CN112138682A - Electrochemical deposition Pt-porous copper-based whisker catalyst material - Google Patents
Electrochemical deposition Pt-porous copper-based whisker catalyst material Download PDFInfo
- Publication number
- CN112138682A CN112138682A CN202011113782.1A CN202011113782A CN112138682A CN 112138682 A CN112138682 A CN 112138682A CN 202011113782 A CN202011113782 A CN 202011113782A CN 112138682 A CN112138682 A CN 112138682A
- Authority
- CN
- China
- Prior art keywords
- porous copper
- copper
- temperature
- corrosion
- porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000010949 copper Substances 0.000 title claims abstract description 135
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 133
- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims description 73
- 238000005260 corrosion Methods 0.000 claims description 73
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 38
- 238000011282 treatment Methods 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 30
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000011148 porous material Substances 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 24
- 229910045601 alloy Inorganic materials 0.000 claims description 24
- 239000000956 alloy Substances 0.000 claims description 24
- 230000009467 reduction Effects 0.000 claims description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 238000006722 reduction reaction Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000006056 electrooxidation reaction Methods 0.000 claims description 11
- 238000009713 electroplating Methods 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 239000013077 target material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000005275 alloying Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- PXHVJJICTQNCMI-OUBTZVSYSA-N nickel-60 atom Chemical compound [60Ni] PXHVJJICTQNCMI-OUBTZVSYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 239000000843 powder Substances 0.000 abstract description 11
- 238000012546 transfer Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 229910017767 Cu—Al Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000011946 reduction process Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229940024548 aluminum oxide Drugs 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-AHCXROLUSA-N copper-60 Chemical compound [60Cu] RYGMFSIKBFXOCR-AHCXROLUSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- -1 poly (4-hydroxybenzene methyl ester Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 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 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TUZBYYLVVXPEMA-UHFFFAOYSA-N butyl prop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C=C TUZBYYLVVXPEMA-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 210000001258 synovial membrane Anatomy 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- 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
- B01J37/06—Washing
-
- 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
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0408—Light metal alloys
- C22C1/0416—Aluminium-based alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/12—Alloys based on aluminium with copper as the next major constituent
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0623—Sulfides, selenides or tellurides
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/04—Etching of light metals
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides an electrochemical deposition Pt-porous copper-based whisker catalyst material, wherein the catalyst is a monolithic non-powder catalyst, and the specific surface area of the catalyst is 50-80m higher2Excellent mechanical strength, compressive strength of 4-5Mpa, high heat transfer performance, and heat conductivity of 70-90W m‑1 K‑1Effectively improves the gas-solid phase mass transfer process and has obvious CO-PROX catalytic performance.
Description
Technical Field
The invention relates to a Pt-porous copper-based whisker catalyst material obtained by an electrochemical and pulse laser burning method, which is used in the field of gas-solid phase catalytic reaction, in particular to CO-PROX reaction under a hydrogen-rich condition.
Technical Field
First, regarding whiskers: a whisker is a naturally occurring or artificially synthesized fiber that grows in the form of a single crystal, with a small diameter, on the order of microns. The whisker has less defects, the strength of the whisker is close to the theoretical value of a complete crystal, and the mechanical strength of the whisker is equal to the force between adjacent atoms. The highly oriented structure of the whisker not only enables the whisker to have high strength, high modulus and high elongation, but also has electric, optical, magnetic, dielectric and super-conductive properties. The strength of the whisker is far higher than that of other chopped fibers, and the whisker is mainly used as a reinforcement of a composite material and used for manufacturing a high-strength composite material.
Whiskers can be classified into two major classes, organic whiskers and inorganic whiskers. The organic whisker mainly comprises several types such as cellulose whisker, poly (butyl acrylate-styrene) whisker, poly (4-hydroxybenzene methyl ester) whisker (PHB whisker) and the like, and is widely applied to polymers. The inorganic whiskers mainly include ceramic whiskers (SiC, potassium titanate, aluminum borate, etc.), inorganic salt whiskers (calcium sulfate, calcium carbonate, etc.), metal whiskers (copper, iron, nickel, tin, aluminum oxide, zinc oxide, etc.), and the like. The ceramic-based whiskers and the inorganic salt whiskers can be applied to a plurality of fields such as ceramic composite materials, polymer composite materials and the like. The metal whisker is mainly applied to improving the metal strength or metal matrix composite materials.
The preparation method of the copper whisker is less, and the method is mainly a chemical solution method which is reported at present, needs to use a large amount of chemical reagents, and has slower whisker growth.
Refer to patent literature: the Shanghai microsystems and information technology research institute of CN201810468715A Chinese academy of sciences provides a preparation method of copper whiskers, which comprises the following steps: 1) providing a copper substrate, and placing the copper substrate in a sulfur source solution for a sulfurization reaction to form a copper sulfide on the surface of the copper substrate; 2) cleaning and drying the copper base material with the copper sulfide on the surface; 3) and placing the copper substrate with the copper sulfide on the surface in a reducing atmosphere to perform a reduction reaction so as to grow and form copper whiskers on the surface of the copper substrate. The invention relates to a hydrocarbon electrode prepared by electrochemical reduction of carbon dioxide and preparation and application thereof, and belongs to the institute of chemical and physical research of the university of the Chinese academy of sciences CN201410310490, wherein the electrode consists of a substrate layer, a thin film layer consisting of porous copper nanoparticles and an ordered layer; a thin film layer composed of porous nano particles is attached to the outer surface of the flaky substrate layer, and a copper whisker layer is attached to the surface of the thin film layer composed of the porous copper nano particles; the thickness of the substrate layer is 100-500 μm; the thickness of the porous nano film layer is 100-200 mu m; the thickness of the copper whisker layer is about 100 nm-500 mu m. The electrode with the structure effectively increases the reaction active area, improves the mass transfer of reactants, and is beneficial to reducing the reaction polarization resistance and the mass transfer polarization resistance, thereby improving the conversion efficiency of CO 2; the selectivity of the ERC reaction product can be improved by regulating and controlling active substances with different morphologies; this structure can improve the stability of the Cu metal, thereby improving the lifetime of the ERC reaction catalyst. From the above, it can be seen that the existence of copper whiskers can broaden the performance of the metal substrate to a certain extent, for example, in the CN201810468715A patent, the growth of whiskers on copper wires, copper plates, copper powders, etc. can be realized by using different copper substrates, and the performance of the substrate is enhanced or expanded, specifically, in the CN201410310490 patent, the reaction active area is effectively increased, the mass transfer of reactants is improved, and the reduction of reaction polarization resistance and mass transfer polarization resistance is facilitated, that is, the whiskers can improve the contact sites of copper base.
