyst.
It is molten that graphene oxide is dispersed in first by the preparation method of chemical nickel plating composite catalyst provided by the invention first
In agent, the first solution is obtained.
The specific choice of the graphene oxide is not particularly limited in the present invention, with oxygen well known to those skilled in the art
Graphite alkene, those skilled in the art can carry out according to the requirement of practical situations, raw material situation and product
Selection and adjustment, performance of the present invention to ensure and improving nickel coating, graphene oxide composite material of the present invention is preferably function
The graphene oxide of change；More preferably carboxylated or hydroxylated graphene oxide.
First solution of the present invention is preferably selected from one kind or several in water, methanol, ethyl alcohol, propyl alcohol and dimethylformamide
Kind；More preferably water.
In the present invention, concentration of the graphene oxide in the first solution is preferably 1wt%~30wt%；More preferably
For 3wt%~28wt%；Most preferably 5wt%~25wt%.
In the present invention, the milliliter number of the grams g of the substrate and graphene oxide dispersion solution (being the first solution)
It is 1：50~100.
The present invention for the dispersion concrete mode without limit, it is well known to those skilled in the art.This hair
Bright above-mentioned solvent is the good solvent of graphene oxide, and graphene oxide has good dissolubility wherein.
Nickel salt is dispersed in the second solvent by the present invention, obtains the second solution.
The specific choice of nickel salt is not particularly limited in the present invention, with nickel salt well known to those skilled in the art,
Those skilled in the art can be selected and adjusted, this hair according to practical situations, raw material situation and product requirement
The bright performance to ensure and improving catalyst, the nickel salt are preferably selected from nickel sulfate, nickel chloride, nickel nitrate, nickel acetate and oxalic acid
It is one or more in nickel；It is more preferably one or more in nickel sulfate, nickel chloride, nickel nitrate and nickel acetate.
According to the present invention, the concentration that the nickel salt is dispersed in the second solution is preferably 0.1wt%~60wt%；More preferably
For 1wt%~58wt%；Most preferably 2wt%~55wt%.
Second solution of the present invention is preferably selected from one kind or several in water, methanol, ethyl alcohol, propyl alcohol and dimethylformamide
Kind；More preferably one or more of methanol, ethyl alcohol, propyl alcohol and dimethylformamide.
Good solvent of second solution of the invention for nickel salt, the poor solvent of graphene oxide.That is, in the solution
Nickel ion can easily be adsorbed onto surface of graphene oxide, while be difficult by graphene oxide dispersion in this solution.
After obtaining the first solution, substrate is immersed in the first solution, obtains the substrate of graphene oxide cladding.
The material of chemical nickel plating substrate is not particularly limited in the present invention, with material well known to those skilled in the art
Material, those skilled in the art can be selected and adjusted according to practical situations, raw material condition and product requirement,
Substrate of the present invention is preferably selected from melamine sponge, polyurethane sponge, cotton, in engineering plastics, timber and metal product
One or more.
The shape of the substrate is not particularly limited in the present invention, with chemical nickel plating base well known to those skilled in the art
Bottom Shape, those skilled in the art can be selected according to practical situations, raw material condition and product requirement and
Adjustment, shape of the present invention are cuboid block or sponge.
The present invention preferably cleans substrate, and the concrete mode of the invention for the cleaning is without limiting, with this
Cleaning way known to field technology personnel, those skilled in the art can according to practical situations, raw material condition with
And product requirement is selected and is adjusted, and is cleaned by ultrasonic preferably in acetone or methanol 20~30 minutes, then 80~100 DEG C
Drying 10~14 hours；More preferably it is cleaned by ultrasonic in acetone 25~30 minutes, then dries 10~12 hours for 80~90 DEG C.
Substrate after cleaning is immersed in the first solution, is dried, obtains the substrate of graphene oxide cladding.
The present invention for it is described dipping and drying concrete mode without limit, it is well known to those skilled in the art i.e.
