CN107970922A - 具有原子级分散的铂族金属络合物的催化剂 - Google Patents
具有原子级分散的铂族金属络合物的催化剂 Download PDFInfo
- Publication number
- CN107970922A CN107970922A CN201710974012.8A CN201710974012A CN107970922A CN 107970922 A CN107970922 A CN 107970922A CN 201710974012 A CN201710974012 A CN 201710974012A CN 107970922 A CN107970922 A CN 107970922A
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- Prior art keywords
- pgm
- platinum
- atom
- metal
- alkali
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- -1 platinum group metal complex compound Chemical class 0.000 title claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 86
- 125000004429 atom Chemical group 0.000 claims abstract description 70
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 42
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 40
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 40
- 239000003513 alkali Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims description 119
- 229910052783 alkali metal Inorganic materials 0.000 claims description 61
- 150000001340 alkali metals Chemical class 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 53
- 229910052697 platinum Inorganic materials 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 238000005470 impregnation Methods 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 7
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052705 radium Inorganic materials 0.000 claims description 6
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 5
- CWQSNJSRIUPVNR-UHFFFAOYSA-M [OH-].[Fr+] Chemical compound [OH-].[Fr+] CWQSNJSRIUPVNR-UHFFFAOYSA-M 0.000 claims description 5
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- ZDYCQQFBTFDFOK-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O ZDYCQQFBTFDFOK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052730 francium Inorganic materials 0.000 claims description 2
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 43
- 238000007598 dipping method Methods 0.000 description 35
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 description 26
- 239000000843 powder Substances 0.000 description 26
- 230000008569 process Effects 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 230000032683 aging Effects 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 17
- 238000001354 calcination Methods 0.000 description 13
- 238000011068 loading method Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 9