Next, with respect to the porous metal: the porous metal is a porous material with a large number of directional or random holes dispersed therein, and the diameter of the holes is between about 2um and 25 mm. The porous metal material not only retains the conductivity, ductility, weldability and the like of the metal material, but also has the excellent characteristics of small specific gravity, large specific surface area, high specific strength, energy absorption, shock absorption, noise reduction, electromagnetic shielding, low heat conductivity and the like, and the conventional hierarchical porous material mainly comprises a micropore-mesopore material, a micropore-macropore material, a macropore-mesopore material, a micropore-mesopore-macropore material and a mesopore-mesopore material containing two or more different pore diameters. The main preparation methods comprise a template method, a hydrothermal method, a foaming method, a sol-gel method, a molten salt method and the like, and because the method usually relates to a chemical synthesis method in the synthesis process, the preparation steps are multiple, and the process is complex, the synthesis cost of the existing hierarchical pore material is high, the pore structure control difficulty is large, the process stability is poor, and the large-scale production is difficult. The dealloying method utilizes the potential difference of electrodes of different metal elements in the multi-element alloy to carry out free corrosion in electrolyte solutions such as acid and alkali or promote corrosion to remove relatively active components in the electrolyte solutions by applying voltage, and relatively inert components are reserved to form a bicontinuous open porous structure. The method is simple, convenient and feasible, is easy to repeat, is suitable for preparing the nano porous material on a large scale, and can realize the control of the pore diameter/pore wall size distribution of the porous material by controlling the processes of corrosion, subsequent heat treatment and the like.
Such as the patent: the method comprises the steps of mixing and tabletting nickel-aluminum powder in a certain proportion, smelting the mixture into a porous alloy membrane in a sintering mode, and chemically corroding the porous alloy membrane to form a microporous shape inside the porous alloy membrane, wherein the nickel-aluminum alloy is corroded by sodium hydroxide to form a nanopore structure with high specific surface area and high catalytic activity, so that the membrane separation and electrocatalysis function integration are realized without adding a supported catalyst, the treatment capacity of the alloy membrane on dye wastewater is greatly improved, the decolorization rate of the alloy membrane under the maximum flux is increased from 55% to more than 95%, the pore diameter of the prepared porous alloy membrane is distributed between 5 and 20 micrometers, and the specific surface area is 10-40 m 2/g. The specific surface area of the patent is to be increased, and the inventorA porous nickel supported perovskite catalyst as described in the same series of days, said porous nickel having a pore size distribution of 5-30 μm and a specific surface area of 30-60m2The main reason why/g, porosity 50-70%, CN201810567439 is inferior to porous nickel prepared by dealloying of the present inventors is that the dealloying method is different, and furthermore, the specific surface area obtained by preliminary and deep dealloying is 30-60m2G, although sufficiently high, the specific surface area decreases significantly after loading the catalytically active component, e.g. 20 to 50m after loading the perovskite2There is a significant reduction in/g, and there is a need for a more recent method of increasing the specific surface area of porous copper-based materials.
Patent No. JPH 07150270A proposes a high-strength porous metal body obtained by applying a coating material containing reinforcing fine particles of an oxide, carbide, nitride, or the like of an element belonging to groups II to VI of the periodic table to the surface of a skeleton of a three-dimensional network resin having interconnected pores, further forming a metal plating layer of a Ni alloy or a Cu alloy on the coating film of the coating material, and then dispersing the fine particles in the metal plating layer by heat treatment. WO2013099532 proposes a method for producing a porous body, in which, when the surface of a resin-formed body having a three-dimensional network structure is subjected to a conductive treatment, a metal powder is mixed in a carbon coating material to coat, and then a desired metal is plated and subjected to a heat treatment to obtain a homogeneous alloy porous body; US2018030607 discloses a method for manufacturing a nickel alloy porous body, comprising: a step of applying a coating material containing nickel having a volume average particle diameter of 10 [ mu ] m or less and a metal-added nickel alloy powder onto a surface of a skeleton of a resin-formed body having a three-dimensional network structure; a step of plating nickel on the surface of the skeleton of the resin-formed body to which the coating material is applied; a step of removing the resin formed body; and a step of diffusing the additive metal into nickel by heat treatment. Patent 2019111611425 discloses a method for preparing monolithic catalyst for CO oxidation, which comprises coating conductive material on a cork plate as a substrate, electroplating, reversely obtaining a metal carrier, and preparing Pt/porous metal material by electrochemical deposition, wherein the monolithic catalyst has high mechanical strength and good thermal conductivity, the loading amount of Pt is not more than 1wt%, the temperature for complete conversion of the catalyst can be effectively reduced, the catalytic activity has high stability, and the water and carbon dioxide resistance is strong. However, the mechanical strength and the thermal conductivity of the catalyst are to be improved, which is mainly caused by the complex and difficult control of the preparation method.
Disclosure of Invention
In view of the defects of the prior art, the invention provides an electrochemical deposition Pt-porous copper-based whisker catalyst material aiming at the current situations of low specific surface area, process loading and the like of porous metal material preparation in the prior art, firstly, a high-strength alloy block is prepared by using powder metallurgy, then, a dealloying method is combined to prepare a porous high-strength nickel material, after drying and reduction, tungsten sulfide is burnt by pulse laser, tungsten sulfide is deposited on the surface of porous copper, then, a porous copper-based whisker catalyst carrier with high specific surface area is obtained by growing micro-nano copper whiskers through high-temperature treatment, then, a Pt active component is loaded on the surface of the catalyst carrier through an electrochemical method, and the material obtained by hydrogen mixed gas reduction pretreatment has practical guiding significance for three-dimensional catalysts applied on the contrary to gas-solid, the specific contents are as follows:
the electrochemical deposition Pt-porous copper-based whisker catalyst material is a monolithic material, and is characterized in that the catalyst takes Pt obtained by electrochemical deposition as an active component, takes porous copper obtained by dealloying treatment and a porous copper-based whisker material for in-situ growth of copper whiskers on a porous copper pore window as a carrier, wherein the pore diameter of the porous copper and the pore diameter of the porous copper are distributed in the range of 5-30 mu m, and the specific surface area is 30-60m2The porosity is 50-70%, and the specific surface area of the Pt-porous copper-based whisker catalyst is 50-80m2The catalyst has the advantages of a macroporous range of 2-6 mu m, a mesoporous range of 10-30nm, a Pt loading amount of 0.5-0.8wt.%, a compressive strength of 4-5Mpa, a thermal conductivity coefficient of 70-90W m-1 K-1。
Further, the Pt-free acid solution adopted for electrochemical deposition of the loaded active component is sulfuric acid and sodium sulfateThe mixed solution is prepared by taking a porous copper-based whisker material as a cathode, a platinum wire as an anode, and the electroplating solution is an aqueous solution containing 0.1-02M of tartaric acid and 0.5-0.7M of oxalic acid, and has a current density of 50-100A/M2The electrodeposition time is 5-6h, and the temperature is 40-50oC, after electrodeposition, vacuum drying and reduction for 3-5H through 3-5vol.% H2/N2.