It can.According to the present invention, the dipping time is 2~3 times；The time impregnated every time is 10~20min；The time as always impregnated
For 30~60min；The temperature of the dipping be room temperature, as 20~35 DEG C.The temperature of the drying is preferably 80~100 DEG C；
More preferably 80~90 DEG C；The time of the drying is preferably 30~40min.
In the present invention, the milliliter number of the grams g of the substrate and graphene oxide dispersion solution (being the first solution)
It is 1：50~100.
After the substrate of graphene oxide cladding is prepared, the substrate of graphene oxide cladding is impregnated in the second solution,
Drying, obtains catalyst precursor.
In the present invention, the grams 1g of substrate of the graphene oxide cladding and the milliliter number of the second solution are 1：50~
100。
The present invention for it is described dipping and drying concrete mode without limit, it is well known to those skilled in the art i.e.
It can.According to the present invention, the dipping time is 2~3 times；The time impregnated every time is 10~20min；The time as always impregnated
For 30~60min；The temperature of the dipping be room temperature, as 20~35 DEG C.The temperature of the drying is preferably 80~100 DEG C；
More preferably 80~90 DEG C；The time of the drying is preferably 10~20min.
After obtaining catalyst precursor, the catalyst precursor is restored in the presence of a reducing agent, obtains chemical plating
Nickel composite catalyst.
According to the present invention, above-mentioned steps preferably be specially the catalyst precursor is immersed in the solution of reducing agent,
Washing, drying, obtain chemical nickel plating composite catalyst.
In the present invention, the time of the dipping is preferably 10~20min；More preferably 10~15min；The dipping
Temperature is room temperature, as 20~35 DEG C.
After dipping, without drying, directly cleaned with methanol or acetone, then dried.
The present invention for the cleaning concrete operations and mode without limit, it is well known to those skilled in the art i.e.
It can.The number of the cleaning is preferably 2~3 times.
It is drying after cleaning；The temperature of the drying is 80~100 DEG C；More preferably 80~90 DEG C；The drying when
Between preferably 30~40min；More preferably 30~35min.
The graphene oxide-loaded nano nickle granules of catalyst reduction at this time are by uniform fold on the surface of substrate.
The chemical reducing agent for preparing nano nickel particles is not particularly limited in the present invention, ripe with those skilled in the art
That knows can the carry out material of above-mentioned reaction, those skilled in the art can according to practical situations, raw material situation with
And product requirement is selected and is adjusted, for the present invention in order to ensure the performance of formed chemical Ni-plating layer, above-mentioned reducing agent is preferred
Sodium borohydride, potassium borohydride.
The concentration of reducing agent solution of the present invention is preferably 0.1wt%~20wt%；More preferably 1wt%~
18wt%；Most preferably 2wt%~16wt%.Solvent in the reducing agent solution is preferably selected from water, methanol, ethyl alcohol and propyl alcohol
One or more of；More preferably one or more of methanol, ethyl alcohol and propyl alcohol.
Catalyst of the present invention is the redox graphene of nano nickel particles load.Compared with prior art, this hair
The use of bright non precious metal palladium, simultaneously because the presence of graphene solves the nickel particle formed in nickel chemical plating technology process
Between contact impedance problem, improve the electric conductivity of chemical Ni-plating layer.
The present invention provides a kind of chemical nickel plating composite catalysts, include the nickel nanometer of redox graphene load
Grain.The present invention starts with from traditional chemical nickel plating technology, and the palladium catalyst of high cost is substituted for cheap redox graphene
The nano nickel catalyst of load, significantly reduces cost.Simultaneously because large stretch of graphene and the metallic nickel plated layer formed
Between synergistic effect so that the more traditional nickel plating mode of electric conductivity of compound after chemical nickel plating significantly improves.Experimental result table
Bright, the electric conductivity that the catalyst that the present invention is prepared carries out the coating of chemical plating is up to 24390S m-1The present invention provides one
Kind nickel chemical plating technology, including：
The chemical nickel plating composite catalyst described in above-mentioned technical proposal, 70~100 DEG C of guarantors are added in chemical nickel-plating solution
50~70min is held, obtains nickel coating.