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910002321 LaFeO3 Inorganic materials 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 4
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 3
- XTIMETPJOMYPHC-UHFFFAOYSA-M beryllium monohydroxide Chemical compound O[Be] XTIMETPJOMYPHC-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 3
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- ZLRANBHTTCVNCE-UHFFFAOYSA-N 2-phenyl-3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C1=CC=CC=C1 ZLRANBHTTCVNCE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZJYSTCMILDFRDL-UHFFFAOYSA-N N.[Os+4] Chemical compound N.[Os+4] ZJYSTCMILDFRDL-UHFFFAOYSA-N 0.000 description 2
- 239000012696 Pd precursors Substances 0.000 description 2
- YESAPVFTAYLNBZ-UHFFFAOYSA-N [Ir].S(O)(O)(=O)=O Chemical compound [Ir].S(O)(O)(=O)=O YESAPVFTAYLNBZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- XRWSZZJLZRKHHD-WVWIJVSJSA-N asunaprevir Chemical compound O=C([C@@H]1C[C@H](CN1C(=O)[C@@H](NC(=O)OC(C)(C)C)C(C)(C)C)OC1=NC=C(C2=CC=C(Cl)C=C21)OC)N[C@]1(C(=O)NS(=O)(=O)C2CC2)C[C@H]1C=C XRWSZZJLZRKHHD-WVWIJVSJSA-N 0.000 description 2
- CBPDZOCGZCDPGA-UHFFFAOYSA-K azane ruthenium(3+) trichloride Chemical class [Ru+3].[Cl-].N.[Cl-].[Cl-] CBPDZOCGZCDPGA-UHFFFAOYSA-K 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229940125961 compound 24 Drugs 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- SJFQCJZXOTZTMU-UHFFFAOYSA-J osmium(4+);tetrachloride;hydrate Chemical compound O.[Cl-].[Cl-].[Cl-].[Cl-].[Os+4] SJFQCJZXOTZTMU-UHFFFAOYSA-J 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- 229910002328 LaMnO3 Inorganic materials 0.000 description 1
- NKJZWIUNCYAIGW-UHFFFAOYSA-L NN.[Ru](Cl)Cl Chemical compound NN.[Ru](Cl)Cl NKJZWIUNCYAIGW-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 229910019603 Rh2O3 Inorganic materials 0.000 description 1
- 229910019834 RhO2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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Abstract
一种催化转化器包括催化剂。该催化剂包括非改性金属氧化物载体和在非改性金属氧化物载体上原子级分散的铂族金属(PGM)络合物。PGM络合物包括PGM物质,该PGM物质选自由铂族金属原子、包括2个至小于10个原子铂族金属的簇以及它们的组合构成的组。碱金属或碱土金属结合到PGM物质。该碱金属或碱土金属是包括氧原子和氢原子的结构的一部分。
Description
背景技术
具有内燃机(ICE)的车辆包括用于处理来自发动机的排气的排气处理系统。处理系统的配置部分地取决于发动机是否是柴油机(其通常在稀薄燃烧下工作且在所有工作条件下排气中含高浓度的氧气)或理想配比火花点火发动机(其在几乎理想配比的空燃比(A/F)下工作)。柴油机的处理系统包括柴油氧化催化剂(DOC),其能氧化一氧化碳(CO)和烃类(HC)。理想配比火花点燃发动机的处理系统包括三元催化剂(WTC),其根据NOx被CO和HC的非选择性催化还原的原理而工作。
发明内容
一种催化转化器,其包括催化剂。该催化剂包括非改性金属氧化物载体和在非改性金属氧化物载体上原子级分散的铂族金属(PGM)络合物。PGM络合物包括PGM物质,该PGM物质选自由铂族金属原子、包括2个原子至小于10个原子铂族金属的原子簇以及它们的组合构成的组。碱金属或碱土金属结合到PGM物质。该碱金属或碱土金属是包括氧原子和氢原子的结构的一部分。
在用于形成催化剂的方法的一个实施例中,原子级分散的铂族金属(PGM)络合物形成于非改性金属氧化物载体上。原子级分散的铂族金属(PGM)络合物可以通过各种方法形成,其中有些方法包括共浸渍和干磨。
附图说明
本公开实施例的特征将通过参考以下详细描述和附图而变得清楚,其中相同的附图标记对应于类似尽管可能不相同的部件。为了简洁,具有前述功能的附图标记或特征可以结合或不结合示出它们的其他附图进行描述。
图1是示出PGM颗粒生长或烧结的两种机制的示意图;
图2A~2D示出本文所公开的PGM络合物的不同实施例;
图3是本文所公开催化剂的一个实施例的示意图;
图4A是部分切去的催化转化器一个实施例的立体图;
图4B是图4A一部分的放大图;
图5是示出基线例(1)和包括本文所公开的PGM络合物的实施例(2)在新鲜制备(F)时和老化后(A)的铂分散度(即,表面金属原子数与金属原子总数的比,显示为Y轴上的百分比)的图;
图6是示出老化的基线例(1)和老化的包括本文所公开PGM络合物的实施例(2)的作为温度(显示为X轴上的℃)函数的一氧化碳(CO)转化率(显示为Y轴上的百分比)的图;
图7是示出两个对比例(3、4)和包括本文所公开PGM络合物的两个实施例(5、6)老化后(A)的铂分散度(显示为Y轴上的百分比)的图;以及
图8A和8B是示出分别用于两个对比例(3、4)和包括本文所公开PGM络合物的两个实施例(5、6)的一氧化碳(CO)转化率和C3H6(丙烯(propene或propylene))转化率的起燃温度(以℃计)的图。
具体实施方式
DOC和TWC通常包括加载有铂族金属(PGM)作为活性催化/催化剂材料的载体。由于来自车辆发动机的排气温度升高(例如,至范围在150℃至大约1000℃的温度),加载在载体上的PGM可能变得不稳定并遭受生长(即,烧结)。图1示出了车辆工作期间PGM生长的两种机制。该机制涉及原子和/或微晶PGM迁移。第一种机制涉及通过气相的PGM迁移,标记为12,第二种机制涉及通过表面扩散的PGM迁移,标记为14。在第一种机制中,从加载在载体18上的PGM物质18释放出的移动物质(未示出)可以行进穿过气相12并与气相12中的其他金属颗粒20附聚形成更大的PGM颗粒16’(例如,纳米颗粒,其具有几十至几千个原子)。在第二种机制中,从PGM物质16中释放出的移动物质(未示出)可以沿载体18的表面18a扩散并与表面18a上的其他金属颗粒22附聚形成更大的PGM颗粒16’。第二种机制可能涉及Ostwald熟化,在Ostwald熟化中移动物质的迁移由自由能和载体18a上的局部原子浓度的差驱动。
PGM颗粒16’尺寸的增大导致低的PGM利用率和不期望的催化剂物质老化。更具体地,增大的颗粒尺寸降低了PGM分散度,PGM分散度是催化剂中表面PGM原子数与催化剂中PGM原子总数之比。PGM颗粒16’具有许多埋在内部的PGM原子,它们对催化反应贡献甚微。例如,在有些PGM颗粒16’中,超过80%的原子可能是未参与催化物质,或者是不是活性催化反应位点的物质。降低的PGM分散度直接与活性金属表面积的减少(由于颗粒生长)相关,因而表明活性催化反应位点的损失,其等效于催化活性的降低。活性催化反应位点的损失导致低PGM利用效率,表明催化剂不必要地老化了或失活了。
在本文所公开的实施例中,形成了PGM络合物,其利用含碱金属原子或碱土金属原子、氧原子和氢原子的结构稳定单个的PGM原子或PGM原子簇(包括2个原子至10个原子)。该稳定结构直接结合到PGM原子或原子簇,因而防止结合的物质发生气相或表面迁移。更小PGM单元(即,单个原子或小簇原子)可能将PGM效率最大化,因为更少配位的原子对于CO和HC氧化以及NOx减少具有极高的活性。本文所公开的PGM络合物减缓或防止PGM颗粒生长/烧结,并随时间推移维持更多的活性PGM位点,因而该催化剂比没有使PGM络合物稳定结构的催化剂老化得更慢。而且,当烧结减少或被防止时,可以防止催化剂的工作温度随时间向上偏移。
本文所公开的PGM络合物24包括PGM原子或PGM原子簇以及结合到该PGM原子或PGM原子簇的一个原子的稳定结构。该稳定结构由碱金属原子或碱土金属原子、氧原子以及氢原子组成。PGM络合物24的有些实施例在图2A至2D中示出了,分别标记为A、B、C和D。在图2A至2D的每一幅中,PGM原子(标记为PGM)呈条纹状,氧原子(其中之一标记为O)呈斑点状,碱金属原子或碱土金属原子(其中之一标记为A/AE)为灰色,氢原子(其中之一标记为H)为白色。
PGM原子或原子簇可以选自由铂原子、钯原子、铑原子、钌原子、锇原子或铱原子组成的组。碱金属可以选自由锂、钠、钾、铷、铯以及钫组成的组。碱土金属可以选自由铍、镁、钙、锶、钡以及镭组成的组。
在PGM络合物24(A、B、C、D)的每一个中,稳定结构的碱金属或碱土金属原子通过氧原子(或氧键)结合到PGM原子或PGM原子簇的原子中心。在有些实施例中,诸如PGM络合物24(A)和24(B),一个氧原子将碱金属或碱土金属原子中的每一个键合到PGM原子或PGM原子簇的原子中心。在其他实施例中,诸如PGM络合物24(C)和24(D)中,有些碱金属或碱土金属原子通过一个氧原子键合到PGM原子或PGM原子簇的原子中心,而其他碱金属或碱土金属原子在其自身与PGM原子或PGM原子簇的原子中心之间具有数个原子(例如,两个氧原子和另一个碱金属或碱土金属原子)。
在PGM络合物24中,PGM物质与碱金属或碱土金属原子的摩尔比在1∶3至1∶10的范围。在一个实施例中,PGM物质与碱金属或碱土金属原子的摩尔比在1∶5至1∶10的范围。PGM络合物24中存在的氧和/或氧原子数可以变化,以便平衡络合物24的零电荷。
PGM络合物24(A)包括九个氧原子O、九个碱金属或碱土金属原子A/AE以及两个氢原子H。PGM络合物24(B)包括八个氧原子O、九个碱金属或碱土金属原子A/AE以及两个氢原子H。PGM络合物24(C)包括十个氧原子O、九个碱金属或碱土金属原子A/AE以及七个氢原子H。PGM络合物24(D)包括十一个氧原子O、九个碱金属或碱土金属原子A/AE以及九个氢原子H。虽然这些络合物显示为单一PGM原子PGM,应当理解该原子可以是原子簇的一部分。
虽然示出了PGM络合物24的数个实施例(A、B、C、D),应当理解稳定结构可以包括任意数量的碱金属原子或碱土金属原子A/AE、氧原子O以及氢原子H。
催化剂10的实施例包括在非改性金属氧化物载体结构26上原子级分散的PGM络合物24。原子级分散,是指PGM络合物24(A、B、C、D)在非改性金属氧化物载体结构扩散,使得PGM络合物24(A、B、C、D)的PGM原子和PGM原子簇通常不附聚在一起成颗粒形式。PGM络合物24(A、B、C、D)可以(以物理和/或化学方式)结合到非改性金属氧化物载体结构26的表面26a,还可以存在于非改性金属氧化物载体结构26的孔(未示出)内。
催化剂10含占催化剂10总重量大于0wt%至大约5wt%的PGM物质(即,PGM原子或PGM原子簇)。
非改性金属氧化物载体结构26选自由Al2O3、CeO2、ZrO2、CeO2-ZrO2、SiO2、TiO2、ZnO、沸石、钙钛矿材料(例如,La09FeO3、LaFeO3、LaAlO3、Sr促进的LaFeO3(Sr-promoted LaFeO3)、Ce促进的LaFeO3(Ce-promoted LaFeO3)、LaMnO3或LaCoO3)以及它们的组合组成的组。非改性载体不具有被痕量杂原子成分减弱的某些氧化结构域。
非改性金属氧化物载体结构26可以呈粉末、球状或任何其他合适构型的形式。非改性金属氧化物载体结构26可以包括数个小孔。更多的孔增大表面积以在小体积中装下很多PGM络合物24(A、B、C、D)。在一个实施例中,非改性金属氧化物载体结构26的孔体积在大约0.5mL/g至大约2mL/g的范围。
为了形成催化剂10,在非改性金属氧化物载体26上形成原子级分散的PGM络合物24。选择PGM物质前体、碱金属前体或碱土金属前体以及方法,使得形成PGM-Ox-M键(其中,M是碱金属或碱土金属原子,x=1~6)。在有些实施例中,x可以在2至4的范围。碱金属或碱土金属物质在催化剂制备过程中应该容易桥接到PGM原子或PGM原子簇的原子之一的原子中心。在本文所公开的实施例中,碱金属或碱土金属离子不使金属氧化物载体26在任何特性明显的水平改性,相反,它们利用稳定结构使PGM物质变成期望的构型。有些PGM物质还可以通过氧键结合到非改性金属氧化物载体结构26(例如,PGM-Ox-S,其中S是载体结构26,x=1~6,或者有些情况下x=2~4)。
在形成催化剂10的方法的一个实施例中,使用了铂前体和碱金属前体。铂前体的示例包括硝酸四氨合铂(II)、氯化四氨合铂(II)、氢氧化四氨合铂(II)、氯铂酸、硝酸铂、乙酸铂以及二亚硝基二氨铂。碱金属前体的示例包括氢氧化钾、硝酸钾、氢氧化锂、硝酸锂、氢氧化钠、硝酸钠、氢氧化铷、硝酸铷、氢氧化铯、硝酸铯、氢氧化钫、硝酸钫以及它们的组合。
在本实施例方法中,铂前体和碱金属前体被共浸渍在非改性金属氧化物载体26上。共浸渍方法可以是干(或初始润湿)共浸渍工艺或湿共浸渍工艺。这些共浸渍中的任一种使用共同前体溶液。共同前体溶液可以是含水、铂前体以及碱金属前体的水溶液。这些特定的前体不会从溶液中沉淀出来。
前体溶液的浓度取决于载体26上和催化剂10中PGM物质和碱金属的期望加载量。例如,有1.5%铂和7.5%碱金属的总量10克催化剂10相当于0.15克铂(即,10克的1.5%)和0.75克碱金属(即,10克的7.5%)。纯铂与铂前体的质量比可用于确定应该用多少铂前体来达到催化剂10铂的期望质量。纯碱金属与碱金属前体的质量比可用于确定应该用多少碱金属前体来达到催化剂10碱金属的期望质量。制备水溶液所添加的水总量取决于共浸渍的类型。对于干浸渍,制备水溶液所添加的水总量取决于将充满孔体积(即,达到初始润湿)的水的体积。对于湿浸渍,制备水溶液所添加的水总量取决于前体的溶解度。可以将本实施例的溶液添加到9.1克干的载体26(即,10克总量-0.15克铂-0.75克碱金属=载体克数)。
对于干浸渍,将共同前体溶液添加到载体26至该溶液充满载体26的所有孔。不超出充满孔(即,初始润湿)所需的量添加额外的溶液。毛细管作用将前体溶液吸入到孔中。
对于湿浸渍,载体26首先用共同前体溶液的相同溶剂(例如,水)充满。接下来用共同前体溶液处理湿的载体26。在本实施例中,载体18的孔中不产生高压,相反,前体逐渐从共同前体溶液迁移进入到孔中。
然后对共浸渍载体进行干燥除水并煅烧以将铂前体转化成铂物质(即,单一原子或原子簇)和将碱金属前体转化成稳定结构(使碱金属通过氧键结合到铂物质)。干燥可以在空气中于在室温(例如,18℃至大约25℃)至大约150℃范围内的温度进行在大约12小时至大约24小时,煅烧可以在大约300℃至大约650℃范围内的温度下进行在大约1小时至大约4小时。在一个实施例中,煅烧在大约550℃下进行大约2小时。这一过程将铂前体和碱金属前体分解并在载体26的孔内和载体26的至少有些表面上形成PGM络合物24。
在形成催化剂10的方法的另一实施例中,使用任何PGM前体和任何碱金属前体或碱土金属前体。PGM前体可以选自由硝酸四氨合铂(II)、氯化四铵合铂(II)、氢氧化四铵合铂(II)、氯铂酸(H2PtCl6)、硝酸铂、乙酸铂、二亚硝基二氨铂、硝酸钯、乙酸钯、双(乙酰丙酮酰)钯、硝酸铑、乙酸铑、六水氯铱酸(H2IrCl6·6H2O)、氯化钌(III)、乙酰丙酮化钌(III)、六氨二氯化钌(II)、六氨三氯化钌(III)、水合氯化锇(III)、六氯锇铵、氯化铱(IV)、六氯铱酸铵、氯化铱(III)、硫酸铱以及它们的组合组成的组。碱金属前体可以选自由氢氧化钾、硝酸钾、氢氧化锂、硝酸锂、氢氧化钠、硝酸钠、氢氧化铷、硝酸铷、氢氧化铯、硝酸铯、氢氧化钫、硝酸钫以及它们的组合组成的组;或者碱土金属前体可以选自由氢氧化钡、硝酸钡、氢氧化镁、硝酸镁、氢氧化铍、硝酸铍、氢氧化钙、硝酸钙、氢氧化锶、硝酸锶、氢氧化镭、硝酸镭以及它们的组合组成的组。
在方法的本实施例中,使用了顺序浸渍,各次浸渍之间进行干燥。不进行干燥的话,第二前体的浸渍会洗掉第一前体。干燥也在低于前体煅烧温度的温度下进行。假如对前体分开煅烧(即,紧接着它们各自的浸渍之后),碱金属或碱土金属将更容易停留在它们的阳离子形式,而不结合到PGM物质。在这些情况下,PGM物质和碱金属或碱土金属将保持分开,不形成本文所公开的络合物。
方法的本实施例涉及将前体之一,i)PGM前体或者ii)碱金属前体或碱土金属前体中的任一种,浸渍在非改性金属氧化物载体26上以形成浸渍的非改性金属氧化物载体。
此浸渍步骤可以是干(或初始润湿)浸渍过程或湿浸渍过程。这些浸渍中的任一种使用PGM前体溶液(假如先加载PGM前体)或碱金属前体溶液或碱土金属前体溶液(假如先加载碱金属前体或碱土金属前体)。
PGM前体溶液可以是含水和PGM前体的水溶液。PGM前体溶液的浓度取决于催化剂10中PGM物质的期望加载量。例如,有1.5%钯的总量10克的催化剂10相当于0.15克钯(即,10克的1.5%)。纯钯与钯前体的质量比可用于确定应该用多少钯前体来达到催化剂10钯的期望质量。
碱金属前体溶液可以是含水和碱金属前体的水溶液。碱土金属前体溶液可以是含水和碱金属前体的水溶液。碱金属前体溶液或碱土金属前体溶液的浓度取决于载体26上和催化剂10中碱金属或碱土金属的期望加载量。例如,有8.5%碱金属或碱土金属的总量10克的催化剂10相当于0.85克碱金属或碱土金属(即,10克的8.5%)。纯碱金属与碱金属前体或纯碱土金属与碱土金属前体的质量比可用于确定分别应该用多少碱金属前体或碱土金属前体来达到催化剂10的期望碱金属质量。
制备PGM前体溶液或碱金属前体溶液或碱土金属前体溶液所添加的水总量取决于浸渍的类型。对于干浸渍,制备水溶液所加水的总量取决于将充满孔体积(即,达到初始润湿)的水的体积。对于湿浸渍,制备水溶液所加水的总量取决于各自前体的溶解度。
将PGM前体溶液或碱金属前体溶液或碱土金属前体溶液添加到干的载体26来如前所述进行干浸渍或湿浸渍。此过程形成浸渍的非改性金属氧化物载体。
浸渍的非改性金属氧化物载体在低于PGM前体或碱金属前体或碱土金属前体(此时浸渍了哪一种前体则是哪一种)煅烧温度的温度下干燥。合适干燥温度(低于煅烧温度)的示例在大约室温至大约120℃的范围。在一个实施例中,干燥温度为大约80℃。
方法的本实施例然后涉及浸渍其余尚未浸渍的前体。例如,假如PGM前体已经加载在载体26上了,则此浸渍将加载碱金属前体或碱土金属前体。此浸渍将如前所述使用碱金属前体溶液或碱土金属前体溶液。可选地,假如碱金属前体或碱土金属前体已加载在载体26上了,则此浸渍将加载PGM前体。此浸渍将如前所述使用PGM前体溶液。此浸渍过程产生浸渍的非改性金属氧化物载体。
浸渍的非改性金属氧化物载体在低于PGM前体和碱金属前体或碱土金属前体(因为此时浸渍了这两种前体)煅烧温度的温度下干燥。
接下来对共浸渍的非改性金属氧化物载体进行煅烧。在本实施例中,煅烧在大约350℃至大约550℃范围内的温度进行大约2小时至大约10小时。这一过程将PGM前体和碱金属前体或碱土金属前体分解并在载体26的孔内和载体26的至少有些表面上形成PGM络合物24。
在方法的又一实施例中,使用固态浸渍来引入碱金属前体或碱土金属前体。此方法避免了碱金属前体溶液和碱土金属前体溶液的使用。
在固态浸渍方法中,可以使用任何PGM前体和任何碱金属前体或碱土金属前体。为了重复,PGM前体可以选自由硝酸四氨合铂(II)、氯化四铵合铂(II)、氢氧化四铵合铂(II)、氯铂酸、硝酸铂、乙酸铂、二亚硝基二氨铂、硝酸钯、乙酸钯、双(乙酰丙酮酰)钯、硝酸铑、乙酸铑、六水氯铱酸、氯化钌(III)、乙酰丙酮化钌(III)、六氨二氯化钌(II)、六氨三氯化钌(III)、水合氯化锇(III)、六氯锇铵、氯化铱(IV)、六氯铱酸铵、氯化铱(III)、硫酸铱以及它们的组合组成的组;碱金属前体可以选自由氢氧化钾、硝酸钾、氢氧化锂、硝酸锂、氢氧化钠、硝酸钠、氢氧化铷、硝酸铷、氢氧化铯、硝酸铯、氢氧化钫、硝酸钫以及它们的组合组成的组;碱土金属前体可以选自由氢氧化钡、硝酸钡、氢氧化镁、硝酸镁、氢氧化铍、硝酸铍、氢氧化钙、硝酸钙、氢氧化锶、硝酸锶、氢氧化镭、硝酸镭以及它们的组合组成的组。
在方法的本实施例中,PGM前体通过浸渍方法分散在非改性金属氧化物载体26上和非改性金属氧化物载体26中。此浸渍可以是干(或初始润湿)浸渍过程或湿浸渍过程。这些浸渍中任一种利用了前述的PGM前体溶液。
PGM前体浸渍之后,对浸渍的载体进行干燥以去除水和形成粉末。干燥可以在空气中在室温(例如,大约18℃至大约25℃的范围)持续大约7小时至大约12小时来完成。
然后将粉末与碱金属前体或碱土金属前体(其在本实施例中不是前体溶液的形式)一起研磨。一起研磨的粉末和前体的量可以以催化剂10中存在的PGM物质与碱金属或碱土金属的期望摩尔比为基础。如本文所提及的,PGM物质与碱金属或碱土金属之比可以在1∶3至1∶10的范围。在有些实施例中,该比在1∶5至1∶10的范围。
粉末和碱金属前体或碱土金属前体的研磨可以是干磨过程,其形成粉末混合物。在干磨过程中,粉末的温度在大约18℃至大约80℃的范围,或者有些情况下至大约70℃。干磨可以进行大约10分钟至大约10小时的时间。干磨可以通过小规模手动研磨,或者利用研磨机械(例如,研磨机、珠磨机、超微磨碎机等)来完成。
然后在大约18℃至大约80℃范围内的温度下对粉末混合物干燥大约8小时至大约12小时。接下来如前所述煅烧干燥的粉末混合物。
在前述实施例(例如,共浸渍、顺序浸渍以及固态浸渍)中,应当理解,可以用煅烧来形成PGM络合物24并烧掉可能结合到PGM络合物24的多余自由基(例如,硝酸盐、乙酸盐、氨等)。
在方法的又一实施例中,PGM络合物24在分散于非改性金属氧化物载体26之中和之上之前形成。本实施例方法利用单独含PGM物质、碱金属或碱土金属、氧以及氢的前体和溶剂,使得所生成的PGM络合物24中不存在额外的自由基。然后在本实施例中,PGM前体是PGM氧化物(例如,PdO、PtO2、RuO2、RhO2或Rh2O3、OsO2、IrO2)或者PGM氢氧化物(例如,Pd(OH)2、Pt(OH)4、Ru(OH)3、Rh(OH)3、Os(OH)4、Ir(OH)3),碱金属前体或碱土金属前体是碱金属氢氧化物或碱土金属氢氧化物。碱金属氢氧化物前体的示例包括:氢氧化钾、氢氧化锂、氢氧化钠、氢氧化铷、氢氧化铯、氢氧化钫以及它们的组合;碱土金属氧化物前体的示例包括:氢氧化钡、氢氧化镁、氢氧化铍、氢氧化钙、氢氧化锶、氢氧化镭以及它们的组合。
为了形成PGM络合物24,首先制备PGM氧化物或PGM氢氧化物的水溶液。PGM氧化物或PGM氢氧化物的浓度以催化剂10中PGM物质的期望加载量为基础,可以如前所述确定。加热此水溶液至大约80℃的温度,在此温度下将碱金属氢氧化物或碱土金属氢氧化物混入该水溶液。添加的碱金属氢氧化物或碱土金属氢氧化物的量可以以催化剂10中存在的PGM物质与碱金属或碱土金属的期望摩尔比为基础。如本文所提及的,PGM物质与碱金属或碱土金属之比可以在1∶3至1∶10的范围。在有些实施例中,该比在1∶5至1∶10的范围。添加碱金属氢氧化物或碱土金属氢氧化物之后,该水溶液可以在相同温度下回流大约7小时至大约12小时的时间。由于此过程,PGM络合物24在水溶液中形成。
以下是PGM络合物24通过方法的本实施例如何形成的一个实施例。将指定量的PdO或Pd(OH)2在30mL水中伴随着N2吹扫而淤浆化。加热该溶液至80℃。在相同温度下将NaOH粉末(Pd∶Na的摩尔比=1∶10)加到淤浆中。在80℃下回流混合物过夜,形成透明溶液。当降低碱/碱土金属浓度时,该透明溶液可能是无色的,在更高的碱/碱土金属浓度下,该透明溶液可能是浅黄色。此溶液在80℃连续搅拌下不会沉淀。
然后含PGM络合物24的溶液可以用于将PGM络合物24浸渍在非改性金属氧化物载体26上。此浸渍过程可以是干或湿浸渍,取决于溶液中水的总量和非改性金属氧化物载体26的孔体积。
接下来可以对浸渍后的载体进行干燥。干燥可以在空气中大约室温(例如,18℃至大约25℃)至大约150℃范围内的温度下持续大约12小时至大约24小时而完成。
在该方法的本实施例中,可以使用或不用煅烧,因为PGM络合物24已形成,没有需要除去的多余自由基。如果进行,煅烧可以在大约300℃至大约650℃范围内的温度进行大约1小时至大约4小时。当催化剂10被用于催化剂工作温度较低(例如,大约100℃)的应用中时,在该方法的本实施例中进行煅烧可以是可取的。在较低的工作温度下,催化剂10由于可以粘到催化剂10内部孔中的水分子而可能遇到扩散问题。在工作使用之前进行煅烧可以去除水分子,从而降低催化剂扩散限制的可能性。
在本文所公开的任一方法中,在PGM络合物24加载在非改性金属氧化物载体26上之前,应当理解,可以对非改性金属氧化物载体26进行减少其表面积的过程。在形成催化剂10之前减少载体26的表面积意味着可用于PGM络合物24的表面26可能更少。更少的PGM络合物24减小最终催化剂10的重量增加。
在载体26预处理的一个实施例中,在大约350℃至大约450℃范围内的温度对非改性金属氧化物载体26煅烧大约9小时至大约11小时。在载体26预处理的另一个实施例中,在真空中大约60℃至大约80℃范围内的温度对非改性金属氧化物载体26加热大约10小时至大约72小时。
催化剂10可以通过本文所公开的方法而形成,然后可以施用到整体式基材并在催化转化器中使用。图4A中示出了催化转换器30的一个实施例,图4A和图4B中示出了整体式基材32的一个实施例。
催化转化器30包括整体式基材32。整体式基材32可以由能够耐受高温(例如,100℃或更高)的陶瓷或金属合金制成。合成堇青石是适合用作整体式基材32的镁铝硅酸盐陶瓷材料。铁素体铁铬铝合金是适合用作整体式基材32的金属合金的一个实施例。整体式基材32具有蜂窝状或其他三维结构。
图4B中示出了整体式基材32的一部分的放大图。整体式基材32包括大量的平行流路34,以便允许排气35与催化剂10(包含于涂层36中)之间足够的接触面积而不产生过多的压力损失。
涂层36包括本文所公开的催化剂10。在有些情况下,涂层36还可以包括粘合剂材料(例如,凝胶粘合剂等)。涂层36可以通过洗涂或一些其他类似的过程而被施涂到整体式基材32。
再次参考图4A,在催化转化器30中,整体式基材32被垫构件38包围,而垫构件38又被绝缘构件40包围。上壳42和下壳44(由金属制成)可以置于垫构件38与绝缘构件40之间。绝缘盖46可以置于上壳42和其上的绝缘构件40上方,屏蔽件48可以置于与下壳44和绝缘构件40相邻。
催化转化器30可以是DOC,DOC用在柴油发动机中。DOC是二元催化转化器,其通过将烃类和CO分别氧化成水和CO2来清除它们。DOC还可以在车辆冷启动期间展现出NOx储存能力。在这类柴油发动机中,还原NOx成水和N2可以在独立单元中进行,且可以涉及尿素喷入到排气中。
催化转化器30还可以是TWC,TWC用在理想配比火花点燃发动机中。TWC是三元催化转化器,其将NOx还原成N2,将HC和CO分别氧化成水和CO2。
为了进一步说明本公开,在此给出实施例。应当理解,本实施例是为了说明性目的而提供的,不应被解释为限制本公开的范围。
实施例1
本实施例用于测试含钾的稳定结构对铂分散度的影响。
对比样品1包括浸渍过程中在上面加载有铂金属的氧化铝载体。在此过程中,将硝酸四氨合铂(II)水溶液添加到氧化铝粉末直至氧化铝粉末的所有孔都被充满。设计的Pt加载量是1.5wt.%。未添加过量溶液。在黑暗真空中于室温下对浸渍的粉末干燥过夜,然后在空气中于350℃至550℃下煅烧2~4小时以在氧化铝载体上形成铂金属物质。
样品2包括共浸渍过程中在上面负载有PGM络合物的氧化铝载体。在此过程中,将硝酸四氨合铂(II)和氢氧化钾的水溶液添加到氧化铝粉末直至氧化铝粉末的所有孔被充满。设计的Pt加载量为1.4wt.%,Pt∶K原子按摩尔计的比例为1∶5至1∶10。未添加过量溶液。在黑暗真空中于室温下对浸渍的粉末干燥过夜,然后在空气中于350℃至550℃下煅烧2~4小时以在氧化铝载体上形成PGM络合物。
对对比样品1和样品2进行老化过程。老化过程涉及在添加10体积%水的情况下将样品在空气中于650℃暴露2小时。
通过化学吸附确定对比样品1和样品2在老化之前(即,新鲜样品,图5中的“F”)和老化之后(即,图5中的“A”)的铂分散度(表面Pt原子数与Pt原子总数之比)。利用化学吸附,测量分子(像CO或H2)在PGM金属上的吸附。此测量和样品中PGM的总质量能够确定有多少PGM在表面上。一般而言,分散度越高,催化剂工作期间PGM使用效率越高。
图5示出了铂分散度结果。如图所示的,对比样品1(标记为“1”,无含铂的稳定结构)的铂分散度在新鲜时为大约65%,老化后为大约17%,而样品2(标记为“2”)的铂分散度在新鲜时为大约55%,老化后为大约45%。与样品2的老化结果相比,对比样品1的老化结果显著减小。这些结果表明对比样品1非被稳定的铂经历了烧结和颗粒生长。因此,与样品2相比,对比样品1的催化剂在老化后可用于催化作用的表面Pt原子数减少了。
然后在以每分钟2℃的速率上升的进气温度(100℃至350℃)下将对比样品1和样品2暴露于排气(含5000ppm CO、5%H2O和余量N2)。空速(SV)为1,500,000cm3克催化剂-1h-1,其中空速是指单位时间内反应物的进入体积流速除以反应器体积(或催化剂床体积)的商。确定了CO的转化率。
图6是作为以℃计的进气温度(X轴)函数的CO转化率百分比(%,Y轴)的曲线图。线1说明了对比样品1的CO氧化率或CO转化率,线2说明了样品2的CO氧化率或CO转化率。图6具体示出了T50处的CO转化率,T50是达到50%转化率时的温度。T50越低越好。如图所示的,当铂用含钾的稳定结构(样品2)稳定时,起燃温度(在T50处)大大降低。样品2起燃温度的下降(ΔT=15℃)(与对比样品1对比)是有利的,部分因为催化剂能在更低温度下有CO氧化活性。还预计这能转化成相同性能所要求的显著更低的PGM加载量(~50%),这导致催化剂中所用贵重金属成本的降低。
实施例2
对比样品3和4包括浸渍过程中在上面加载有不同量铂金属的氧化铝载体。在此过程中,将硝酸四氨合铂(II)的水溶液添加到氧化铝粉末直至氧化铝粉末的所有孔都被充满。对于对比样品3,设计的Pt加载量为1.5wt.%,对于对比样品4,设计的Pt加载量为0.5wt.%。未添加过量溶液。在黑暗真空中于室温下对浸渍的粉末干燥过夜,然后在空气中于350℃至550℃下煅烧2~4小时以在氧化铝载体上形成铂金属物质。
样品5包括共浸渍过程中在上面加载有PGM络合物的氧化铝载体。在此过程中,将硝酸四氨合铂(II)和氢氧化钾的水溶液添加到氧化铝粉末直至氧化铝粉末的所有孔都被充满。设计的Pt加载量为0.4wt.%,Pt∶K原子按摩尔计的比例为1∶5至1∶10。未添加过量溶液。在黑暗真空中于室温下对浸渍的粉末干燥过夜,然后在空气中于350℃至550℃下煅烧2~4小时以在氧化铝载体上形成PGM络合物。
样品6包括固态浸渍过程中在上面加载有PGM络合物的氧化铝载体。在此过程中,将氯铂酸的水溶液添加到氧化铝粉末直至氧化铝粉末的所有孔都被充满。设计的Pt加载量是0.4wt.%。未添加过量溶液。在空气中于室温下对浸渍的粉末干燥过夜。然后将干燥的粉末与指定量的硝酸钡(按摩尔计,Pt∶Ba=1∶5~1∶10)在室温下一起研磨大约30分钟。在黑暗真空中于室温下对得到的混合物干燥过夜,然后在空气中于350℃至550℃下煅烧2~4小时以在氧化铝载体上形成PGM络合物。
对对比样品3和4以及样品5和6进行老化过程。老化过程涉及在添加10体积%水的情况下将样品在空气中于650℃暴露2小时。
通过化学吸附确定对比样品3和4以及样品5和6老化之后的铂分散度(表面Pt原子数与Pt原子总数之比)。图7中示出了铂分散度结果。如图所示的,老化后对比样品3和4(分别标记为“3”和“4”,没有稳定结构)的铂分散度少于40%,而老化后样品5(标记为“5”)的铂分散度接近60%,样品6(标记为“6”)的铂分散度接近80%。与样品5和6的老化结果相比,对比样品3和4的老化结果显著减小。这些结果表明对比样品3和4未被稳定的铂经历了比样品5和6程度更大的烧结和颗粒生长。因此,与样品5和6相比,对比样品3和4的催化剂在老化后可用于催化作用的表面Pt原子数减少了。
然后在以每分钟2℃的速率上升的进气温度(100℃~350℃)下将对比样品3和4以及样品5和6暴露于排气(含5000ppm CO、500ppm HC、1.0%O2、5%H2O和余量N2)。空速(SV)为1,500,000cm3克催化剂-1h-1,其中空速是指单位时间内反应物的进入体积流速除以反应器体积(或催化剂床体积)的商。确定了CO和C3H6的转化率。
确定了对比样品3和4以及样品5和6针对CO和C3H6的起燃温度。在T50处测量起燃温度,T50是CO或C3H6转化率达到50%时的温度。T50越低越好。图8A中示出了CO起燃温度,图8B中示出了C3H6起燃温度。在更少铂的情况下,实施例5表现得比对比例4好。由于少得多的铂烧结(如图7中所证实的),实施例6(0.4wt%Pt,有含钡的稳定结构)的CO和C3H6氧化速率比对比例4(0.5wt%Pt,无稳定结构)的分别低3倍和10倍。这些结果还表明在少得多的铂的情况下实施例6与对比例3活性一样。
应当理解,本文提供的范围包括所述范围和所述范围内的任意值或子范围。例如,大约300℃至大约650℃的范围应当解释为不仅包括明确表述的大约300℃至大约650℃的界限,还包括单个值,例如425℃、480℃、520.5℃等,以及子范围,例如大约415℃至大约575℃等。此外,当用“大约”描述一个值时,这意味着包含所述值的微小变化(高达+/-10%)。
在整个说明书中提及“一个实施例”、“另一实施例”、“实施例”等等,意味着结合该实施例描述的特定元素(例如,特征、结构和/或特性)被包括在本文所描述的至少一个实施例中,可以存在或不存在于其他实施例中。另外,应当理解,除非上下文另外明确指出,针对任一实施例所描述的元素可以以任何合适的方式在各实施例中组合。
除非上下文另外明确指出,在描述或要求保护本文所公开的实施例时,单数形式的“一个(“a”、“an”和“the”)”包括复数对象。
尽管详细描述了若干实施例,应当理解,所公开的实施例是可以变型的。因此,前述描述应当认为是非限制性的。
Claims (10)
1.一种催化转化器,其包含:
催化剂,其包括:
非改性金属氧化物载体;以及
在所述非改性金属氧化物载体上原子级分散的铂族金属(PGM)络合物,所述PGM络合物包括:
PGM物质,其选自由铂族金属原子、包括2个原子至小于10个原子铂族金属的原子簇以及它们的组合构成的组;以及
结合到所述PGM物质的碱金属或碱土金属,其中所述碱金属或所述碱土金属是包括氧原子和氢原子的结构的一部分。
2.根据权利要求1所述的催化转化器,其中所述PGM物质与所述碱金属或所述碱土金属的摩尔比在1∶3至1∶10的范围。
3.根据权利要求1所述的催化转化器,其中所述非改性金属氧化物载体选自由Al2O3、CeO2、ZrO2、CeO2-ZrO2、SiO2、TiO2、ZnO、沸石、钙钛矿以及它们的组合组成的组。
4.根据权利要求1所述的催化转化器,其中:
所述碱金属选自由锂、钠、钾、铷、铯以及钫组成的组;或者
所述碱土金属选自由铍、镁、钙、锶、钡以及镭组成的组。
5.根据权利要求1所述的催化转化器,其中所述PGM物质以范围在占所述催化剂总w%大于0wt%至大约5wt%的量存在。
6.根据权利要求1所述的催化转化器,其中所述铂族金属选自由钯、铂、铑、钌、锇、铱以及它们的组合组成的组。
7.根据权利要求1所述的催化转化器,其中所述碱金属或碱土金属通过氧键结合到所述PGM物质。
8.根据权利要求7所述的催化转化器,进一步包含通过另一氧键结合到所述非改性金属氧化物载体的另外的PGM物质。
9.一种形成催化剂的方法,所述方法包含在非改性金属氧化物载体上形成原子级分散的铂族金属(PGM)络合物,所述PGM络合物包括:
PGM物质,其选自由铂族金属原子、包括2个原子至小于10个原子铂族金属的原子簇以及它们的组合构成的组;以及
结合到所述PGM物质的碱金属或碱土金属,其中所述碱金属或所述碱土金属是包括氧原子和氢原子的结构的一部分。
10.根据权利要求9所述的方法,其中:
所述PGM物质是铂原子或铂原子簇;
所述PGM络合物包括所述碱金属;以及
在所述非改性金属氧化物载体上形成所述原子级分散的铂族金属(PGM)络合物通过以下步骤完成:
将铂前体和碱金属前体共浸渍在所述非改性金属氧化物载体上;以及
煅烧所述共浸渍的非改性金属氧化物载体,其中
所述铂前体选自由硝酸四氨合铂(II)、氯化四氨合铂(II)、氢氧化四氨合铂(II)、氯铂酸、硝酸铂、乙酸铂以及二亚硝基二氨铂组成的组;以及
所述碱金属前体选自由氢氧化钾、硝酸钾、氢氧化锂、硝酸锂、氢氧化钠、硝酸钠、氢氧化铷、硝酸铷、氢氧化铯、硝酸铯、氢氧化钫、硝酸钫以及它们的组合组成的组。
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CN111269086A (zh) * | 2020-03-06 | 2020-06-12 | 厦门大学 | 一种原子级分散钌催化剂在催化加氢上的应用方法 |
CN112169790A (zh) * | 2020-10-12 | 2021-01-05 | 商洛学院 | 原位光还原法制备高负载量的贵金属单原子催化剂的方法 |
CN112169790B (zh) * | 2020-10-12 | 2023-08-25 | 商洛学院 | 原位光还原法制备高负载量的贵金属单原子催化剂的方法 |
CN115337926A (zh) * | 2022-08-19 | 2022-11-15 | 天津大学 | 一种铑基催化剂及其制备方法和应用 |
CN115337926B (zh) * | 2022-08-19 | 2023-07-25 | 天津大学 | 一种铑基催化剂及其制备方法和应用 |
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US10159960B2 (en) | 2018-12-25 |
DE102017124764A1 (de) | 2018-04-26 |
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US20180111112A1 (en) | 2018-04-26 |
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