Further, the dealloyed raw material is a Ni-Al alloy body, and the preparation process of the Ni-Al alloy body is as follows: (a) uniformly mixing 30-40wt.% of 1-5 mu m nickel powder and 60-70wt.% of 5-10 mu m aluminum powder, pressing and molding at 300-400Mpa, and sintering at 1300-1400 ℃ in inert atmosphere or reducing atmosphereoC, high-temperature lasting for 1-3h, naturally cooling, and keeping the pressure for the compression molding for 5-10 min; the inert atmosphere is N2The reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
Further, the dealloying treatment comprises chemical alkaline corrosion preliminary dealloying and electrochemical acid corrosion deep dealloying.
Further, the corrosive liquid used for the preliminary dealloying in the chemical alkaline corrosion is 1-2M NaOH aqueous solution, the corrosion time is 12-24h, and the temperature is 30-35oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
Further, the electrochemical acid liquor corrosion deep dealloying process is as follows: the copper material which is primarily de-alloyed by the corrosion of chemical alkali liquor is taken as an anode, a Pt sheet is taken as a cathode, and 0.6-0.7M HNO is taken3The corrosion voltage is 0.3-0.5V, the corrosion time is 2-3h, and the electrochemical corrosion temperature is normal temperature.
Further, after the dealloying treatment, drying and reduction treatment are carried out, wherein the drying process is to use ethanol-deionized water to wash for removing the corrosive liquid by multiple times in an alternating way, and vacuum drying is carried out, wherein the reduction process is to use 5vol.% of H2/N2Then, reduction treatment is carried out in a tube furnace for 60-90 min.
Further, the whisker is a copper whisker and is obtained by pulse laser burning and high-temperature treatment, wherein the pulse laser burning process comprises the following steps: and placing the porous copper obtained through drying and reduction treatment as a substrate in a vacuum chamber, focusing a laser beam on the tungsten sulfide target material by using Nd-YAG laser after passing through a total reflection mirror and a focusing lens to generate a photoablation reaction, melting and evaporating a target material plume, and depositing the plume on the surface of the porous copper material.
Further, the parameters of the pulse laser cauterizing the tungsten sulfide are as follows: YAG laser with laser beam wavelength of 525nm, maximum output single pulse energy of 50mj, repetition frequency of 100Hz, light spot of 1mm, and vacuum degree less than x 10-6Torr at 200-300 deg.CoC, preferably 250oC, the pulse laser burning time is 30-50 min; the distance between the tungsten sulfide target and the substrate is 2cm, and the tungsten sulfide WS2The purity of (A) is more than 99.9%.
Further, the high-temperature treatment parameters are as follows: the temperature programmed rise is 10/min to 500-700oC, keeping the temperature for 1-5H, naturally cooling to room temperature, and keeping the high-temperature atmosphere at 0.5vol.% H2Mixed gas of/He.
The specific steps are explained as follows:
(1) preparing a Cu-Al alloy block;
(a) uniformly and physically mixing 30-40wt.% of 1-5 mu m copper powder and 60-70wt.% of 5-10 mu m aluminum powder;
(b) pressing and molding under 300-400 Mpa;
(c) sintering at high temperature in inert atmosphere or reducing atmosphere, wherein the sintering temperature is 800-950 DEG CoC, high temperature lasting for 1-3h, natural cooling,
the pressure maintaining time for press forming is 5-10 min; the inert atmosphere is N2The reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
This step should be noted:
the proportion and the size of copper and aluminum powder directly influence the pore size distribution, the specific surface area and the porosity of porous copper obtained subsequently, and the invention has the following limited range: 30-40wt.%1-5 μm copper powder, 60-70wt.%5-10 μm aluminium powder, preferably 33-38wt.% 2-3 μm copper powder, 62-68wt.%,7-8 μm aluminium powder, most preferably 35wt.% 2-3 μm copper powder, 65wt.%,7-8 μm aluminium powder.
The three-dimensional porous catalyst has certain compressibility and deformability, the volume and the size of the three-dimensional porous catalyst are larger than or equal to the size of the reactor, the exceeding range is not higher than 10 percent and cannot be lower than the size or the volume of the reactor, otherwise, the reactor has poor tightness, and reaction gas cannot effectively contact the catalyst.
Thirdly, the impurity degree and the stability of the alloy are determined by the sintering atmosphere, if oxygen is mixed, the state of the Cu-Al alloy is obviously influenced, and the influence of oxides on the state of the alloy is also obviously influenced.
And fourthly, the sintering temperature mainly influences the specific form of the alloy.
(2) Preliminary dealloying by chemical lye corrosion: the corrosive liquid used for preliminary dealloying by chemical alkaline corrosion is 1-2M NaOH aqueous solution, the corrosion time is 12-24h, and the temperature is 30-35oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
The primary de-alloying is mainly based on electroless corrosion, mainly based on the following considerations:
firstly, preliminary dealloying is electroless corrosion, namely, the electroless corrosion is completely eliminated, the electroless corrosion is mainly used for taking the electrified corrosion as an anode, and the Ni-Al alloy is used in the invention, wherein Al does not have corrosion reaction, but forms alumina due to anodic oxidation, or forms an oxide film on the Ni-Al alloy, thus not only a corrosion pore channel can not be formed, but also a protective film can be formed.
Secondly, the corrosive liquid of the electroless corrosion for preliminary alloy removal is sodium hydroxide, Al is known to be an amphoteric compound, both acid and alkali can carry out corrosion reaction, and the problem of selective corrosion is considered by only selecting the sodium hydroxide, so that only the Al in the sodium hydroxide is corroded, but not the Cu is corroded, and the corrosion is very important for the formation of the uniformity of the three-dimensional pore channel.
And thirdly, in the corrosion process, the reaction of aluminum and sodium hydroxide can generate hydrogen which can not be captured by naked eyes, and the ultrasonic wave of the hydrogen can obstruct the contact of the sodium hydroxide and the aluminum, so that the ultrasonic assistance must be added in the electroless corrosion process, and the diffusion and the separation of small bubbles are facilitated.
Fourthly, the concentration, the time and the temperature in the electroless corrosion process are obtained through orthogonal experiments, and the porous nickel aluminum material carrier is preliminarily obtained for optimizing the range.
(3) Deep dealloying by electrochemical acid corrosion: taking the copper material obtained in the step (2) as an anode, taking a Pt sheet as a cathode and taking 0.6-0.7M HNO3The corrosion voltage is 0.3-0.5V, the corrosion time is 2-3h, and the electrochemical corrosion temperature is normal temperature.