The present invention has had clear description for the chemical nickel plating composite catalyst is above-mentioned, and details are not described herein.
Other ingredients in the chemical nickel plating are not particularly limited in the present invention, with well known to those skilled in the artization
Nickel plating solution is learned, those skilled in the art can be selected according to practical situations, raw material condition and product requirement
It selects and adjusts, the present invention is to ensure and improve the performance of chemical Ni-plating layer, in the chemical nickel-plating solution：Nickel source is selected from sulfuric acid
It is one or more in nickel, nickel chloride, nickel nitrate, nickel acetate and nickel oxalate；Reducing agent is selected from sodium hypophosphite, sodium borohydride, boron
One or more of alkane and hydrazine；Complexing agent is selected from sodium acetate or sodium citrate；Inhibitor is thiocarbamide.
The specific choice of the nickel salt is not particularly limited in the present invention, with well known to those skilled in the art for chemistry
The nickel salt of nickel plating, those skilled in the art can carry out according to practical situations, raw material situation and product requirement
Selection and adjustment, the present invention for ensure and improve chemical Ni-plating layer performance, the nickel salt be preferably selected from nickel sulfate, nickel chloride,
It is one or more in nickel nitrate, nickel acetate and nickel oxalate；More preferably nickel sulfate.The ratio of nickel salt in the chemical nickel-plating solution
Example is preferably 0.1wt%~5wt%.
The specific ratio of the electronation agent solution is not particularly limited in the present invention, and those skilled in the art can root
It is selected and is adjusted according to practical situations, raw material situation and product requirement, the present invention is ensures and improve chemical plating
The performance of nickel layer, the ratio of the reducing agent solution is preferably 1wt%~5wt%.
The specific ratio of the chemical plating solution complexing agent, inhibitor and modifying agent is not particularly limited in the present invention,
Those skilled in the art can be selected and adjusted, this hair according to practical situations, raw material situation and product requirement
The bright performance to ensure and improving chemical Ni-plating layer, the summation of the chemical plating solution complexing agent, inhibitor and modifying agent account for
The ratio of the chemical plating solution is preferably 0.5wt%~20wt%.
The detailed process of the present invention is referring to Fig. 1, and as shown in FIG. 1, FIG. 1 is for described in the one of technical solution of the present invention
The graphene oxide loaded using nano nickel particles is as catalyst without palladium chemical nickel plating workflow schematic diagram；Pass through first
Then graphene oxide-loaded substrate surface after cleaning will have been loaded graphene oxide by infiltration and then dry method
Substrate is immersed in the precursor solution of nickel, later, dried substrate is put into the oxygen that nanometer nickel load is formed in reducing solution
The substrate (graphene oxide of nanometer nickel load is as catalyst) of graphite alkene cladding, later using common chemical nickel plating work
Skill forms the smooth nickel coating of one layer of densification in substrate surface.In layer formation process is plated, mainly nickel is along catalyst granules
Growth, ultimately forms the coating that big nickel particle is accumulated mutually, due to the contact impedance between particle, so coating electric conductivity by
To influence.Referring to Fig. 2, Fig. 2 is the schematic diagram provided by the invention that can improve chemical Ni-plating layer electric conductivity.When equal in nickel particle
When on the even graphene oxide being supported on after restoring, electronics can be preferentially by whole graphene so that reduce nickel
Contact impedance between grain, so as to effectively improve the electric conductivity of coating.
The present invention provides it is a kind of using graphene oxide activate without palladium nickel chemical plating technology, from traditional chemical nickel plating work
Skill is started with, and the palladium catalyst of high cost is substituted for the nano nickel catalyst of cheap redox graphene load, significantly
Reduce cost.Simultaneously because the synergistic effect between large stretch of graphene and the metallic nickel plated layer formed causes chemical nickel plating
The more traditional nickel plating mode of electric conductivity of compound afterwards significantly improves.
