CN112844378A - Method for regulating and controlling interaction between nano metal particles and gel type oxide carrier - Google Patents
Method for regulating and controlling interaction between nano metal particles and gel type oxide carrier Download PDFInfo
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- CN112844378A CN112844378A CN202011592894.XA CN202011592894A CN112844378A CN 112844378 A CN112844378 A CN 112844378A CN 202011592894 A CN202011592894 A CN 202011592894A CN 112844378 A CN112844378 A CN 112844378A
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- Prior art keywords
- metal
- gel
- interaction
- nano
- acetylacetone
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- 230000003993 interaction Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002923 metal particle Substances 0.000 title claims abstract description 21
- 230000001276 controlling effect Effects 0.000 title claims abstract description 20
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 239000002184 metal Substances 0.000 claims abstract description 63
- 239000002131 composite material Substances 0.000 claims abstract description 47
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 31
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 26
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 82
- 238000003756 stirring Methods 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 22
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 claims description 19
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000001099 ammonium carbonate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000007769 metal material Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical class [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 239000000969 carrier Substances 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001805 chlorine compounds Chemical group 0.000 claims description 3
- 238000010908 decantation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Chemical class 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical class [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Chemical class 0.000 claims description 3
- 239000004332 silver Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims 2
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 239000012716 precipitator Substances 0.000 abstract description 28
- 239000000203 mixture Substances 0.000 abstract description 11
- 239000012298 atmosphere Substances 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000004220 aggregation Methods 0.000 abstract description 6
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 23
- 238000009210 therapy by ultrasound Methods 0.000 description 22
- 238000010992 reflux Methods 0.000 description 11
- 239000012266 salt solution Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
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- 238000010899 nucleation Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- CHACQUSVOVNARW-LNKPDPKZSA-M silver;(z)-4-oxopent-2-en-2-olate Chemical compound [Ag+].C\C([O-])=C\C(C)=O CHACQUSVOVNARW-LNKPDPKZSA-M 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
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- 230000000171 quenching effect Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B01J35/393—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
Abstract
A method for regulating and controlling the interaction between nano metal particles and a gel type oxide carrier relates to the field of metal inorganic composite materials. The interaction degree between the noble metal nano particles and the gel type oxide carrier is subjected to multilevel intervention regulation and control by adopting comprehensive measures such as a composite carrier, surface acetylacetone, a diphenol gradual reducing agent, multi-atmosphere calcination and the like. On the premise of maintaining the original supported nano system, the control of the population form of the metal component is realized, so that the structural micro-assembly type composite material with multiple advantages of a dispersive nano metal system and a supported metal micro-area structure is prepared. Because the aggregation states of the metal and the carrier can be modulated by the composite precipitator and the composite reducing agent with different compositions, and the reduction load of the metal ions at different temperatures or the same temperature is controlled at the same time, the single metal and the alloy material with controllable size and controllable interaction degree can be prepared.
Description
Technical Field
The invention relates to the field of metal inorganic composite materials, in particular to a method for regulating and controlling the interaction between nano metal particles and a gel type oxide carrier in an oxide-supported metal material system.
Background
With the development of nanotechnology and the popularization and application of nano materials, nano metal materials with microscale effect and high dispersion characteristics show wide application prospects in a plurality of leading-edge fields such as energy, environment, communication, manufacturing industry and the like. Among them, noble metal-based nanomaterials, which are most actively grown, have recently been manufactured as homogeneous or heterogeneous alloy nanoparticles by introducing various transition metal components thereto. The electronic structure is adjusted through charge transfer and synergistic effect among different atoms in alloy composition nano particles, lattice structure parameters are changed, the tendency of the micro-effect of a nano particle system can be controlled, and the parameter index and performance of the material in a specific application field are further expanded and optimized.
The nano metal particle system is supported by a gel-type solid with a large specific surface area, is a necessary measure for preserving the nano size effect and maintaining high dispersion characteristics, and is widely adopted in production practice. Since the gel-type carrier with a large specific surface area has a high surface energy, the gel-type carrier and the supported nano-metal particles tend to release surface energy of each other through interaction to reach a stable structure after contacting with the nano-metal particles. In fact, the interaction existing between the metal component and the carrier has been used for the preparation of various types of supported catalytic materials (chinese patent CN103157469A, CN102895969A), and by this way, the carrier will carry out secondary processing on the supported metal component to make it have specific structural and reaction characteristics, so as to make the composite material better perform specific functions.