Attention is paid to:
the electrochemical corrosion is positioned after the electroless corrosion, and the steps can not be randomly reversed.
The electrochemical corrosion liquid is acid liquid, which can be sulfuric acid, nitric acid, phosphoric acid and oxalic acid, and the nitric acid is preferably selected in consideration of corrosion effect and corrosion rate, in addition, the acid liquid is adopted for corrosion in the electrochemical corrosion process, so that the preparation steps of the catalyst carrier can be reduced, namely, the preliminary corrosion and the deep corrosion directly do not need any cleaning and drying treatment, and certainly, if the steps of water cleaning and air drying can be carried out on the preliminary corrosion copper and aluminum materials, and repeated for multiple times, the porous structure obtained by the subsequent deep corrosion is the best, but for convenience of operation, the acid liquid can be selected to directly neutralize the alkali corrosion liquid to remove the adhesive film on the surface of the nickel-aluminum alloy.
And thirdly, the electrochemical corrosion is preferred because the aluminum can be removed by the electroless corrosion but can not be completely removed, at least within 12-24h of the invention, the aluminum can not be effectively removed by the electroless corrosion, and the existence of the aluminum can obviously reduce the porosity of a three-dimensional pore channel structure, so that the residual aluminum can be effectively removed by the subsequent electrochemical corrosion, and further, mesopores are effectively formed, the generation of the mesopores is favorable for improving the specific surface area of the porous nickel, and the pore size distribution of the obtained porous nickel is 5-30 μm, the specific surface area is 30-60m2/g, and the porosity is 50-70%.
The concentration and the voltage of the corrosive acid liquid are lower, the time is shorter, and the consideration of preventing the anodic oxidation of the aluminum is based on the premise of effective corrosion.
(4) Drying and reducing: the drying process of the step (4) is to use ethanol-deionized water for multiple times of cross-linkingRemoving the corrosive liquid by washing, and drying in vacuum, wherein the reduction process in the step (4) is 5vol.% H2/N2Then, reduction treatment is carried out in a tube furnace for 60-90 min.
The obtained porous material is a porous copper material, and due to the fact that numerous tiny mesopores are formed through electrochemical dealloying, acid liquor in the mesopores cannot be effectively discharged, and if the acid liquor cannot be effectively discharged, the subsequent copper whisker in-situ growth is directly influenced by N elements in nitric acid; therefore, the etching solution, especially the acid solution in the mesopores, is removed by multiple alternate washing with ethanol and deionized water, the number of cyclic washing is 2-5 and preferably 4, and the cyclic washing is accompanied by vacuum drying, and common air furnace drying is not available to prevent the oxidation of the porous copper, and then the reduction is carried out by using a tubular furnace for removing the copper oxygen synovium caused by improper operation in the previous step.
(5) And using the porous copper obtained in the step (4) as a substrate, and performing pulse laser burning on tungsten sulfide;
the pulse laser cauterization PLD is characterized in that pulse laser is guided into a vacuum cavity through a synthetic quartz window to irradiate a film-forming target, the target absorbs high-density energy after irradiation to form a plume-shaped plasma state, then the plume-shaped plasma state is accumulated on a substrate arranged on the opposite side, the plasma state obtained through high energy can be uniformly distributed on the surface of a porous copper material, an excellent foundation is laid for in-situ growth of copper whiskers, and a pulse laser deposition system (PLD) is specifically configured with an ultrahigh vacuum cavity, a molecular pump, a laser scanning system, a substrate heating platinum sheet, a substrate heating structure design and a substrate heating power supply.
As for the laser source, Nd: YAG laser or PrYAG laser can be selected without any significant limitation, and the selected wavelength should be 525nm, which is determined by absorption spectrum, and 1046nm wavelength can not be used, and the maximum single pulse energy output is 50mj and the spot is 1mm at 100Hz, and the vacuum degree is less than x 10-6Under Torr conditions, WS2 ablation can produce a plasma plume evenly distributed over the surface of the porous substrate. .
With respect to the temperature, the range is selected from 200 to 300oC, the PLD temperature range is the first key factor for the growth of subsequent whiskers, such as 200oThe number of whiskers under C is less than 300oThe number of whiskers under C, in contrast, was determined using room temperature PLD and 300oThe effect of the CPLD is most obvious, and meanwhile, within a certain range, the higher the temperature is, the higher the obtained whisker value is, the more the PLD temperature is optimally 250oC, PLD has a significant effect on the subsequent whisker growth, possibly related to the distribution of WS2 in porous copper.
(6) And (4) carrying out high-temperature treatment to obtain the porous copper-based whisker material.
High-temperature treatment parameters: the temperature programmed rise is 10/min to 500-700oC, keeping the temperature for 1-5H, naturally cooling to room temperature, and keeping the high-temperature atmosphere at 0.5vol.% H2Mixed gas of/He.
The temperature range is the second key factor of whisker growth, and only the temperature reaches 800+ under the condition of not introducing reducing gasoThe crystal whisker can be obtained by C, but the requirement on equipment is high, such as the currently common equipment is not higher than 1000oC, while introducing a very small amount of reducing gas, can significantly lower the temperature point of whisker formation, introducing 0.5vol.% H2The mixed gas of the/He can effectively reduce the forming temperature of the crystal whisker at 500+oThe whiskers can be obtained by C.
The time range is a third key factor, the shorter the time is, the smaller the length and width of the whisker is, the longer the time is, the larger the length-width ratio of the whisker is, and the number of the whiskers is obviously increased and decreased along with the increase of the time.
By controlling the PLD temperature and the temperature and time during the high-temperature treatment as described above, the number and aspect ratio of whiskers can be obtained, the whisker heterochronologically grows the contact area of the porous copper significantly increased, the specific surface area of the material is significantly increased, and the whisker is advantageous for the application as a catalyst carrier in industry, thereby providing infinite possibilities for the expanded application of the porous copper.
In addition, with respect to the selection of copper as a base material, through a plurality of attempts, it is found that only copper material is easy to control the growth of whiskers, and other metals, such as nickel, can not obtain the expected whisker growth and specific surface area increase.
(7) And performing electrochemical deposition by taking a Pt electrode as an anode and taking a Pt-free acidic solution as an electrolyte.
Wherein the Pt-free acidic solution is a mixed solution of sulfuric acid and sodium sulfate, the porous copper-based whisker material obtained in the step (6) is used as a cathode, a platinum wire is used as an anode, the electroplating solution is an aqueous solution containing 0.1-02M tartaric acid and 0.5-0.7M oxalic acid, and the current density is 50-100A/M2Electrodeposition is carried out for 5 to 6 hours at a temperature of between 40 and 50oC, after electrodeposition, vacuum drying and reduction for 3-5H through 3-5vol.% H2/N2.