The experimental results showed that proposed by the present invention improved using the graphene oxide that nano nickel particles load as catalyst
Nickel chemical plating technology can improve the electric conductivity of coating now, from the 3600S m that tradition is used to have palladium nickel chemical plating technology-1
It has been increased to the improved 24390S m of this method-1。
In order to further illustrate the present invention, with reference to embodiments to a kind of chemical nickel plating composite catalyzing provided by the invention
Agent, preparation method and nickel chemical plating technology are described in detail.
Embodiment 1
The present embodiment provides the nano nickel particles catalyst that a kind of chemical nickel plating redox graphene loads, specific
Technique can be with shown in reference chart 1.
The choice of the substrates melamine sponge of the present embodiment；
Specific experiment process is as follows：
First, 1g melamines sponge is cleaned by ultrasonic 30 minutes in acetone, then dries 12 hours for 80 degrees Celsius.Then
Melamine sponge after cleaning is immersed in the graphene oxide solution of 100mL.After ten minutes, melamine sponge is taken
Go out.Purpose is to prepare the melamine sponge (GOMF) of graphene oxide cladding to this process in triplicate.Then GOMF is soaked
Enter in the methanol solution that 50mL includes 1g nickel acetates.After ten minutes, GOMF takes out and then dries at 80 degrees celsius, the step
In triplicate.Later, the GOMF for loading nickel acetate is immersed in methanol solutions of the 20mL comprising 0.5g sodium borohydrides 10 minutes.So
Afterwards using being dried at 80 degrees celsius after methanol cleaning three times, the nano nickel catalyst of redox graphene load at this time is equal
The even surface for being covered in melamine sponge.Melamine sponge after activation is put into the chemical nickel-plating solution of 50mL (packet
Containing seven water nickel sulfates of 1g, seven waterside sodium phosphates of 1.5g, 1.5g sodium acetate trihydrates, 0.05mg thiocarbamides), it is kept under 90 degrees Celsius
50-70 minutes.
The coating prepared to above-mentioned steps of the present invention is detected.Referring to Fig. 3, Fig. 3 is prepared by the embodiment of the present invention 1
(a) optical photograph of the melamine sponge after chemical nickel plating.(b) the melamine sponge SEM photograph after chemical nickel plating is inserted into
Figure shows section structure.(c) the amplified SEM photograph of the melamine sponge after chemical nickel plating；It first can from Fig. 3 a
Apparent variation is had occurred with the color for finding out the melamine sponge after chemical nickel plating, becomes silver grey from the white of beginning
Color, it can be seen that melamine sponge surface has obviously coating from Fig. 3 b, it can be seen that melamine from Fig. 3 c
There is one layer of apparent coating on the surface of sponge.Fig. 4 is the XRD spectrum that the embodiment of the present invention 1 prepares the sponge after chemical nickel plating；From
It can be found that the structure of coating is the structure of metallic nickel in Fig. 4.Fig. 5 is the TEM figures that the embodiment of the present invention 1 prepares (a) coating.