In the case of a specific system, the metal-oxide interaction includes interface charge redistribution and structural reorganization, which determine the properties of the metal-oxide interface, and further, the morphology and structural changes, even the size, of the metal and the support affect the degree of interaction, and it is also shown in the above patent that the structure and performance of the composite system of the nano metal particles and the oxide support can be ultimately affected by controlling the precipitation conditions for preparing the support, such as the sequence and speed of feeding, the acidity at the end point of precipitation, and the aging temperature and time of precipitation. Among a plurality of preparation parameters, determining a key technical index capable of continuously adjusting the initial state of the interaction of the two is helpful for realizing effective control on the structure and properties of the metal-inorganic composite material.
The preparation process of the catalyst has two crucial operation links, one is a water phase precipitation process for preparing the precursor of the carrier, wherein the concentration and the type of a precipitator, the precipitation temperature, the aging time and the like have obvious influence on the structure and the performance of the carrier. Another is the reduction process of noble metal ions, and the polyol liquid phase chemical reduction of metal salts is an important preparation method of metal nanoparticles, and the synthesis of metal nanoparticles by the polyol method is usually carried out under anhydrous conditions, because the presence of water accelerates the hydrolysis of organometallic compounds to inhibit the reduction of metal precursors, and thus the reduction in a non-polar medium is selected. A typical polyol synthesis process comprises 3 steps: dissolution of metal precursors, reduction of metal cations, nucleation and growth of metal crystals. The synthesis conditions can be accurately regulated and controlled through the comprehensive strategy, and the controllable synthesis of the size and the shape of the metal nanoparticles is realized. The selection of the reducing agent is particularly important, the polyhydric alcohol with moderate reducing capability is beneficial to fine regulation and control of nucleation and growth kinetics of metal nanoparticles, and the morphology regulation and control of single metal and alloy thereof are greatly dependent on the regulation and control of the synthesis condition of the polyhydric alcohol. Nevertheless, the preparation of alloy materials at present has two problems in the reduction process, and because of the inconsistent nature of the oxophilic, different metals are reduced and separated out at different temperatures, and heterogeneous bimetallic catalysts are formed: different metals are easy to nucleate independently or after one metal ion is reduced to nucleate, the other metal ion is reduced and covers the surface of the seed crystal, and therefore the nano-particle with the core-shell structure is obtained. Another problem is that one of the metals modifies the oxide support while the other nucleates alone due to the fact that the strength of the interaction between the two metals and the oxide support is not uniform and is even weaker than the degree of interaction between the metals.
Disclosure of Invention
The invention aims to provide a method for regulating and controlling the interaction between nano metal particles and a gel type oxide carrier.
The invention utilizes composite precipitant with different compositions to adjust the acidity of aqueous solution of mixed metal salt, thereby preparing soft agglomerated gel type oxide carrier, and then uses composite reducer with different compositions to directly reduce metal ions on site at corresponding temperature and load the metal ions on the oxide carrier. Because the aggregation states of the metal and the carrier can be modulated by the composite precipitator and the composite reducing agent with different compositions, and the reduction load of the metal ions at different temperatures or the same temperature is controlled, the single metal and the alloy material with controllable size and controllable interaction degree can be prepared.
The invention comprises the following steps:
1) preparing composite precipitating agents with different proportions at different temperatures for adjusting the pH value of an aqueous solution of mixed metal salts to form gel, filtering and washing redundant precipitating agents, using acetylacetone to replace hydroxyl groups or other polar groups in the gel and dividing water generated by replacement reaction, so that metal ions can uniformly fall on a carrier when loading is convenient, and obtaining a surface acetylacetone soft agglomerated gel carrier after surface nonpolar modification is completed;
2) simultaneously introducing nonpolar metal ion acetylacetone salt and composite reducing agents with different proportions into the turbid liquid obtained in the step 1), adding a dispersing agent, heating to react at different temperatures, reducing noble metal nano particles on site to be positioned on a carrier until the nano particles are positioned on the surface of the carrier, cooling and settling, and separating organic auxiliary agents and solvents after settling to obtain a precipitate;
3) calcining the precipitate obtained in the step 2) at different temperatures to prepare single metal and alloy materials with controllable sizes and controllable interaction degrees of metal and carriers;
in step 1), the metal salt may be selected from chlorides or nitrates of zirconium, aluminum, or other metal such as alkaline earth or rare earth modified ions, alkaline earth metals may be used: one of magnesium, calcium, strontium, barium, etc.; the rare earth modified ions comprise one of lanthanum, cerium, neodymium, samarium, europium, gadolinium and the like; the pH value of the aqueous solution of the mixed metal salt can be adjusted by adopting an alkaline aqueous solution formed by compounding at least one compound of ammonia water, ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like;
the filtration washing can be washed by deionized water by adopting a decantation method or a suction filtration method;
the displacement of hydroxyl or other polar groups in the gel by acetylacetone and the removal of water generated by the displacement reaction can be carried out under stirring and heating, the heating temperature can be selected from 100-300 ℃, water is removed, and the water is removed by reduced pressure distillation or flowing gas;
the carrier is an oxide or composite oxide carrier formed by zirconia and alumina.