The following points need to be noted here:
(1) the method for loading Pt is limited to be an electrochemical method, mainly the substrate of the method is a metal material, and the surface of the metal material does not have a plurality of adsorbable hydroxyl groups or other groups like the surface of aluminum oxide, titanium oxide, silicon oxide or graphene oxide, so that van der Waals force adsorption in the traditional impregnation can cause low bonding force between an active component and the substrate, so that migration and agglomeration of metal particles can occur, and finally the catalyst has poor dispersity and large particle size, so the method for loading the active component electrochemically is adopted.
(2) The method for electrochemically loading active components adopted by the application is not to add chloroplatinic acid into a solution for electroplating, and the main reason is that the application does not want a Pt coating, but wants to obtain small particles of pT, the electrodeposition amount of directly adding chloroplatinic acid cannot be effectively controlled, in contrast, a Pt inert anode is used, active Pt particles with extremely low loading can be obtained as long as the time and the current density are controlled, in addition, because Pt is used as an inert metal electrode, the active component loading amount higher than 2wt.% is expected to be provided through the Pt electrode, obviously, the Pt electrode is not feasible, and in this case, chloroplatinic acid is required to be used as an electroplating solution, namely, the application prefers to use the Pt electrode for electroplating, and when the active component loading amount is high, a Pt-containing electrolyte can be appropriately added.
(3) The selection of parameters relating to current density, time, temperature is obtained by experimental optimisation of the results.
(4) After the electrodeposition is finished, since the catalyst is used in a gas-solid phase catalyst system, it is inevitable that an oxidation reaction occurs when the catalyst is dried after the electrodeposition is finished or when the catalyst is mounted on a reaction bed, and thus 3 to 5vol.% of H2/N2 is required to be reduced for 3 to 5 hours.
The finally obtained electrochemical deposition Pt-porous copper-based whisker catalyst material takes Pt obtained by electrochemical deposition as an active component, takes porous copper obtained by dealloying treatment and porous copper-based whisker material for in-situ growth of copper whiskers in a porous copper pore window as a carrier, wherein the pore diameter of the porous copper is distributed between 5 and 30 mu m, and the specific surface area is 30 to 60m2The porosity is 50-70%, and the specific surface area of the Pt-porous copper-based whisker catalyst is 50-80m2The catalyst has the advantages of a macroporous range of 2-6 mu m, a mesoporous range of 10-30nm, a Pt loading amount of 0.5-0.8wt.%, a compressive strength of 4-5Mpa, a thermal conductivity coefficient of 70-90W m-1 K-1。
The scheme of the invention has the following beneficial effects:
(1) the invention obtains three-dimensional porous copper material by electroless preliminary dealloying and charged deep dealloying treatment, the obtained macropores and mesopores provide sufficient places for subsequent active site loading and catalytic reaction, the pore diameter of the porous copper is distributed between 5 and 30 mu m, and the specific surface area is 30 to 60m2G, porosity 50-70%.
(2) Through the subsequent laser pulse laser burning tungsten sulfide treatment process, tungsten sulfide can be fully and uniformly distributed on the surface of the porous copper material, and a favorable place is provided for uniform growth of copper whiskers.
(3) The in-situ growth of the whiskers effectively increases the contact area of the porous copper and fully enlarges the specific surface area of the material, and when the copper whiskers are added in situ in the porous copper, the specific surface area of the catalyst carrier is increased to 50-80m2/g。
(4) The porous copper-based whisker material can be used as a carrier of a catalyst, the metal characteristics of the porous copper-based whisker material determine that the thermal conductivity of the catalyst carrier is high, the metal characteristics determine that the catalyst carrier can effectively avoid the hot spot problem of a catalyst bed layer, the inactivation is avoided, the stability of the catalyst is facilitated, the metal carrier has high mechanical strength, adjustable shape and structure and strong applicability, and the basic requirements of a massive catalyst carrier are met.
(5) The porous copper-based whisker material is a three-dimensional porous metal catalyst, wherein the range of macropores is 2-6 mu m, which is favorable for mass transfer of gas, and the range of mesopores is 10-30nm (the mesopores are derived from mesopores formed by electrochemical dealloying and staggered mesopores generated by whisker growth), which is favorable for improving the specific surface area and finally favorable for high space velocity gas-solid phase catalytic reaction.
Drawings
Fig. 1 an optical macroscopic view of porous copper material obtained after preliminary dealloying-deep dealloying.
Figure 2 SEM image of in situ grown copper whisker catalyst support in porous copper.
FIG. 3 PLD200oC. High temperature processing 500oC, SEM image of the porous copper whisker material obtained after treatment time of 15 m.
FIG. 4 PLD250oC. High temperature processing 600oAnd C, SEM image of the porous copper whisker material obtained after treatment for 3 h.
FIG. 5 PLD300oC. High temperature processing 700oAnd C, SEM image of the porous copper whisker material obtained after treatment for 5 h.
FIG. 6 HRTEM image of Pt in the catalyst obtained in example 2 of the present invention.
Detailed Description
Example 1
An electrochemical deposition Pt-porous copper-based whisker catalyst material is characterized by comprising the following processing steps:
(1) preparing a Cu-Al alloy block: (a) uniformly and physically mixing 30wt.% of 2-3 mu m copper powder and 60wt.% of 7-8 mu m aluminum powder, (b) pressing and forming under 300Mpa, (c) sintering at high temperature of 800 ℃ under inert atmosphere or reducing atmosphereoC, keeping the temperature for 1h, and naturally cooling, wherein the pressure maintaining time of the compression molding is 5 min; the inert atmosphere is N2The reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
(2) Preliminary dealloying by chemical lye corrosion: the corrosive liquid used is 1M NaOH aqueous solutionThe etching time is 12h, and the temperature is 30oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
(3) Deep dealloying by electrochemical acid corrosion: taking the copper material obtained in the step (2) as an anode, taking a Pt sheet as a cathode and taking 0.6M HNO3The corrosion voltage is 0.3V, the corrosion time is 2h, and the electrochemical corrosion temperature is normal temperature.
(4) Drying and reducing: the drying process comprises alternately washing with ethanol-deionized water for several times to remove corrosive liquid, and vacuum drying; the reduction process was at 5vol.% H2/N2Then, reduction treatment was carried out in a tube furnace for 60 min.