(b) the details in a play not acted out on stage, but told through dialogues phase of coating；(c) in the P elements scanning figure in Fig. 5 b white edges region；(d) it is scanned in the nickel element in Fig. 5 b white edges region
Figure；(e) in the carbon scanning figure in Fig. 5 b white edges region；(f) the XPS spectrum figure of nickel；(g) the XPS spectrum figure of phosphorus；It can be with from Fig. 5
It was found that nickel coating is the surface that graphene is supported on by nickel particle, whole coating is then formd, it can be with from XPS results
It was found that there is the oxidation of part on the surface of nickel, while find the doping for there are P elements in nickel coating.Then, we are to the present embodiment
In prepared sample carry out four probe conducting performance tests, it is found that prepared sample has high electric conductivity
(24390S m-1)。
Embodiment 2
1g polyurethane sponges are cleaned by ultrasonic 30 minutes in acetone, then dry 10 hours for 90 degrees Celsius.It then will cleaning
15min in the graphene oxide solution of the 5%wt of 30 DEG C of immersion 100mL of polyurethane sponge afterwards, 80 DEG C of drying 30min, will be poly-
Urethane sponge is taken out.In triplicate, the polyurethane sponge of graphene oxide cladding is prepared in this process.Then by polyurethane
Sponge is immersed in the methanol solution that 50mL includes 2g nickel sulfates.After ten minutes, GOMF takes out and then dries at 80 degrees celsius
10min, the step is in triplicate.Later, the GOMF of acetic acid nickel load immersions 20mL is included to the 20mL of 0.5g sodium borohydrides
10 minutes in methanol solution.Then 30min is dried under 90 degrees Celsius after being cleaned three times using methanol, at this time reduction-oxidation graphite
The nano nickle granules catalyst of alkene load is by uniform fold on the surface of polyurethane sponge.Polyurethane sponge after activation is put into
(seven water nickel sulfates of 1g, 1.5g sodium borohydrides, 1.5g borines, 0.05mg thiocarbamides are included in the chemical nickel-plating solution of 50mL), 100
It is kept for 60 minutes under degree Celsius.
Then, we carry out the prepared sample in the present embodiment four probe conducting performance tests, prepared by discovery
Sample have high electric conductivity (35410S m-1)。
Embodiment 3
1g cottons are cleaned by ultrasonic 30 minutes in acetone, then dry 10 hours for 90 degrees Celsius.Then by three after cleaning
10min in the graphene oxide solution of the 5%wt of 30 DEG C of immersion 100mL of poly cyanamid sponge, 80 DEG C of drying 40min, cotton is taken
Go out.In triplicate, the cotton of graphene oxide cladding is prepared in this process.Then melamine sponge is immersed 50mL to protect
It protects in the methanol solution of 2g nickel sulfates.After ten minutes, GOMF takes out and then 10min, the step weight is dried under 90 degrees Celsius
Again three times.Later, the GOMF of acetic acid nickel load is immersed in mL methanol solutions of the 20mL comprising 0.5g potassium borohydrides 10 minutes.So
30min is dried under 90 degrees Celsius after being cleaned three times using methanol afterwards, the graphene oxide-loaded nanometer of catalyst reduction at this time
Nickel particle is by uniform fold on the surface of melamine sponge.Cotton after activation is put into the chemical nickel-plating solution of 50mL
(including seven water nickel sulfates of 1g, 1.5g sodium borohydrides, 1.5g borines, 0.05mg thiocarbamides), is kept for 60 minutes under 100 degrees Celsius.
Then, we carry out the prepared sample in the present embodiment four probe conducting performance tests, prepared by discovery
Sample have high electric conductivity (12500S m-1)。
Comparative example 1
This comparative example provides a kind of traditional nickel coating having prepared by palladium chemical nickel plating method,
The choice of the substrates melamine sponge of this comparative example；
This comparative example specific experiment process is as follows：
First, melamine sponge is cleaned by ultrasonic 30 minutes in acetone, then dries 12 hours for 80 degrees Celsius.Then will
Melamine sponge after cleaning, which is immersed in the tin chloride solution of 50mL, (includes 0.75g stannic chlorides and 3mL38% hydrochloric acid).Five points
Zhong Hou takes out melamine sponge, this process is activation process.Then the melamine sponge after sensitization is immersed into 20mL
In aqueous solution comprising 0.01g palladium bichlorides, the hydrochloric acid of 0.2mL38% is added in solution, is stirred 5 minutes.Later, the trimerization of taking-up
Cyanamide sponge is washed 3 times, this process is activation process.Later, the melamine sponge after activation is put into the chemistry of 50mL
(seven water nickel sulfates of 1g, seven waterside sodium phosphates of 1.5g, 1.5g sodium acetate trihydrates, 0.05mg thiocarbamides are included in nickel plating solution), 90
It is kept for 10-20 minutes under degree Celsius.Then, we carry out the survey of four probe electric conductivities to the prepared sample in the present embodiment
Examination, the electric conductivity for finding prepared sample are 3600S m-1.Fig. 6 prepares nickel chemical plating technology preparation for the embodiment of the present invention 1
Material conductivity and comparative example of the present invention 1 in traditional chemical nickel plating technology prepare material conductivity compare figure.By scheming
6 as can be seen that proposed by the invention is a kind of improved nickel chemical plating technology, due to the presence of graphene, can significantly be carried
The electric conductivity of high nickel coating.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of chemical nickel plating composite catalyst, which is characterized in that include the nano nickel particles of redox graphene load.