In step 2), the in-situ reduced noble metal nanoparticles can be prepared by dissolving acetylacetone salts of ruthenium, rhodium, palladium, iridium, platinum and silver in an acetylacetone solution, adding the above soft aggregated gel carrier with the surface acetylacetone in step 1) into a suspension formed by dispersing the carrier into acetylacetone, and adding a composite reducing agent under stirring, wherein the reducing agent can be prepared by compounding at least one compound of p- (o) diphenol, tert-butyl-p- (o) diphenol, di-tert-butyl-p- (o) diphenol and the like with at least one compound of oleylamine, ethylenediamine, ethanolamine, diethanolamine and the like to form an anisole or n-octylether solution;
the dispersant can adopt at least one of long-chain fatty acid, cetyl trimethyl ammonium bromide and the like; the temperature rise reaction can be maintained at 100-400 ℃ for 40 min; the organic auxiliary solvent can be separated by filtration or centrifugation after the sedimentation.
In the step 3), the calcination can be performed in different atmospheres, and the calcination temperature can be 280-1000 ℃.
The invention adopts an oxide or composite oxide carrier formed by zirconium oxide and aluminum oxide, wherein the oxide carrier forms a composite precipitator by hydroxide or carbonate in the stage of preparing a precursor so that an aqueous solution of mixed metal salt forms gel, nano metal particles are alloy nano particles synthesized in situ, and metal particles are coordinated by hydrophobic protective agent molecules and can form a stable dispersion system in a non-polar solvent.
The metal nano particles of the invention adopt a method of on-site synthesis, under the premise of maintaining the aggregation state of the metal particles, nonpolar ions are positioned on a nonpolar carrier, the interaction between the metal particles and the carrier which are filled in different ways is reduced by a reducing agent, the effect of controlling the degree of the interaction is achieved, and the uniform distribution of the nano metal particles in an oxide carrier is realized and the corresponding reaction characteristics are maintained.
The invention utilizes different proportions of composite precipitant, precipitation temperature and aging time to cause different aggregation states of the carrier, thereby controlling the interaction degree of the metal and the carrier; the composite reducing agents with different proportions are used for controlling the reduction process, so that different metal ions tend to carry out reduction loading at the same or different temperatures, and then the single metal and alloy materials with controllable interaction degree are prepared. The invention firstly utilizes composite precipitants with different compositions to adjust the acidity of aqueous solution of mixed metal salt, thereby preparing a soft agglomerated gel type oxide carrier, and then uses composite reducing agents with different compositions to directly reduce metal ions on site at corresponding temperature and load the metal ions on the oxide carrier. Because the aggregation states of the metal and the carrier can be modulated by the composite precipitator and the composite reducing agent with different compositions, and the reduction load of the metal ions at different temperatures or the same temperature is controlled, the invention can prepare the single metal and the alloy material with controllable size and controllable interaction degree.
Drawings
FIG. 1 is one of the electron microscope characterization graphs (20 nm scale, 10n average particle size) of the precipitating agent and reducing agent with different proportions for controlling the size of the single metal catalyst.
FIG. 2 is a second electron micrograph (50 nm on scale, 25nm average particle size) of the single metal catalyst controlled by the precipitant and the reductant at different ratios.
FIG. 3 is a third electron microscopic representation (scale 100nm, average particle size 50nm) of the size of the single metal catalyst controlled by precipitant and reductant in different proportions.
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
The invention utilizes composite precipitant with different compositions to adjust the acidity of aqueous solution of mixed metal salt, thereby preparing soft agglomerated gel type oxide carrier, and then uses composite reducer with different compositions to directly reduce metal ions on site at corresponding temperature and load the metal ions on the oxide carrier. Because the aggregation states of the metal and the carrier can be modulated by the composite precipitator and the composite reducing agent with different compositions, and the reduction load of the metal ions at different temperatures or the same temperature is controlled, the single metal and the alloy material with controllable size and controllable interaction degree can be prepared.
The embodiment of the invention comprises the following steps:
1. preparing composite precipitant with different proportions at different temperatures for regulating the pH of the aqueous solution of the mixed metal salt to form gel, filtering and washing the redundant precipitant, using acetylacetone to replace hydroxyl groups or other groups in the gel, enabling metal ions to uniformly fall on a carrier when the gel is conveniently loaded, and obtaining the surface acetylacetone soft agglomerated gel carrier after the surface nonpolar transformation is finished. The metal salt concerned can be selected from chlorides or nitrates of zirconium, aluminium, and the other alkaline earth or rare earth modified ions can be alkaline earth metals: magnesium, calcium, strontium, barium, light rare earth elements: one of lanthanum, cerium, neodymium, samarium, europium and gadolinium is introduced into the mixed ionic solution in the form of nitrate, the pH value of the solution can be adjusted by adopting an alkaline aqueous solution formed by compounding at least one compound of ammonia water, ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like, and the filtering and washing method can be washed by deionized water by adopting a decantation method or a suction filtration method; the displacement of the hydroxyl groups in the gel with acetylacetone and the removal of the water formed by the displacement reaction can be carried out with stirring and heating, optionally at temperatures between 100 ℃ and 300 ℃ with removal of water and removal by distillation under reduced pressure or entrainment with flowing gas.
2. And (2) performing acetylacetone modification on metal ions to prepare a solution, introducing nonpolar metal ions and composite reducing agents in different proportions into the solution obtained in the step 1), adding a dispersing agent into the solution, performing temperature rise reaction at different temperatures, performing on-site reduction on the solution to a carrier until the nanoparticles are completely placed on the surface of the carrier, cooling and settling, and removing a solvent layer to obtain a precipitate. The in-situ synthesized noble metal nano-particles can be prepared by dissolving acetylacetone salts of ruthenium, rhodium, palladium, iridium, platinum and silver in acetylacetone solution, adding the solution into the solution, adding a composite reducing agent under stirring, wherein the reducing agent can be at least one compound selected from p- (o) -benzenediol, tert-butyl-p- (o) -benzenediol, di-tert-butyl-p- (o) -diphenol and the like and at least one compound selected from oleylamine, ethylenediamine, ethanolamine and diethanolamine to prepare anisole or n-octyl ether solution, the dispersing agent can be at least one selected from long-chain fatty acid and hexadecyl trimethyl ammonium bromide, the reaction is maintained at 100-400 ℃ for 40min, and the organic auxiliary solvent is separated after sedimentation and a standing filtration or suction filtration method can be adopted.
3. Calcining the precipitate obtained in the step 2) at different temperatures and in different atmospheres, wherein the calcining temperature ranges from 280 ℃ to 1000 ℃, and the single metal and alloy materials with controllable sizes and controllable interaction degrees of metal and carriers are prepared.
Specific examples are given below.
Example 1
Adjusting the pH value of a mixed metal salt solution containing 14g of zirconium chloride and 4.6g of zirconyl nitrate to 8 by using a composite precipitator with the molar ratio of ammonia water to ammonium bicarbonate of 2: 8, filtering and washing redundant precipitator and chloride ions by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of n-octyl ether solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of ruthenium acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding 0.1g of di-tert-butyl hydroquinone, 0.1g of hexadecyl trimethyl ammonium bromide and 0.05g of oleylamine into 30mL of n-octyl ether solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dropwise adding the two solutions into the mixed metal ion basic carbonate gel suspension, stirring at room temperature for 1h, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
And settling the obtained suspension, centrifugally separating out precipitate, introducing air into a tubular furnace, calcining at 400 ℃ for 3 hours, and naturally cooling to room temperature after calcining.
Example 2
Adjusting the pH value of a mixed metal salt solution containing 14g of zirconium chloride and 4.6g of cerium nitrate to 9 by using a composite precipitator with the molar ratio of ammonia water to ammonium carbonate being 1: 9, filtering and washing redundant precipitator and chloride ions by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of n-octyl ether solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of rhodium acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding catechol, 0.1g of oleic acid and 0.05g of diethanolamine into 30mL of n-octyl ether solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dropwise adding the two solutions into the mixed metal ion basic carbonate gel suspension, stirring for 1h at room temperature, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
And settling the obtained suspension, filtering to separate out precipitate, introducing air into a tubular furnace, calcining at 700 ℃ for 1h, and quenching to room temperature after calcining.
Example 3
Adjusting the pH value of a mixed metal salt solution containing 14g of zirconyl chloride and 1.2g of neodymium nitrate to 8 by using a composite precipitator with the molar ratio of sodium hydroxide to ammonium bicarbonate of 1: 9, filtering and washing redundant precipitator and chloride ions by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of n-octyl ether solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of iridium acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding 0.1g of hydroquinone, 0.1g of hexadecyl trimethyl ammonium bromide and 0.05g of oleylamine into 30mL of n-octyl ether solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dropwise adding the two solutions into the mixed metal ion basic carbonate gel suspension, stirring at room temperature for 1h, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
And settling and filtering the obtained suspension to separate out precipitate, calcining the precipitate in a muffle furnace at 450 ℃ for 2 hours, and naturally cooling to room temperature after the calcination is finished.
Example 4
Adjusting the pH value of a mixed metal salt solution containing 14g of zirconium nitrate and 1.0g of samarium nitrate to 8 by using a composite precipitator with the molar ratio of potassium hydroxide to ammonium carbonate being 2: 8, filtering and washing redundant precipitator by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of anisole solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of platinum acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding 0.3g of di-tert-butylhydroquinone and 0.05g of ethanolamine into 30mL of anisole solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dripping the two solutions into the mixed metal ion basic carbonate gel suspension, stirring for 1h at room temperature, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
And settling the obtained suspension, centrifugally separating out precipitate, calcining in a muffle furnace at 450 ℃ for 2h, and naturally cooling to room temperature after calcining.
Example 5
Adjusting the pH value of a mixed metal salt solution containing 14g of aluminum nitrate and 0.5g of magnesium nitrate to 7 by using a composite precipitator with the molar ratio of sodium hydroxide to ammonium bicarbonate of 2: 8, filtering and washing redundant precipitator by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of n-octyl ether solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of palladium acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding di-tert-butyl hydroquinone, 0.1g of lauric acid and 0.05g of ethylenediamine into 30mL of n-octyl ether solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dripping the two solutions into the mixed metal ion basic carbonate gel suspension together, stirring for 1h at room temperature, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
And settling the obtained suspension, centrifugally separating out precipitate, introducing oxygen into a tubular furnace, calcining at 400 ℃ for 3 hours, and naturally cooling to room temperature after calcining.
Example 6
Adjusting the pH value of a mixed metal salt solution containing 14g of aluminum nitrate and 0.8g of strontium nitrate to 9 by using a composite precipitator with the molar ratio of ammonia water to sodium bicarbonate being 5: 5, filtering and washing redundant precipitator by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of anisole solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of silver acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding 0.21g of di-tert-butyl catechol and 0.1g of hexadecyl trimethyl ammonium bromide into 30mL of anisole solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dripping the two solutions into the mixed metal ion basic carbonate gel suspension together, stirring for 1h at room temperature, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
And settling the obtained suspension, centrifugally separating out precipitate, calcining in a muffle furnace at 450 ℃ for 2h, and naturally cooling to room temperature after calcining.
Example 7
Adjusting the pH value of a mixed metal salt solution containing 14g of zirconyl nitrate and 2.8g of lanthanum nitrate to 8 by using a composite precipitator with the molar ratio of potassium hydroxide to ammonium bicarbonate of 1: 9, filtering and washing redundant precipitator by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of anisole solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of palladium acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding 0.15g of di-tert-butyl hydroquinone and 0.05g of oleylamine into 30mL of anisole solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dripping the two solutions into the mixed metal ion basic carbonate gel suspension, stirring for 1h at room temperature, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
The suspension obtained above was settled and centrifuged to separate the precipitate, and simulated air (21 vol.% O) was introduced into the tube furnace2/79vol.％N2) Calcining at 650 ℃ for 3h, and after calcining, maintaining the purging atmosphere to naturally reduce to room temperature.
Example 8
Adjusting the pH value of a mixed metal salt solution containing 14g of zirconyl nitrate and 4.6g of cerium nitrate to 8 by using a composite precipitator with the molar ratio of ammonia water to ammonium bicarbonate of 2: 8, filtering and washing redundant precipitator by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of n-octyl ether solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of platinum acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding 0.1g of catechol and 0.05g of oleylamine into 30mL of n-octyl ether solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dripping the two solutions into the mixed metal ion basic carbonate gel suspension, stirring for 1h at room temperature, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
The suspension obtained above was settled and centrifuged to separate the precipitate, and simulated air (21 vol.% O) was introduced into the tube furnace2/79vol.％N2) Calcining at 850 deg.C for 3h, and maintaining purging atmosphere to naturally cool to room temperature.
Example 9
Adjusting the pH value of a mixed metal salt solution containing 14g of zirconyl chloride and 1.6g of barium nitrate to 7 by using a composite precipitator with the molar ratio of ammonia water to sodium bicarbonate of 5: 5, filtering and washing redundant precipitator and chloride ions by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of n-octyl ether solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of palladium acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding 0.1g of tert-butyl catechol, 0.1g of hexadecyl trimethyl ammonium bromide and 0.05g of oleylamine into 30mL of n-octyl ether solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dropwise adding the two solutions into the mixed metal ion basic carbonate gel suspension, stirring at room temperature for 1h, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
And centrifugally separating and drying the obtained suspension, heating the suspension to 700 ℃ in a muffle furnace, calcining the suspension for 2 hours, and naturally cooling the suspension to room temperature after constant temperature treatment.
Example 10
Adjusting the pH value of a mixed metal salt solution containing 14g of zirconium chloride and 1.2g of gadolinium nitrate to 9 by using a composite precipitator with the molar ratio of ammonia water to ammonium carbonate being 1: 9, filtering and washing redundant precipitator and chloride ions by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of n-octyl ether solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of silver acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding 0.1g of tert-butyl hydroquinone, 0.1g of hexadecyl trimethyl ammonium bromide and 0.05g of oleylamine into 30mL of n-octyl ether solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dropwise adding the two solutions into the mixed metal ion basic carbonate gel suspension, stirring at room temperature for 1h, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
And (3) spray-drying the obtained suspension, introducing inert atmosphere into a tubular furnace, heating to 1000 ℃ for calcining for 2h, maintaining the inert atmosphere at 5 ℃/min, cooling to 150 ℃, and naturally cooling to room temperature.
Example 11
Adjusting the pH value of a mixed metal salt solution containing 14g of zirconyl nitrate and 1.6g of cerium nitrate to 10 by using a composite precipitator with the molar ratio of ammonia water to ammonium bicarbonate of 2: 8, filtering and washing redundant precipitator by adopting normal pressure, adding the prepared mixed ion basic carbonate gel into 100mL of acetylacetone solution, stirring overnight at room temperature, adding 150mL of n-octyl ether solution, stirring for 1h at normal temperature, and heating to 150 ℃ to evaporate redundant acetylacetone.
Adding 0.29g of ruthenium acetylacetonate into 20mL of acetylacetone solution, performing ultrasonic treatment for 30min, adding 0.1g of hydroquinone, 0.1g of hexadecyl trimethyl ammonium bromide and 0.05g of oleylamine into 30mL of n-octyl ether solution, performing ultrasonic treatment for 30min, uniformly mixing the two solutions, dropwise adding the two solutions into the mixed metal ion basic carbonate gel suspension, stirring at room temperature for 1h, heating to 200 ℃, refluxing for 2h, cooling to room temperature, and standing for precipitation.
The suspension obtained above was settled and centrifuged to separate the precipitate, and a low hydrogen reducing gas (3 vol.% H) was introduced into the tube furnace2/97vol.％N2) Calcining at 280 deg.C for 3 hr, and maintaining reducing atmosphere to naturally cool to room temperature.
The electron microscope characterization images of the sizes of the single metal catalysts controlled by the precipitating agent and the reducing agent in different proportions are shown in figures 1-3.
The invention adopts comprehensive measures such as composite carrier, surface acetylacetone, diphenol gradual reducing agent, multi-atmosphere calcination and the like to perform multilevel intervention regulation and control on the interaction degree between the noble metal nanoparticles and the gel type oxide carrier. On the premise of maintaining the original supported nano system, the control of the population form of the metal component is realized, so that the structural micro-assembly type composite material with multiple advantages of a dispersive nano metal system and a supported metal micro-area structure is prepared.
Claims (10)
1. The method for regulating and controlling the interaction between the nano metal particles and the gel type oxide carrier is characterized by comprising the following steps of:
1) preparing composite precipitating agents with different proportions at different temperatures for adjusting the pH value of an aqueous solution of mixed metal salts to form gel, filtering and washing redundant precipitating agents, using acetylacetone to replace hydroxyl groups or other polar groups in the gel and dividing water generated by replacement reaction, so that metal ions can be uniformly positioned on a carrier when loading is convenient, and dispersing surface acetylacetone soft clustered gel carriers into acetylacetone to form suspension after surface nonpolar modification is completed;
2) simultaneously introducing nonpolar metal ion acetylacetone salt and composite reducing agents with different proportions into the turbid liquid obtained in the step 1), adding a dispersing agent, heating to react at different temperatures, reducing noble metal nano particles on site to be positioned on a carrier until the nano particles are positioned on the surface of the carrier, cooling and settling, and separating organic auxiliary agents and solvents after settling to obtain a precipitate;
3) calcining the precipitate obtained in the step 2) at different temperatures to prepare the single metal or alloy material with controllable size and controllable interaction degree of the metal and the carrier.
2. The method for controlling the interaction between the nano-metal particles and the gel-type oxide support according to claim 1, wherein in step 1), the metal salt is selected from chlorides or nitrates of zirconium and aluminum, or metals thereof such as alkaline earth metal or rare earth modified ions, and the alkaline earth metal can be one of magnesium, calcium, strontium and barium; the rare earth modified ions comprise one of lanthanum, cerium, neodymium, samarium, europium and gadolinium; the pH value of the aqueous solution of the mixed metal salt can be adjusted by adopting an alkaline aqueous solution formed by compounding at least one compound of ammonia water, ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
3. The method for controlling the interaction between the nano-metal particles and the gel-type oxide support according to claim 1, wherein in the step 1), the filtration washing is performed by using deionized water through decantation or suction filtration.
4. The method for controlling the interaction between the metal nanoparticles and the gel-type oxide support according to claim 1, wherein in step 1), the substitution of the hydroxyl group or other polar groups in the gel with acetylacetone and the removal of the water generated by the substitution reaction are performed under stirring and heating at a temperature of 100 to 300 ℃ to remove water and carry out the water by vacuum distillation or flowing gas.
5. The method for controlling interaction between nano-metal particles and a gel-type oxide support according to claim 1, wherein in the step 1), the support is an oxide formed of zirconia, alumina, or a composite oxide support.
6. The method for controlling the interaction between the metal nanoparticles and the gel-type oxide support according to claim 1, wherein in step 2), the in-situ reduction of the noble metal nanoparticles is performed by dissolving acetylacetone salts of ruthenium, rhodium, palladium, iridium, platinum and silver in acetylacetone solution, adding the solution into the suspension in step 1), and adding a composite reducing agent under stirring, wherein the composite reducing agent is a solution prepared by mixing at least one compound selected from p- (o) -benzenediol, t-butyl-p- (o) -benzenediol and di-t-butyl-p- (o) -diphenol with at least one selected from oleylamine, ethylenediamine, ethanolamine and diethanolamine to form anisole or n-octylether solution.
7. The method for controlling interaction between nano-metal particles and a gel-type oxide support according to claim 1, wherein in the step 2), at least one of a long chain fatty acid and cetyltrimethylammonium bromide is used as the dispersant.
8. The method for controlling the interaction between the metal nanoparticles and the gel-type oxide support according to claim 1, wherein in the step 2), the temperature-raising reaction is maintained at 100 to 400 ℃ for 40 min.
9. The method for controlling interaction between nano-metal particles and a gel-type oxide support according to claim 1, wherein in step 2), the organic auxiliary and the solvent are separated after the precipitation by filtration or centrifugation.
10. The method for controlling the interaction between the nano-metal particles and the gel-type oxide support according to claim 1, wherein in the step 3), the calcination is performed under different atmospheres, and the calcination temperature is 280 to 1000 ℃.
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