(5) And (3) taking the porous copper obtained in the step (4) as a substrate, and performing pulse laser burning on tungsten sulfide: YAG laser is used to focus laser beam on the tungsten sulfide target material after passing through a holophote and a focusing lens, a photoablation reaction occurs, a target material plume is evaporated by melting and deposited on the surface of the porous copper material, and the parameters of tungsten sulfide are burned by pulse laser: YAG laser with wavelength of 525nm, maximum output single pulse energy of 50mj, repetition frequency of 100Hz and light spot of 1mm; vacuum degree less than x 10-6Torr, temperature 200oC, the pulse laser burning time is 30 min; the distance between the tungsten sulfide target and the substrate is 2 cm.
(6) And (3) obtaining the porous copper-based whisker material by high-temperature treatment: the temperature programmed at high temperature is increased to 500 ℃ from 10/minoC, keeping the temperature for 1H, naturally cooling to room temperature, and keeping the high-temperature atmosphere at 0.5vol.% H2Mixed gas of/He.
(7) And (3) performing electrochemical deposition by taking a Pt electrode as an anode and taking a Pt-free acid solution as an electrolyte: taking the porous copper-based whisker material obtained in the step (6) as a cathode, a platinum wire as an anode, electroplating solution as aqueous solution containing 0.1M tartaric acid and 0.5M oxalic acid, and current density of 50A/M2Electrodeposition time 5h, temperature 40oC, after electrodeposition, vacuum drying and reduction for 3H over 3vol.% H2/N2.
Finally, the porous copper-based whisker material is in a block shape and is not powder, soTungsten sulfide WS2The purity of (A) is more than 99.9%.
Example 2
An electrochemical deposition Pt-porous copper-based whisker catalyst material is characterized by comprising the following processing steps:
(1) preparing a Cu-Al alloy block: (a) the preparation method comprises the following steps of (a) physically and uniformly mixing 35wt.% of 2-3 mu m copper powder and 65wt.% of 7-8 mu m aluminum powder, (b) press forming under 350Mpa, (c) high-temperature sintering under inert atmosphere or reducing atmosphere, wherein the sintering temperature is 900 DEG CoC, the high temperature lasts for 2h, and the product is naturally cooled, wherein the pressure maintaining time of the compression molding is 8 min; the inert atmosphere is N2The reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
(2) Preliminary dealloying by chemical lye corrosion: the used corrosion solution is 1.5M NaOH aqueous solution, the corrosion time is 18h, and the temperature is 33oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
(3) Deep dealloying by electrochemical acid corrosion: taking the copper material obtained in the step (2) as an anode, taking a Pt sheet as a cathode and taking 0.65M HNO3The corrosion voltage is 0.4V, the corrosion time is 2.5h, and the electrochemical corrosion temperature is normal temperature.
(4) Drying and reducing: the drying process comprises alternately washing with ethanol-deionized water for several times to remove corrosive liquid, and vacuum drying; the reduction process was at 5vol.% H2/N2Then, the mixture was reduced in a tube furnace for 75 min.
(5) And (3) taking the porous copper obtained in the step (4) as a substrate, and performing pulse laser burning on tungsten sulfide: YAG laser is used to focus laser beam on the tungsten sulfide target material after passing through a holophote and a focusing lens, a photoablation reaction occurs, a target material plume is evaporated by melting and deposited on the surface of the porous copper material, and the parameters of tungsten sulfide are burned by pulse laser: YAG laser with wavelength of 525nm, maximum output single pulse energy of 50mj, repetition frequency of 100Hz and light spot of 1mm; vacuum degree less than x 10-6Torr, temperature 250oC, the pulse laser burning time is 40 min; the distance between the tungsten sulfide target and the substrate is 2 cm.
(6) And (3) obtaining the porous copper-based whisker material by high-temperature treatment: the temperature programmed at high temperature is increased to 600 ℃ from 10/minoC, keeping the temperature for 3 hours, naturally cooling to room temperature, and keeping the high-temperature atmosphere at 0.5vol.% H2Mixed gas of/He.
Finally, the porous copper-based whisker material is in a block shape and is not powder, and the tungsten sulfide WS is2The purity of (A) is more than 99.9%.
(7) And (3) performing electrochemical deposition by taking a Pt electrode as an anode and taking a Pt-free acid solution as an electrolyte: taking the porous copper-based whisker material obtained in the step (6) as a cathode, a platinum wire as an anode, electroplating solution as aqueous solution containing 0.15M tartaric acid and 0.6M oxalic acid, and current density of 75A/M2Electrodeposition time 5.5h, temperature 45oC, after electrodeposition, vacuum drying and reduction for 4H with 4vol.% H2/N2, the specific surface area of the obtained catalyst is 76 m2The compressive strength of the catalyst is 4.36Mpa, and the thermal conductivity is 82.7W m-1 K-1。
Example 3
An electrochemical deposition Pt-porous copper-based whisker catalyst material is characterized by comprising the following processing steps:
(1) preparing a Cu-Al alloy block: (a) uniformly mixing 30-40wt.% of 2-3 mu m copper powder and 60-70wt.% of 7-8 mu m aluminum powder, pressing and molding under 400Mpa, and sintering at high temperature of 950 ℃ in inert atmosphere or reducing atmosphereoC, maintaining the temperature for 3 hours, and naturally cooling, wherein the pressure maintaining time of the compression molding is 10 min; the inert atmosphere is N2The reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
(2) Preliminary dealloying by chemical lye corrosion: the used corrosive liquid is 2M NaOH aqueous solution, the corrosion time is 24h, and the temperature is 35oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
(3) Deep dealloying by electrochemical acid corrosion: the copper material obtained in the step (2) is used asAnode, Pt plate as cathode, 0.7M HNO3The corrosion voltage is 0.5V, the corrosion time is 3h, and the electrochemical corrosion temperature is normal temperature.
(4) Drying and reducing: the drying process comprises alternately washing with ethanol-deionized water for several times to remove corrosive liquid, and vacuum drying; the reduction process was at 5vol.% H2/N2Then, reduction treatment was carried out in a tube furnace for 90 min.
(5) And (3) taking the porous copper obtained in the step (4) as a substrate, and performing pulse laser burning on tungsten sulfide: YAG laser is used to focus laser beam on the tungsten sulfide target material after passing through a holophote and a focusing lens, a photoablation reaction occurs, a target material plume is evaporated by melting and deposited on the surface of the porous copper material, and the parameters of tungsten sulfide are burned by pulse laser: YAG laser with wavelength of 525nm, maximum output single pulse energy of 50mj, repetition frequency of 100Hz and light spot of 1mm; vacuum degree less than x 10-6Torr, temperature 300oC, the pulse laser burning time is 50 min; the distance between the tungsten sulfide target and the substrate is 2 cm.
(6) And (3) obtaining the porous copper-based whisker material by high-temperature treatment: the temperature programmed at high temperature is increased to 700 from 10/minoC, keeping the temperature for 1-5H, naturally cooling to room temperature, and keeping the high-temperature atmosphere at 0.5vol.% H2Mixed gas of/He.