2. catalyst according to claim 1, which is characterized in that the grain size of the nano nickel particles is 5~100nm.
3. a kind of preparation method of chemical nickel plating composite catalyst, which is characterized in that including：
A) graphene oxide is dispersed in the first solvent, obtains the first solution；
Nickel salt is dispersed in the second solvent, obtains the second solution；
B) substrate is immersed in the first solution, obtains the substrate of graphene oxide cladding；
C) substrate of graphene oxide cladding is impregnated in the second solution, drying obtains catalyst precursor；
D) catalyst precursor is restored in the presence of a reducing agent, obtains chemical nickel plating composite catalyst.
4. preparation method according to claim 3, which is characterized in that concentration of the graphene oxide in the first solution
For 1wt%~30wt%；The one kind or several of first solution in water, methanol, ethyl alcohol, propyl alcohol and dimethylformamide
Kind；The nickel salt is dispersed in a concentration of 0.1wt%~60wt% in the second solution；Second solution is selected from water, methanol, second
One or more of alcohol, propyl alcohol and dimethylformamide.
5. preparation method according to claim 4, which is characterized in that the nickel salt is selected from nickel sulfate, nickel chloride, nitric acid
It is one or more in nickel, nickel acetate and nickel oxalate；The substrate is selected from melamine sponge, polyurethane sponge, cotton, engineering
One or more of plastics, timber and metal product.
6. preparation method according to claim 3, which is characterized in that step B) time of the dipping is 30~60min；
Step C) time of the dipping is 10~20min；Drying is further included after the dipping；The temperature of the drying for 80 DEG C~
100℃；The time of drying is 10~20min.
7. preparation method according to claim 3, which is characterized in that the step D is specially by the complex catalyst precursor
Body is immersed in the solution of reducing agent, washs, dries, and obtains chemical nickel plating composite catalyst；The time of the dipping for 10~
20min；The temperature of the drying is 80~100 DEG C；The time of the drying is 30~40min.
8. preparation method according to claim 7, which is characterized in that the reducing agent is sodium borohydride or hydroboration
Potassium；A concentration of 0.1wt%~20wt% of the reducing agent solution；Solvent in the reducing agent solution is selected from water, methanol, second
One or more of alcohol and propyl alcohol.
9. a kind of nickel chemical plating technology, which is characterized in that including：
Chemical nickel plating composite catalyst in chemical nickel-plating solution described in addition claim 1~8 any one, 70~100
DEG C keep 50~70min, obtain nickel coating.
10. nickel chemical plating technology according to claim 9, which is characterized in that in the chemical nickel-plating solution：Nickel source is selected from
It is one or more in nickel sulfate, nickel chloride, nickel nitrate, nickel acetate and nickel oxalate；Reducing agent is selected from sodium hypophosphite, hydroboration
One or more of sodium, borine and hydrazine；Complexing agent is selected from sodium acetate or sodium citrate；Inhibitor is thiocarbamide.
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| CN110760825A (en) * | 2019-11-27 | 2020-02-07 | 江苏大亿智能科技有限公司 | Surface coating anticorrosive material and preparation method thereof |
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