Finally, the porous copper-based whisker material is in a block shape and is not powder, and the tungsten sulfide WS is2The purity of (A) is more than 99.9%.
(7) And (3) performing electrochemical deposition by taking a Pt electrode as an anode and taking a Pt-free acid solution as an electrolyte: taking the porous copper-based whisker material obtained in the step (6) as a cathode, a platinum wire as an anode, electroplating solution as aqueous solution containing 0.2M tartaric acid and 0.7M oxalic acid, and current density of 100A/M2Electrodeposition time 6h, temperature 50oC, after electrodeposition, vacuum drying and reduction for 5H over 5vol.% H2/N2.
Referring to the attached figure 1, an optical photo of a porous copper material is obtained after preliminary alloy removal and deep alloy removal, wherein the porous copper material is a three-dimensional network porous structure and is an integral block structure.
As shown in the attached figure 2, a plurality of filamentous whiskers grow in situ on the pore wall of the macropore, and the staggered growth of the whiskers obviously improves the specific surface area of the porous copper.
As shown in FIG. 3, PLD200oC. High temperature processing 500oC, the treatment time is 15m, and obvious in-situ convex can be found, and the copper whisker is in an initial form for growth.
As shown in FIG. 4, PLD250oC. High temperature processing 600oAnd C, treating for 3h to obtain an SEM image of the porous copper whisker material, and forming filament whiskers to a certain extent.
As shown in FIG. 5, PLD300oC. High temperature processing 700oC, SEM images of the porous copper whisker material obtained after the treatment time is 5h, and the excess amount of the whiskers is increased along with the increase of the time and the temperature.
As shown in FIG. 6, the HRTEM image of single-particle Pt has a particle size of about 4-5nm and is highly dispersed on the surface of the catalyst.
Using the catalyst obtained in example 2 as a sample, the catalyst was dissolved in a solution of 1 vol.% CO +1 vol.% O2+98 vol.% N2 at a space velocity of 24000 mL.g-1.h-1Performing activity on S-1, wherein the catalyst is in a range of 130 to 250oC can completely convert CO, and the selectivity is 50 percent and is 100 to 120oThe main reason that the C can not completely convert the CO is that the loading capacity of the active component of the catalyst is low, so that the low-temperature activity is low, and the loading capacity of the active component on the surface of the catalyst is improved by properly introducing the active component of the catalyst into the electrolyte, so that the low-temperature catalytic activity can be effectively improved.
At 130oC, testing the stability of the catalyst, wherein the time for completely converting CO is more than 300+ h.
Airspeed test, test 100 respectivelyoC. Airspeed of 24000 mL.g-1.h-1、48000 mL.g-1.h-1、96000 mL.g-1.h-1The conversion rates of the Pt-porous copper-based whisker catalyst and the catalyst are respectively 92.7%, 91.8% and 92.1%, namely, the Pt-porous copper-based whisker catalyst can also maintain higher catalyst activity under high space velocity.
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.
Claims (10)
1. The electrochemical deposition Pt-porous copper-based whisker catalyst material is a monolithic material, and is characterized in that the catalyst takes Pt obtained by electrochemical deposition as an active component, takes porous copper obtained by dealloying treatment and a porous copper-based whisker material for in-situ growth of copper whiskers on a porous copper pore window as a carrier, wherein the pore diameter of the porous copper and the pore diameter of the porous copper are distributed in the range of 5-30 mu m, and the specific surface area is 30-60m2The porosity is 50-70%, and the specific surface area of the Pt-porous copper-based whisker catalyst is 50-80m2The catalyst has the advantages of a macroporous range of 2-6 mu m, a mesoporous range of 10-30nm, a Pt loading amount of 0.5-0.8wt.%, a compressive strength of 4-5Mpa, a thermal conductivity coefficient of 70-90W m-1 K-1。
2. The electrochemical deposition Pt-porous copper-based whisker catalyst material as claimed in claim 1, wherein the Pt-free acidic solution adopted by the electrochemical deposition supported active component is a mixed solution of sulfuric acid and sodium sulfate, the porous copper-based whisker material is used as a cathode, a platinum wire is used as an anode, the electroplating solution is an aqueous solution containing 0.1-02M tartaric acid and 0.5-0.7M oxalic acid, and the current density is 50-100A/M2The electrodeposition time is 5-6h, and the temperature is 40-50oC, after electrodeposition, vacuum drying and reduction for 3-5H through 3-5vol.% H2/N2.
3. An electrochemically deposited Pt-porous copper-based whisker catalyst material according to claim 1, characterized in that the de-alloyed raw material is a Ni-Al alloy body prepared by the following process: (a) uniformly mixing 30-40wt.% of 1-5 mu m nickel powder and 60-70wt.% of 5-10 mu m aluminum powder, pressing and molding at 300-400Mpa, and sintering at 1300-1400 ℃ in inert atmosphere or reducing atmosphereoC, high temperature lasting for 1-3h, natural cooling, wherein the material is prepared byThe pressure maintaining time for press forming is 5-10 min; the inert atmosphere is N2The reducing atmosphere is H2(ii) a Temperature programming rate of the high temperature sintering 10oC/min。
4. An electrochemically deposited Pt-porous copper-based whisker catalyst material according to claim 1, characterized in that the dealloying treatment comprises chemical alkaline etching preliminary dealloying and electrochemical acid etching deep dealloying.
5. The electrochemically deposited Pt-porous copper-based whisker catalyst material as claimed in claim 4, wherein the etching solution used for the preliminary dealloying by the chemical alkaline etching is 1-2M NaOH aqueous solution, the etching time is 12-24h, and the temperature is 30-35oAnd C, removing bubbles by ultrasonic assistance in the corrosion process, and washing with deionized water for multiple times after corrosion.
6. An electrochemically deposited Pt-porous copper-based whisker catalyst material according to claim 4, characterized in that the electrochemical acid etch deep dealloying process is as follows: the copper material which is primarily de-alloyed by the corrosion of chemical alkali liquor is taken as an anode, a Pt sheet is taken as a cathode, and 0.6-0.7M HNO is taken3The corrosion voltage is 0.3-0.5V, the corrosion time is 2-3h, and the electrochemical corrosion temperature is normal temperature.
7. The electrochemically deposited Pt-porous copper-based whisker catalyst material of claim 4, wherein the de-alloying treatment is followed by a drying and reduction treatment, wherein the drying is performed by washing with ethanol-deionized water alternately for a plurality of times to remove the corrosive solution, and vacuum drying, and wherein the reduction is performed at 5vol.% H2/N2Then, reduction treatment is carried out in a tube furnace for 60-90 min.
8. An electrochemically deposited Pt-porous copper-based whisker catalyst material according to claim 1, characterized in that the whiskers are copper whiskers obtained by pulsed laser firing and high temperature treatment, wherein the pulsed laser firing is performed as follows: and placing the porous copper obtained through drying and reduction treatment as a substrate in a vacuum chamber, focusing a laser beam on the tungsten sulfide target material by using Nd-YAG laser after passing through a total reflection mirror and a focusing lens to generate a photoablation reaction, melting and evaporating a target material plume, and depositing the plume on the surface of the porous copper material.
9. An electrochemically deposited Pt-porous copper-based whisker catalyst material according to claim 8, characterized in that the pulsed laser burns tungsten sulfide with parameters: YAG laser with laser beam wavelength of 525nm, maximum output single pulse energy of 50mj, repetition frequency of 100Hz, light spot of 1mm, and vacuum degree less than x 10-6Torr at 200-300 deg.CoC, preferably 250oC, the pulse laser burning time is 30-50 min; the distance between the tungsten sulfide target and the substrate is 2cm, and the tungsten sulfide WS2The purity of (A) is more than 99.9%.
10. An electrochemically deposited Pt-porous copper-based whisker catalyst material according to claim 8, characterized in that the high temperature processing parameters are: the temperature programmed rise is 10/min to 500-700oC, keeping the temperature for 1-5H, naturally cooling to room temperature, and keeping the high-temperature atmosphere at 0.5vol.% H2Mixed gas of/He.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011113782.1A CN112138682A (en) | 2020-10-17 | 2020-10-17 | Electrochemical deposition Pt-porous copper-based whisker catalyst material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011113782.1A CN112138682A (en) | 2020-10-17 | 2020-10-17 | Electrochemical deposition Pt-porous copper-based whisker catalyst material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112138682A true CN112138682A (en) | 2020-12-29 |
Family
ID=73952170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011113782.1A Pending CN112138682A (en) | 2020-10-17 | 2020-10-17 | Electrochemical deposition Pt-porous copper-based whisker catalyst material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112138682A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624200A (en) * | 2014-12-30 | 2015-05-20 | 西安交通大学 | Preparation method of nano porous copper oxide loaded precious metal catalytic material |
| CN106206254A (en) * | 2016-07-13 | 2016-12-07 | 合肥工业大学 | There is the preparation method of the large-area two-dimensional stratified material of excellent photoluminescence property |
| CN106391007A (en) * | 2016-09-12 | 2017-02-15 | 吉林大学 | Catalyst for catalytic removal of carbon monoxide and formaldehyde under conditions of ambient temperature and humidity and preparation method of catalyst |
| CN108570710A (en) * | 2018-05-16 | 2018-09-25 | 中国科学院上海微系统与信息技术研究所 | The preparation method of copper whisker |
| CN108855098A (en) * | 2018-05-24 | 2018-11-23 | 天津工业大学 | A kind of multistage pore canal nickel alumin(i)um alloy film and preparation method thereof with electrocatalysis characteristic |
-
2020
- 2020-10-17 CN CN202011113782.1A patent/CN112138682A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624200A (en) * | 2014-12-30 | 2015-05-20 | 西安交通大学 | Preparation method of nano porous copper oxide loaded precious metal catalytic material |
| CN106206254A (en) * | 2016-07-13 | 2016-12-07 | 合肥工业大学 | There is the preparation method of the large-area two-dimensional stratified material of excellent photoluminescence property |
| CN106391007A (en) * | 2016-09-12 | 2017-02-15 | 吉林大学 | Catalyst for catalytic removal of carbon monoxide and formaldehyde under conditions of ambient temperature and humidity and preparation method of catalyst |
| CN108570710A (en) * | 2018-05-16 | 2018-09-25 | 中国科学院上海微系统与信息技术研究所 | The preparation method of copper whisker |
| CN108855098A (en) * | 2018-05-24 | 2018-11-23 | 天津工业大学 | A kind of multistage pore canal nickel alumin(i)um alloy film and preparation method thereof with electrocatalysis characteristic |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Juarez et al. | Nanoporous metals with structural hierarchy: A review | |
| CN110635141B (en) | Non-noble metal hydrazine oxidation catalyst based on synergistic modification and preparation method thereof | |
| JP7045662B2 (en) | Photocatalyst manufacturing method and hydrogen generation method | |
| CN111483999A (en) | Preparation method of nitrogen-doped carbon nanotube, nitrogen-doped carbon nanotube and application of nitrogen-doped carbon nanotube | |
| Khosrow-pour et al. | Large-scale synthesis of uniform lanthanum oxide nanowires via template-free deposition followed by heat-treatment | |
| CN112108158B (en) | Preparation method of electrochemical deposition Pt-porous copper-based whisker catalyst material | |
| Wu et al. | 3D ordered macroporous copper nitride–titanium oxynitride as highly efficient electrocatalysts for universal-pH hydrogen evolution reaction | |
| JP2007173109A (en) | Membrane-electrode conjugate for fuel cell, its manufacturing method, and fuel cell | |
| CN112111789B (en) | Preparation method of porous copper-based whisker material | |
| CN112126984A (en) | Porous copper-based whisker material | |
| CN116445971B (en) | Preparation method and application of self-derived nanorod containing active nickel and nickel hydroxide on foam nickel | |
| CN112138682A (en) | Electrochemical deposition Pt-porous copper-based whisker catalyst material | |
| CN116288462B (en) | Method for improving electrochemical oxygen evolution catalytic performance of Fe-based amorphous alloy | |
| CN114015903B (en) | Preparation method of high-porosity black porous metal film | |
| CN107899598B (en) | Preparation method of cobalt and nitrogen co-doped nano particle-carbon nano tube composite material | |
| RU2394849C1 (en) | Metal-carbon nanocomposite and method of preparing said composite | |
| CN116676612A (en) | Electrolytic water catalytic electrode with high-entropy alloy eutectic structure regulation and control hierarchical pore structure and preparation method thereof | |
| CN115212882A (en) | Porous copper silicide intermetallic compound material and preparation and application thereof | |
| CN114477144A (en) | Preparation method of carbon nanotube array | |
| CN113088988A (en) | Cobalt-doped foam carbon pyrolysis derived carbon material and preparation method thereof | |
| CN106917079B (en) | Chemically plating for Au-Pt alloy nanotube method | |
| CN110760875A (en) | All-solid-state rapid preparation method of alkaline electrolytic water electrode | |
| CN117548663A (en) | Preparation method of cubic cone-shaped porous silver micro-nano material | |
| CN116623133B (en) | Preparation method of metal needle point array type plasma photocatalyst | |
| KR100741139B1 (en) | Carbon nanosphere having one or more open portion, method for preparing the same, carbon nanosphere impregnated catalyst using the carbon nanosphere and fuel cell adopting the catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |