CN101767018A - Loading type Pd base metal nanometer cluster catalyst, preparing method and applications thereof - Google Patents
Loading type Pd base metal nanometer cluster catalyst, preparing method and applications thereof Download PDFInfo
- Publication number
- CN101767018A CN101767018A CN200910076223A CN200910076223A CN101767018A CN 101767018 A CN101767018 A CN 101767018A CN 200910076223 A CN200910076223 A CN 200910076223A CN 200910076223 A CN200910076223 A CN 200910076223A CN 101767018 A CN101767018 A CN 101767018A
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- China
- Prior art keywords
- metal
- catalyst
- water
- iron oxide
- compound
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 248
- 239000010953 base metal Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000011068 loading method Methods 0.000 title claims abstract description 42
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052751 metal Inorganic materials 0.000 claims abstract description 76
- 239000002184 metal Substances 0.000 claims abstract description 76
- 239000002245 particle Substances 0.000 claims abstract description 69
- 239000011164 primary particle Substances 0.000 claims abstract description 33
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 18
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 15
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 14
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 161
- 229910001566 austenite Inorganic materials 0.000 claims description 94
- 230000009467 reduction Effects 0.000 claims description 79
- -1 basic salt compound Chemical class 0.000 claims description 65
- 239000000084 colloidal system Substances 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000002105 nanoparticle Substances 0.000 claims description 50
- 239000007864 aqueous solution Substances 0.000 claims description 47
- 229910052763 palladium Inorganic materials 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 39
- 239000002082 metal nanoparticle Substances 0.000 claims description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 27
- 229910000859 α-Fe Inorganic materials 0.000 claims description 27
- 238000001465 metallisation Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 229960004887 ferric hydroxide Drugs 0.000 claims description 25
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 24
- 229910052723 transition metal Inorganic materials 0.000 claims description 23
- 150000002736 metal compounds Chemical class 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 150000003624 transition metals Chemical class 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 17
- 150000001298 alcohols Chemical class 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000013049 sediment Substances 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 150000001340 alkali metals Chemical class 0.000 claims description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 230000001476 alcoholic effect Effects 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 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 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229940015043 glyoxal Drugs 0.000 claims description 6
- 150000001261 hydroxy acids Chemical class 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 3
- 238000001935 peptisation Methods 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 8
- 238000002156 mixing Methods 0.000 claims 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 238000006298 dechlorination reaction Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 16
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 150000004982 aromatic amines Chemical class 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000001491 aromatic compounds Chemical class 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 242
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 87
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 81
- 238000002360 preparation method Methods 0.000 description 79
- 238000006243 chemical reaction Methods 0.000 description 67
- 238000006722 reduction reaction Methods 0.000 description 67
- 230000003197 catalytic effect Effects 0.000 description 57
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 28
- 239000001257 hydrogen Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 26
- 238000006555 catalytic reaction Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- 238000013019 agitation Methods 0.000 description 21
- 239000010948 rhodium Substances 0.000 description 21
- 230000036571 hydration Effects 0.000 description 20
- 238000006703 hydration reaction Methods 0.000 description 20
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 19
- 230000005291 magnetic effect Effects 0.000 description 18
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 16
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 238000012512 characterization method Methods 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 12
- 238000007086 side reaction Methods 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 239000012453 solvate Substances 0.000 description 9
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- UFWLOPUHRFEZLX-UHFFFAOYSA-N 1-chloro-3-nitro-5-phenylbenzene Chemical group ClC=1C=C(C=C(C1)C1=CC=CC=C1)[N+](=O)[O-] UFWLOPUHRFEZLX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000007659 chevron notched beam method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 208000030208 low-grade fever Diseases 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 4
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- 238000005660 chlorination reaction Methods 0.000 description 2
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- QIFZRTGHATXWQI-UHFFFAOYSA-N 1-chloro-2-nitro-3-phenylbenzene Chemical group [O-][N+](=O)C1=C(Cl)C=CC=C1C1=CC=CC=C1 QIFZRTGHATXWQI-UHFFFAOYSA-N 0.000 description 1
- FIQBDKFALPAHOK-UHFFFAOYSA-N 1-chloro-2-nitro-4-phenylbenzene Chemical group C1=C(Cl)C([N+](=O)[O-])=CC(C=2C=CC=CC=2)=C1 FIQBDKFALPAHOK-UHFFFAOYSA-N 0.000 description 1
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 1
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- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
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- 229910020203 CeO Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 1
- 244000208060 Lawsonia inermis Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
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- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
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- 125000001246 bromo group Chemical group Br* 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
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- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- OMTOXKFYSXJLQI-UHFFFAOYSA-M lithium ethane-1,2-diol hydroxide Chemical compound [Li+].[OH-].OCCO OMTOXKFYSXJLQI-UHFFFAOYSA-M 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical compound INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 description 1
- AXNCVDQWNPJQOM-UHFFFAOYSA-N n-triethoxysilylpropan-1-amine Chemical compound CCCN[Si](OCC)(OCC)OCC AXNCVDQWNPJQOM-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention discloses a loading type Pd base metal nanometer cluster catalyst, a preparing method and applications thereof. The catalyst comprises Pd metal nanometer particles of 1-25nm, or bimetal or polymetal nanometer particles containing Pd, and ferric oxide nanometer particles, wherein the ferric oxide nanometer particle is used as the carrier, has the primary particle size of 5-200nm, and has the general formula of FeyOx; the bimetal or polymetal nanometer particles are selected from one or a plurality of Pt, Rh, Ru, Os, Ir and Re; when the metal nanometer particles are Pd nanometer particles, x/y is greater than 1, but is smaller than 4/3, or is greater than 4/3, but is smaller than 3/2; and when the metal nanometer particles are bimetal or polymetal nanometer particles containing Pd, x/y is greater than 1, but is smaller than or equal to 3/2. The catalyst has excellent activity, selectivity and stability on the selective hydrogenating synthesis chlorinated arylamine of the chlorinated aromatic compounds, solves the problems of hydrogenolysis and dechlorination of products in the process of the Pd catalyst catalyzing the chlorinated aromatic compounds to hydrogenate to prepare the chlorinated arylamine, and has important industrial application values.
Description
Technical field
The present invention relates to loading type Pd base metal nanometer cluster catalyst and preparation method thereof and application.
Background technology
Iron oxide particularly magnetic oxide (comprises γ-Fe
2O
3And Fe
3O
4) have special electronics, magnetics and an optical property.Metal is carried on magnetic oxide or contains on the carrier of magnetic oxide and can realize that the magnetic of catalyst separates.
Hara etc. are with the γ-Fe of hydroxyapatite parcel
2O
3Be carrier, prepared Pd-hydroxyapatite-γ-Fe
2O
3Catalyst.But a series of chloride aromatics hydrogenolysis dechlorinations apace such as this catalyst catalysis chlorobenzene, chloro aminobenzen, chloroacetophenone, be the very high dechlorination catalyst of activity (T.Hara, et al., Green Chem., 2007,9,1246-1251).In addition, applying external magnetic field can separate catalyst and reuse easily from reaction system.
Wang etc. use 3-Propylamino triethoxysilane (APTS) to prepared Fe
3O
4Nano particle (average grain diameter is 8nm) is modified, thereby at Fe
3O
4The outer clad that forms APTS hydrolysis condensation product (APS), the coordination that utilizes its surperficial amido and Pd ion again on carrier, has prepared Pd-APS-Fe with the Pd reduce deposition
3O
4Catalyst, and investigated this catalyst in acrylic acid and the iodobenzene coupling reaction catalytic activity and stability (Z.F.Wang, et al., Chem.Eng.J.2005,113,27-34).
Seino etc. are light source with the gamma-radiation, and under the situation that polyvinyl alcohol (PVA) exists, Au, Pt that the PVA that original position is produced with metal ion in the photoreduction aqueous solution protects and Pd metal particle are deposited on and are purchased γ-Fe
2O
3(average grain diameter 26nm) and Fe
3O
4On (average grain diameter 100nm) carrier, prepared one metalloid-PVA-ferric oxide nano compound magnetic material (S.Seino, et al., Scripta Materialia 2004,51,467-472).Iron oxide concentration is smaller among this preparation method, about 1g/l, thereby preparation efficiency is not too high.In addition, the Pt of part PVA protection and Pd nano particle can not oxidized iron absorption.The existence of PVA makes the interaction of iron oxide and noble metal nano particles and the regulating effect of catalytic performance is restricted.
The reaction that chloro aromatic nitro compound selective hydration prepares the chloro aromatic amine is an important reaction in many organic dyestuff, spices, herbicide, pesticide, plant growth regulator, anticorrisive agent and the pharmaceutical industries building-up process.Yet the hydrogenolysis dechlorination side reaction of reactant and product is difficult to avoid when using this type of reaction of conventional metals catalyst.When having other to scold electron group in the product, this problem is even more serious, and (US 6034276 for R.J.Maleski, et al.; R.J.Maleski, et al., WO 0056698).Therefore suppress the dechlorination side reaction is to improve one of important goal of this synthetic method always.
In chloro aromatic nitro compound selective hydrogenation, Pt is catalyst based to have than higher activity and selectivity, thereby is studied widely and use.In recent years, the inventor is a structural motif with " non-protection type " metallic colloid, developed Pt/ magnetic ferric oxide nano complex catalyst, this catalyst prepares this class chemical reaction of halo aniline to the halogenated nitrobenzene selective hydration and shows excellent catalytic activity and selectivity (Wang Yuan etc., Chinese invention patent, ZL 200410086479.1; Y.Wang, et al., J.Catal.2005,229,114-118; Y.Wang, et al., J.Catal.2008,255,335-342).Reach at 100% o'clock at the halogenated nitrobenzene conversion ratio, activated Pt/ γ-Fe
2O
3Nano-complex all is higher than 99.9% to the selectivity of chloro, bromo and iodo aniline, has thoroughly solved the difficult problem of product hydrogenolysis-dehalogenation element in this type of reaction of platinum based catalyst catalysis.
Compare with Pt is catalyst based, the catalyst based catalytic selectivity to this type of reaction of Pd is lower, dechlorination side reaction serious (J.R.Kosak, in Catalysisi in Organic Syntheses; Academic Press:New York, 1980; Pp.107-117).The catalyst based advantage of Pd is that it has advantages of high catalytic activity usually, and price is far below platinum class catalyst.Existing researcher has adopted multiple diverse ways to suppress hydrogenolysis dechlorination on the Pd catalyst.
People such as Kratky (V.Krathy, et al., Appl.Catal.A:Gereral 2002,235,225-231) use the styrene of sulfonation and divinylbenzene copolymerized macromolecule to be preparing carriers loading type Pd catalyst, compare with traditional Pd/C catalyst, this catalyst shows good catalytic activity and selectivity in adjacent chlorine, hydrogenation to chlorine, m-chloro-nitrobenzene (CNBs).Yet this catalyst can not suppress the hydrogenolysis of C-Cl key in the chloro aminobenzen (CANs) fully, and the selectivity of its catalysis parachloronitrobenzene hydrogenation system parachloroanilinum is about 90%.
(J.Mol.Catal.A 2008,282 for C.Y.Xi, et al., 80-84) for reducing the hydrogenolysis dechlorination side reaction of o-chloraniline on the Pd/C catalyst, at the CO of 8-13MPa for people such as Xi
2Carry out this reaction in the supercritical fluid media, make the selectivity of o-chloraniline reach 94%, obviously, this technology requires very high to equipment, and still can't block the dechlorination side reaction.
Adding metal cation modified dose in reaction system also is a kind of method that suppresses the dechlorination side reaction.(J.Mol.Catal.A 2006,260 for Q.Xu, et al., 299-305) at PVP-Pd/ γ-Al for people such as Xu and Li
2O
3Add solubility Sn in the catalyst p-CNB hydrogenation system
4+Salt makes the selectivity of p-CAN reach 96.6%.Add a large amount of Sn
4+Though can further improve the selectivity of p-CAN, also can cause the remarkable decline of catalyst activity, make intermediate product be difficult to thorough hydrogenation, simultaneously a large amount of dressing agents also can cause difficulty to the product separation.
In sum, create new Pd class catalyst, when keeping high catalytic activity, suppress the dechlorination side reaction of products such as chloro aminobenzen fully and produce high-purity chloro for arylamine, be challenging research topic and good application prospects is arranged to realize efficient hydrogenation.
Summary of the invention
The purpose of this invention is to provide a class loading type Pd metal nanometre cluster Catalysts and its preparation method and an application.
Loading type Pd base metal nanometer cluster catalyst provided by the invention is by the Pd metal nanoparticle or contain the bimetallic of Pd or multi-metal nanoparticles and be Fe as the general formula of carrier
yO
xFerric oxide nano particles constitute;
Wherein, contain in the bimetallic or multi-metal nanoparticles of Pd, bimetallic or many metals are selected from any one or a few among Pt, Rh, Ru, Os, Ir and the Re.
Above-mentioned catalyst specifically can be following two class catalyst: 1) by the Pd metal nanoparticle be Fe as the general formula of carrier
yO
xThe loading type Pd base metal nanometer cluster catalyst that constitutes of ferric oxide nano particles;
Wherein, 1＜x/y＜4/3 or 4/3＜x/y＜3/2.
2) be Fe by the bimetallic that contains Pd or multi-metal nanoparticles and as the general formula of carrier
yO
xThe loading type Pd base metal nanometer cluster catalyst that constitutes of ferric oxide nano particles;
Wherein, contain in the bimetallic or multi-metal nanoparticles of Pd, described bimetallic or many metals are selected from any one or a few among Pt, Rh, Ru, Os, Ir and the Re; 1＜x/y≤3/2.
In the above-mentioned loading type Pd base metal nanometer cluster catalyst, Pd metal nanoparticle or contain the bimetallic of Pd or the particle diameter of multi-metal nanoparticles is 1-25nm, described general formula as carrier is Fe
yO
xThe particle diameter of primary particle of ferric oxide nano particles be 5-200nm.Pd metal nanoparticle or contain the bimetallic of Pd or the quality percentage composition of multi-metal nanoparticles is 0.1-15%.
Loading type Pd base metal nanometer cluster catalyst provided by the invention can be prepared according to following three kinds of methods:
First method comprises the steps:
1) preparation Pd based metallization compound colloid: the soluble-salt of Pd or the soluble-salt or the acid of acid or Pd and at least a other transition metal are dissolved in alcohol or water or the pure water mixed solution, and being mixed with concentration is the transistion metal compound solution of 0.01-100g/L; The alcoholic solution of the solubility hydroxide of alkali metal or alkaline-earth metal or carbonate or bicarbonate or the aqueous solution or pure water mixed solution are mixed under the 243-373K temperature with above-mentioned transistion metal compound solution, the gained mixed liquor is handled at 243-373K, obtained Pd based metallization compound colloid; Described alcohol is monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol or its mixture of 1-4 for the carbon atom number; The mol ratio of the salt of the hydroxide of described alkali metal or alkaline-earth metal, carbonate or bicarbonate and described transition metal or acid is 1-20: 1;
2) preparation ferric hydroxide colloid: in the aqueous solution of molysite, add aqueous slkali, regulate pH to 4-12, generate ferric hydroxide precipitate, then ferric hydroxide precipitate is joined peptization in the peptizing agent, obtain the ferric hydroxide colloid that concentration is 1-300g/L, described peptizing agent is ferric chloride solution, iron nitrate solution or hydrochloric acid;
3) Pd based metallization compound colloid and step 2 that step 1) is prepared) prepared ferric hydroxide colloid mixes in proportion, to wherein adding one or more reducing agents, heat treatment 1-200h under the 303-473K temperature separates the gained sediment then, washing, drying or oxidation obtain with γ-Fe
2O
3And Fe
3O
4Loading type Pd base metal nanometer cluster catalyst for carrier;
4) with step 3) prepared with γ-Fe
2O
3And Fe
3O
4For the loading type Pd base metal nanometer cluster catalyst of carrier reduces processing, promptly make loading type Pd base metal nanometer cluster catalyst provided by the invention.The reducing agent that uses during described reduction is handled comprises H
2, NaBH
4, KBH
4, hydrazine hydrate, the medium that uses during described reduction is handled comprises organic solvent, water, H
2And H
2Mixed atmosphere with inert gas.The temperature that described reduction is handled is 300-523K.
Among this preparation method, described other transition metal salt of step 1) or the acid that contains described transition metal are generally and contain Pt, Rh, Ru, Ir, Os, the salt of Re or contain the acid of these metals.Described Pd based metallization compound comprises Pd Base Metal oxide, hydroxide, basic salt compound or its mixture.
Step 2) concentration of described iron salt solutions is 0.01-4mol/L; Described alkali is ammoniacal liquor (mass percent concentration is 1-25%), potassium hydroxide, NaOH, lithium hydroxide, tetramethyl ammonium hydroxide etc.; The temperature of described generation ferric hydroxide precipitate is 278-373K; Described peptizing agent concentration is 0.01-2mol/L; The temperature of described peptization is 278-373K.
In the described Pd based metallization of the step 3) compound colloid in Pd based metallization compound and the ferric hydroxide colloid mass ratio of iron hydroxide be 1: 6-1250; Described reducing agent comprises H
2, the carbon atom number is monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, formaldehyde, glycolic acid, hydroxy acid sodium, glyoxal, the oxalic acid of 1-4; Described heat treatment method comprises solvent heat treatment, conventional heat treated or microwave heating treatment, and baking temperature is 278-523K, and oxidizing temperature is for being 313-523K, and this oxidation step is oxidation in the mist of air or oxygen and inert gas.
The time that the described reduction of step 4) is handled is 1 minute-100 hours.
Second method comprises the steps:
1) preparation Pd based metallization compound colloid: the soluble-salt of Pd or the soluble-salt or the acid of acid or Pd and at least a other transition metal are dissolved in alcohol or water or the pure water mixed solution, and being mixed with concentration is the transistion metal compound solution of 0.01-100g/L; The alcoholic solution of the solubility hydroxide of alkali metal or alkaline-earth metal or carbonate or bicarbonate or the aqueous solution or pure water mixed solution are mixed under the 243-373K temperature with above-mentioned transistion metal compound solution, the gained mixed liquor is handled at 243-373K, obtained Pd based metallization compound colloid; Described alcohol is monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol or its mixture of 1-4 for the carbon atom number; The mol ratio of the salt of the hydroxide of described alkali metal or alkaline-earth metal, carbonate or bicarbonate and described transition metal or acid is 1-20: 1;
2) dispersing iron oxide carrier: with specific area is 20-210m
2The iron oxide of/g is scattered in the mixed liquor of water or organic solvent that can be water-soluble or described organic solvent and water, and stirring or ultrasonic dispersion make iron oxide suspension, and wherein the quality of the iron oxide that is disperseed in every liter of suspension is 0.1-1000g; Described iron oxide comprises magnetic oxide and α-Fe
2O
3, described magnetic oxide is Fe
3O
4, γ-Fe
2O
3And Fe
yO
xIn one or more any combination, wherein Fe
yO
xIn, 1＜x/y＜1.5;
3) preparation loading type Pd base metal nanometer cluster catalyst intermediate: Pd based metallization compound colloid and step 2 that step 1) is prepared) prepared iron oxide carrier suspension stir or ultrasonic condition under mix in proportion, to wherein adding one or more reducing agents, heat treatment 1-200h under the 303-473K temperature then, with the gained sediment through separate, after the washing under the 278-523K condition drying promptly make described with γ-Fe
2O
3, α-Fe
2O
3And Fe
3O
4Loading type Pd base metal nanometer cluster catalyst for carrier.
4) with step 3) prepared with γ-Fe
2O
3, α-Fe
2O
3And Fe
3O
4For the loading type Pd base metal nanometer cluster catalyst of carrier reduces processing, promptly make loading type Pd base metal nanometer cluster catalyst provided by the invention.The reducing agent that uses during described reduction is handled comprises H
2, NaBH
4, KBH
4, hydrazine hydrate, the medium that uses during described reduction is handled comprises organic solvent, water, H
2And H
2Mixed atmosphere with inert gas.The temperature that described reduction is handled is 300-523K.
Among this preparation method, described other transition metal salt of step 1) or the acid that contains described transition metal are generally and contain Pt, Rh, Ru, Ir, Os, the salt of Re or contain the acid of these metals.Described Pd based metallization compound comprises Pd Base Metal oxide, hydroxide, basic salt compound or its mixture.
Step 2) the water-soluble organic solvent of described energy is monohydric alcohol, dihydroxylic alcohols or the trihydroxylic alcohol of 1-4 for the carbon atom number, acetone, oxolane and N, any combination of one or more in the dinethylformamide.
In the described Pd based metallization of the step 3) compound colloid in Pd based metallization compound and the carrier suspension mass ratio of iron oxide carrier be 1: 5-900; Described reducing agent comprises H
2, the carbon atom number is monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, formaldehyde, glycolic acid, hydroxy acid sodium, glyoxal, the oxalic acid of 1-4; Described heat treatment method comprises solvent heat treatment, heating reflow treatment or microwave heating treatment.
The time that the described reduction of step 4) is handled is 1 minute-100 hours.
The third method comprises the steps:
1) soluble-salt of Pd or the soluble-salt or the acid of acid or Pd and at least a other transition metal are dissolved in alcohol or water or the pure water mixed solution, being mixed with concentration is the transistion metal compound solution of 0.01-100g/L;
2) dispersing iron oxide carrier: with specific area is 20-210m
2The iron oxide of/g is scattered in the mixed liquor of water or organic solvent that can be water-soluble or described organic solvent and water, and stirring or ultrasonic dispersion make iron oxide suspension, and wherein the quality of the iron oxide that is disperseed in every liter of suspension is 0.1-1000g; Described iron oxide comprises magnetic oxide and α-Fe
2O
3, described magnetic oxide is Fe
3O
4, γ-Fe
2O
3And Fe
yO
xIn one or more any combination, wherein Fe
yO
xIn, 1＜x/y＜1.5;
3) transistion metal compound solution and the step 2 that step 1) is prepared) prepared iron oxide carrier suspension stir or ultrasonic condition under mix in proportion, then the alcoholic solution of the solubility hydroxide of alkali metal or alkaline-earth metal or carbonate or bicarbonate or the aqueous solution or pure water mixed solution are joined in the said mixture, after continuing stirring or ultrasonic processing 0-200h under the 273-473K temperature, isolate sediment and washing, the gained sediment is scattered in the mixed liquor of water or organic solvent that can be water-soluble or described organic solvent and water, to wherein adding one or more reducing agents, heat treatment 1-200h under the 303-473K temperature then, sediment in the system is separated, washing, drying promptly makes described with γ-Fe under the 278-523K condition
2O
3, α-Fe
2O
3And Fe
3O
4Loading type Pd base metal nanometer cluster catalyst for carrier.The mol ratio of the salt of the transition metal in the hydroxide of described alkali metal or alkaline-earth metal, carbonate or bicarbonate and the described transistion metal compound solution or acid is 1-100: 1.
4) with step 3) prepared with γ-Fe
2O
3, α-Fe
2O
3And Fe
3O
4For the loading type Pd base metal nanometer cluster catalyst of carrier reduces processing, promptly make loading type Pd base metal nanometer cluster catalyst provided by the invention.The reducing agent that uses during described reduction is handled comprises H
2, NaBH
4, KBH
4, hydrazine hydrate, the medium that uses during described reduction is handled comprises organic solvent, water, H
2And H
2With the mixed atmosphere of inert gas, the temperature that described reduction is handled is 300-523K.
In this preparation method, described other transition metal salt of step 1) or the acid that contains described transition metal are generally and contain Pt, Rh, Ru, Ir, Os, the salt of Re or contain the acid of these metals.
Step 2) the water-soluble organic solvent of described energy is monohydric alcohol, dihydroxylic alcohols or the trihydroxylic alcohol of 1-4 for the carbon atom number, acetone, oxolane and N, any combination of one or more in the dinethylformamide.
The mass ratio of carrier is 1 in transition metal in the described transistion metal compound of step 3) and the carrier suspension: 5-1000; The water-soluble organic solvent of described energy is monohydric alcohol, dihydroxylic alcohols or the trihydroxylic alcohol of 1-4 for the carbon atom number, acetone, oxolane and N, any combination of one or more in the dinethylformamide; Described reducing agent comprises H
2, the carbon atom number is monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, the NaBH of 1-4
4, KBH
4, hydrazine hydrate, formaldehyde, glycolic acid, hydroxy acid sodium, glyoxal, oxalic acid; Described heat treatment method comprises solvent heat treatment, conventional heat treated or microwave heating treatment.
The time that the described reduction of step 4) is handled is 1 minute-100 hours.
In addition, the application of Pd base metal nanometer cluster catalyst provided by the invention aspect the synthetic chloro arylamine reaction of catalysis chloro aromatic nitro compound selective hydration also belongs to protection scope of the present invention.
Experiment showed, that loading type Pd base metal nanometer cluster catalyst of the present invention has excellent catalytic performance, thereby be with a wide range of applications.Pd base metal nanometer cluster catalyst of the present invention has very high activity and selectivity to synthetic this course of industrialization of chloro arylamine of chloro aromatic nitro compound selective hydration, has excellent stability simultaneously.More common chloro aromatic nitro compound, as chloronitrobenzene, chloro dinitro benzene or chloro nitrobiphenyl etc., all can adopt of the present invention year type Pd base metal nanometer cluster catalyst to carry out the nitro-catalytic hydrogenation reaction, and side reaction such as product catalytic hydrogenolysis dechlorination can not occur.For example, by the inventive method preparation contain palladium 0.25wt.% by Pd nano particle and the Fe that is in the partial reduction state
3O
4(be designated as Pd/Fe
3O
4-load type metal the nanocluster catalyst that PR) constitutes shows the catalytic activity and the selectivity of excellence in catalysis p-CNB hydrogenation process.When p-CNB and intermediate product transformed fully, the selectivity of p-CAN was greater than 99%, and prolonged the reaction time and do not observe p-CAN and optionally descend.Again for example, use the Pd/Fe that contains palladium 1wt.% of the present invention
3O
4-PR load type metal nanocluster catalyst catalysis 5-chloro-3-nitrobiphenyl selective hydrogenation, when reaction-ure conversion-age reached 100%, the selectivity of 5-chloro-3-amido biphenyl was greater than 99%, and the dechlorination process of product can be suppressed fully.In using Pd base metal nanometer cluster catalyst catalysis chloro aromatic nitro compound hydrogenation of the present invention, can adopt the moderate hydrogen atmospheric pressure to make to be swift in response and carry out up hill and dale.Generally, the hydrogenation condition is: temperature, 273-353K; Pressure, 0.1-10MPa; Solvent can adopt alcohol or other organic solvent (for example, oxolane (THF)), N, dinethylformamide (DMF), toluene etc.).Reaction can adopt after finishing modes such as magnetic separates, centrifugal or filtration with catalyst and reactants separate, reuses.
Loading type Pd base metal nanometer cluster catalyst provided by the invention has excellent catalytic performance, thereby is with a wide range of applications.
In these chloro aromatic nitro compounds, the representational chloro aromatic nitro compound that is structure suc as formula I, among the formula I, X=H, R, COOR, RO, Cl, NO
2, or NH
2, wherein R is C
1To C
4The saturated alkane base.
(formula I)
Perhaps, general structure is suc as formula the chloro aromatic nitro compound of II,
In the formula II general structure, X, X ', Y=H, R, COOR, RO, Cl, Z=H, NO
2, or NH
2, wherein R is C
1To C
4The saturated alkane base.
The present invention utilizes the catalytic action of Pd base metal nanometer cluster to make the iron oxide carrier by partial reduction, utilization is in the catalytic performance of the special interaction regulation and control catalyst of iron oxide carrier under the partial reduction state and Pd base metal nanometer cluster, under the prerequisite that keeps high catalytic activity, solved the difficult problem of product hydrogenolysis dechlorination in the synthetic chloro arylamine reaction of the catalyst based catalysis chloro of Pd aromatic nitro compound selective hydration, thoroughly suppressed the hydrogenolysis dechlorination side reaction of product, can be used for the efficient production high-purity chloro for arylamine.Pd base metal nanometer cluster catalyst of the present invention shows excellent properties in this type of reaction basic reason is that the Pd base metal nanometer cluster directly contacts with the iron oxide carrier of partial reduction and metal-carrier interaction of the uniqueness that produces.Under the contrast, Pd-hydroxyapatite-γ-Fe
2O
3Catalyst but has very high catalytic activity to the hydrogenolysis dechlorination of chloro aminobenzen.In addition, the inventor studies show that without reduction handle with γ-Fe
2O
3, α-Fe
2O
3And Fe
3O
4Then can't thoroughly suppress the hydrogenolysis dechlorination side reaction of product when the above-mentioned reaction of catalysis for the loading type Pd base metal nanometer cluster catalyst of carrier.Hence one can see that, and the catalyst that loading type Pd base metal nanometer cluster catalyst of the present invention and forefathers' report contain Pd and iron oxide has essential distinction.
When adopting magnetic oxide to be carrier in the Pd base metal nanometer cluster catalyst of the present invention, catalyst has good magnetic, can implement the separation of catalyst by applying magnetic field.
Adopt the Pd base metal nanometer cluster/ferric oxide catalyst of synthetic method provided by the invention preparation, have the metal dispersity height, characteristics such as catalytic activity is good, catalytic selectivity and excellent in stability.This method has good universality simultaneously, and selecting carbon or other oxide is carrier, as CNT, activated carbon, carbon black, α-Fe
2O
3, Al
2O
3, SiO
2, TiO
2, SnO
2, CeO
2, ZrO
2, ZnO etc., can prepare corresponding loading type Pd base metal nanometer cluster catalyst.
Description of drawings
Fig. 1 is a palladium metal compound nano particle electromicroscopic photograph in the palladium metal compound colloid;
Fig. 2 is the Pd/ γ-Fe of embodiment 1 preparation
2O
3Load type metal nanocluster catalyst electromicroscopic photograph;
Fig. 3 is the Pd/ γ-Fe of embodiment 1 preparation
2O
3-PR load type metal nanocluster catalyst electromicroscopic photograph;
Fig. 4 is the Pd/ γ-Fe of embodiment 1 preparation
2O
3With Pd/ γ-Fe
2O
3The Fe 2p XPS spectrum figure of-PR load type metal nanocluster catalyst.
Fig. 5 is the Pd/ γ-Fe of embodiment 1 preparation
2O
3With Pd/ γ-Fe
2O
3The XRD spectra of-PR load type metal nanocluster catalyst.
The specific embodiment
In order to be described more specifically the present invention, now provide some embodiment, but content involved in the present invention also not only is confined to these embodiment.Method therefor is conventional method if no special instructions among the following embodiment.
Embodiment 1: preparation is by Pd nano-cluster and the γ-Fe that is in the partial reduction state
2O
3Catalyst (Pd:3wt.%) that constitutes and catalytic performance test thereof.(wt.% is the quality percentage composition, down together)
One, Preparation of Catalyst
The sodium hydrate aqueous solution of getting 10ml concentration and be 0.20mol/L joins in the palladium chloride aqueous solution of 20ml (2.82 * 10 under vigorous stirring
-2Mol/L), stir 1min under the room temperature and make palladium metal compound colloid, the content of Pd is 2.00g/L in the colloid.The electromicroscopic photograph of palladium metal compound nano particle as shown in Figure 1 in the palladium metal compound colloid.Transmission electron microscope (TEM) the analysis showed that the average grain diameter of palladium metal compound nano particle is 2nm, and particle diameter is distributed as 1-3nm.
Preparing mass percent concentration respectively is 10% ammoniacal liquor and 4% iron chloride (0.25mol/L) aqueous solution, gets an amount of ammonia spirit and slowly is added drop-wise in the 100ml ferric chloride solution, finally controls pH about 7.5, aging 5min.The ferric hydroxide precipitate that generates is filtered, washed to there not being Cl
-Ion, filter cake pulled an oar in the 60ml1.2% ferric chloride solution and under 323K the low-grade fever slurries, make ferric hydroxide colloid, it is standby to be cooled to room temperature.
The above-mentioned palladium metal compound of 30ml colloid under agitation is added drop-wise to above-mentioned Fe (OH)
3In the colloid, obtain the rufous complex sol, behind the stirring 0.5h, 90ml ethylene glycol is injected above-mentioned complex sol, continue to stir 0.5h, at N
2Protection down is heated to backflow with system, behind the backflow 2h to wherein adding 1ml NaOOCCH
2The OH aqueous solution (0.5g/ml) continues backflow 20h, and the black precipitate that generates is separated with externally-applied magnetic field, and washing in 353K oxidation drying 20h, promptly makes Pd/ γ-Fe in air
2O
3The load type metal nanocluster catalyst.Pd/ γ-Fe
2O
3The electromicroscopic photograph of load type metal nanocluster catalyst as shown in Figure 2, tem study shows, prepared Pd/ γ-Fe
2O
3The average grain diameter of Pd metal nanoparticle is 13nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 7-21nm, carrier γ-Fe
2O
3The average grain diameter of primary particle is 16nm, and particle diameter is distributed as 8-25nm.
0.6g is pressed the Pd/ γ-Fe of said process preparation
2O
3Be scattered in the methyl alcohol, place autoclave, at 303K, 1.0MPa Hydrogen Vapor Pressure reduction is down handled 3h, henna Pd/ γ-Fe in this process
2O
3Change the solid of black into.X-ray photoelectron power spectrum (XPS) analyzes (see figure 4) and X-ray diffraction (XRD) analysis (see figure 5) shows, the gained catalyst is by Pd nano particle and the γ-Fe that is in the partial reduction state
2O
3Nano particle constitutes and (is designated as Pd/ γ-Fe
2O
3-PR).Tem study shows, prepared Pd/ γ-Fe
2O
3The average grain diameter of Pd metal nanoparticle is 13nm in the-PR catalyst, and particle diameter is distributed as 7-21nm, is in the γ-Fe of partial reduction state
2O
3(γ-Fe
2O
3-PR) average grain diameter of primary particle is 16nm, particle diameter is distributed as 8-25nm.Icp analysis shows that the content of Pd in the prepared catalyst is 3wt.%, and O/Fe is 1.45 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 117m
2/ g.
Two, Pd/ γ-Fe
2O
3The reaction of catalyst p-chloronitrobenzene
Add in reactor that step 1 prepares among this embodiment of 0.015g Pd/ γ-Fe
2O
3Catalyst to wherein adding the methanol solution contain 1mmol p-chloronitrobenzene, under agitation, is 303K in temperature, and Hydrogen Vapor Pressure is to implement catalytic hydrogenation under the condition of 0.1MPa, the product gas chromatographic analysis, and experimental result is listed in table 1.
Table 1Pd/ γ-Fe
2O
3The hydrogenation of load type metal nanocluster catalyst catalysis p-chloronitrobenzene
Reaction condition: methanol solvate, 20ml; Temperature, 303K; Pressure, 0.1MPa; The p-chloronitrobenzene, 1mmol.
The above results shows that this catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Three, Pd/ γ-Fe
2O
3The test of-PR catalyst p-chloronitrobenzene reactivity worth
(1) be to implement catalytic hydrogenation reaction under the 0.1MPa condition at hydrogen pressure
Pd/ γ-the Fe that in reactor, adds step 1 preparation among the 0.015g embodiment 1
2O
3-PR catalyst to wherein adding the methanol solution contain 1mmol p-chloronitrobenzene, under agitation, is 303K in temperature, and Hydrogen Vapor Pressure is to implement catalytic hydrogenation under the condition of 0.1MPa, the product gas chromatographic analysis, and experimental result is listed in table 1.
(2) be respectively under 2MPa and the 4MPa condition at hydrogen pressure and implement catalytic hydrogenation reaction
Pd/ γ-the Fe that in autoclave, adds the step 1 preparation of 0.015g embodiment 1
2O
3-PR catalyst to wherein adding the methanol solution contain the p-chloronitrobenzene, under agitation, is 303K in temperature, and Hydrogen Vapor Pressure is respectively 2.0, implement catalytic hydrogenation under the condition of 4.0MPa, the product gas chromatographic analysis, and experimental result is listed in table 2.
Table 2Pd/ γ-Fe
2O
3-PR load type metal nanocluster catalyst catalysis p-chloronitrobenzene hydrogenation performance
Reaction condition: methanol solvate, 20ml; Catalyst amount, 0.015g; Temperature, 303K.
The above results shows that this catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.The dechlorination side reaction of product p-chloro aminobenzen is suppressed fully, shows Pd/ γ-Fe
2O
3The catalytic selectivity of-PR is much better than Pd/ γ-Fe
2O
3
Embodiment 2: preparation is by Pd nano-cluster and the Fe that is in the partial reduction state
3O
4Catalyst (Pd:0.25wt.%) that constitutes and catalytic performance test thereof.
One, Preparation of Catalyst
The 1g palladium bichloride is scattered in the 300ml ethylene glycol, adds 1ml hydrochloric acid (30wt.%), be mixed with the ethylene glycol solution (1.88 * 10 of palladium chloric acid
-2Mol/L).The palladium bichloride ethylene glycol solution and the NaOH aqueous solution (0.25mol/L) of preparation newly are cooled to 263K.Get the NaOH aqueous solution that 4.5ml fully cools off and under agitation join in the ethylene glycol solution of 12ml palladium bichloride, continue to stir 120min under the 273K temperature, obtain palladium metal compound colloid, the content of Pd is 1.45g/L in the colloid.
Fe
3O
4Nano structural material prepares by the following method: 10g six Ferric Chloride Hydrateds and 10g urea are dissolved in the 60ml ethylene glycol; be warming up to 468K backflow 30min; after being cooled to room temperature; with sedimentation and filtration, the washing that generates; with the gained filter cake after the 333K vacuum drying; under nitrogen protection,, be cooled to room temperature, promptly make Fe in 673K heat treatment 3h
3O
4Nano structural material.Tem study shows, this Fe
3O
4The primary particle average grain diameter of material is 25nm, and particle diameter is distributed as 10-50nm.
Get the palladium metal compound colloid of the above-mentioned preparation of 3.4ml, under stirring fast, it is added drop-wise to the Fe that 50ml is dispersed with the above-mentioned preparation of 2.0g
3O
4In the ethylene glycol of nano structural material, at room temperature continue to stir 1h after, put it into the stirred in water bath reaction 5h of 303K, then with warming-in-water to 313K, continue to stop heating behind the stirring reaction 1h.Apply magnetic field precipitation is separated from dispersion, washing in the dry 12h of 353K, promptly makes Pd/Fe in air
3O
4The load type metal nanocluster catalyst.Tem study shows, prepared Pd/Fe
3O
4The average grain diameter of Pd metal nanometre cluster is 3nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 1-6nm, Fe
3O
4The primary particle average grain diameter is 25nm, and particle diameter is distributed as 10-50nm.
0.4g is pressed the Pd/Fe of said process preparation
3O
4Be scattered in the methyl alcohol, place autoclave, at 303K, 2.0MPa Hydrogen Vapor Pressure reduction is down handled 5h.XPS and XRD analysis show that the gained catalyst is by Pd nano particle and the Fe that is in the partial reduction state
3O
4Nano particle constitutes and (is designated as Pd/Fe
3O
4-PR).Tem study shows, prepared Pd/Fe
3O
4The average grain diameter of Pd metal nanoparticle is 3nm in the-PR catalyst, and particle diameter is distributed as 1-6nm, is in the Fe of partial reduction state
3O
4(Fe
3O
4-PR) average grain diameter of primary particle is 25nm, particle diameter is distributed as 10-50nm.Icp analysis shows that the content of Pd in the prepared catalyst is 0.25wt.%, and O/Fe is 1.31 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 40m
2/ g.
Two, catalyst p-chloronitrobenzene hydrogenation
1) 4.0MPa hydrogen pressure reaction down
The Pd/Fe that in autoclave, adds the step 1 preparation of 0.05g embodiment 2
3O
4-PR catalyst to wherein adding the methanol solution contain 6mmol p-chloronitrobenzene, under agitation, is 4.0MPa in Hydrogen Vapor Pressure, and temperature is to implement catalytic hydrogenation under the condition of 303K, and the product gas chromatographic analysis behind the 180min is answered in negate.
Pd/Fe under the above-mentioned reaction condition
3O
4-PR load type metal nanocluster catalyst catalytic activity and catalytic selectivity result are as shown in table 3.
Table 3Pd/Fe
3O
4-PR load type metal nanocluster catalyst catalysis p-chloronitrobenzene hydrogenation performance
Reaction condition: methanol solvate, 20ml; Pressure, 4.0MPa; The p-chloronitrobenzene, 6mmol; Temperature, 303K.
2) stability test of catalyst
The Pd/Fe that in autoclave, adds the step 1 preparation of 0.05g embodiment 2
3O
4--the PR catalyst to wherein adding the methanol solution contain the 11.7mmolp-chloronitrobenzene, under agitation, is 4.0MPa in Hydrogen Vapor Pressure, and temperature is to implement catalytic hydrogenation, the product gas chromatographic analysis under the condition of 303K.After reaction finishes, utilize externally-applied magnetic field that catalyst is separated with reaction system, with reusing after the methanol wash, under the situation that reactant p-chloronitrobenzene transforms fully, catalyst is reused seven times, and as calculated as can be known, the total turnover number in this catalysis experiment is 70,000.
The above results shows that this catalyst shows excellent catalytic selectivity and stability in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Embodiment 3: preparation is by Pd nano-cluster and the γ-Fe that is in the partial reduction state
2O
3The catalyst (Pd:15wt.%) that constitutes
Method by step 1 among the embodiment 1 prepares palladium metal compound colloid.
Prepare the KOH aqueous solution of 2% (quality percentage composition) and the iron nitrate aqueous solution of 0.17mol/L respectively, get an amount of KOH aqueous solution and under agitation slowly be added drop-wise in the 150ml iron nitrate solution, finally control pH about 4, aging 10min.With the ferric hydroxide precipitate that generates filter, washing, filter cake pulled an oar in 30ml1% watery hydrochloric acid and under 333K the low-grade fever slurries, make ferric hydroxide colloid, it is standby to be cooled to room temperature.
The above-mentioned freshly prepd palladium metal compound colloid drops of 176.6ml is added in the above-mentioned ferric hydroxide colloid, again to the mixed solution that wherein injects 100ml ethylene glycol and glycerine (ethylene glycol/glycerin volume ratio=4: 1), put into autoclave and heat-treat, treatment temperature 473K, time 60h.With sedimentation and filtration, the washing that generates, in air,, promptly make Pd/ γ-Fe in the dry 24h of 333K
2O
3The load type metal nanocluster catalyst.Tem study shows, prepared Pd/ γ-Fe
2O
3The average grain diameter of Pd metal nanometre cluster is 14nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 6-28nm, carrier γ-Fe
2O
3The primary particle average grain diameter is 20nm, and particle diameter is distributed as 8-27nm.
0.5g is pressed the Pd/ γ-Fe of said process preparation
2O
3Be scattered in the water, to wherein adding the NaBH that 10ml concentration is 0.5M
4The aqueous solution is handled 2h in the 303K reduction.XPS and XRD analysis show that the gained catalyst is by Pd nano particle and the γ-Fe that is in the partial reduction state
2O
3Nano particle constitutes and (is designated as Pd/ γ-Fe
2O
3-PR).Tem study shows, prepared Pd/ γ-Fe
2O
3The average grain diameter of Pd metal nanoparticle is 14nm in the-PR catalyst, and particle diameter is distributed as 6-28nm, is in the γ-Fe of partial reduction state
2O
3(γ-Fe
2O
3-PR) average grain diameter of primary particle is 20nm, particle diameter is distributed as 8-27nm.Icp analysis shows that the content of Pd in the prepared catalyst is 15wt.%, and O/Fe is 1.42 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 96m
2/ g.
This catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Embodiment 4: preparation is by Pd nano-cluster and the Fe that is in the partial reduction state
3O
4Catalyst (Pd:1wt.%) that constitutes and catalytic performance test thereof
One, Preparation of Catalyst
Compound concentration is 1.41 * 10
-2The palladium chloride aqueous solution of mol/L.
Method by step 1 among the embodiment 2 prepares Fe
3O
4Nano structural material.
Get the palladium chloride aqueous solution of the above-mentioned preparation of 3.3ml, under stirring fast, it is added drop-wise to the Fe that 50ml is dispersed with the above-mentioned preparation of 0.5g
3O
4In the water of nano structural material, after at room temperature stirring 1h, adding 3ml concentration is the aqueous sodium carbonate of 0.20mol/L, continues to stir 2h, apply magnetic field with precipitate and separate, washing is scattered in the 50ml ethylene glycol again, is warming up to 353K then, stopping heating behind the reaction 5h under this temperature, sediment is separated, washes, in air,, promptly obtain Pd/Fe in the dry 10h of 373K
3O
4The load type metal nanocluster catalyst.Tem study shows, prepared Pd/Fe
3O
4The average grain diameter of Pd metal nanometre cluster is 2nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 1-5nm, Fe
3O
4The primary particle average grain diameter is 25nm, and particle diameter is distributed as 10-50nm.
0.6g is pressed the Pd/Fe of said process preparation
3O
4The load type metal nanocluster catalyst is scattered in the methyl alcohol, places autoclave, and at 303K, 2.0MPa Hydrogen Vapor Pressure reduction is down handled 8h.XPS and XRD analysis show that the gained catalyst is by Pd nano particle and the Fe that is in the partial reduction state
3O
4Nano particle constitutes and (is designated as Pd/Fe
3O
4-PR).Tem study shows, prepared Pd/Fe
3O
4The average grain diameter of Pd metal nanoparticle is 2nm in the-PR catalyst, and particle diameter is distributed as 1-5nm, is in the Fe of partial reduction state
3O
4(Fe
3O
4-PR) average grain diameter of primary particle is 25nm, particle diameter is distributed as 10-50nm.Icp analysis shows that the content of Pd in the prepared catalyst is 1wt.%, and O/Fe is 1.30 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 38m
2/ g.
Two, Pd/Fe
3O
4Load type metal nanocluster catalyst (Pd:1wt.%) catalysis p-chloronitrobenzene hydrogenation performance
The Pd/Fe that the step 1 of this embodiment of adding 0.045g prepares in reactor
3O
4Catalyst to wherein adding the methanol solution contain 1mmol p-chloronitrobenzene, under agitation, is 0.1MPa in Hydrogen Vapor Pressure, and temperature is to implement catalytic hydrogenation under the condition of 303K, and the product gas chromatographic analysis behind the 120min is answered in negate.
Pd/Fe under the above-mentioned reaction condition
3O
4Load type metal nanocluster catalyst catalytic activity and catalytic selectivity result are as shown in table 4.
Table 4Pd/Fe
3O
4The hydrogenation of load type metal nanocluster catalyst catalysis p-chloronitrobenzene
Reaction condition: methanol solvate, 20ml; Temperature, 303K; Pressure, 0.1MPa; The p-chloronitrobenzene, 1mmol.
The above results shows that this catalyst shows excellent catalytic performance in the reaction of p-chloronitrobenzene hydrogenation.
Three, Pd/Fe
3O
4-PR catalyst 4-chloro-3-nitrobiphenyl hydrogenation performance
The Pd/Fe that the step 1 of this embodiment of adding 0.01g prepares in autoclave
3O
4-PR catalyst, to wherein adding the tetrahydrofuran solution that contains 10mmol 5-chloro-3-nitrobiphenyl, under agitation, be 5.0MPa in Hydrogen Vapor Pressure, temperature is to implement catalytic hydrogenation under the condition of 303K, and the product gas chromatographic analysis behind the 100min is answered in negate.
Pd/Fe under the above-mentioned reaction condition
3O
4-PR load type metal nanocluster catalyst catalytic activity and catalytic selectivity result are as shown in table 5.
Table 5Pd/Fe
3O
4The hydrogenation of-PR load type metal nanocluster catalyst catalysis 5-chloro-3-nitrobiphenyl
Reaction condition: tetrahydrofuran solvent, 20ml; Temperature, 303K; Pressure, 5.0MPa; 5-chloro-3-nitrobiphenyl, 10mmol.
The above results shows that this catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.In summary, the Pd/Fe that handles without reduction
3O
4The catalytic selectivity of catalyst is undesirable.
Embodiment 5: preparation is by Pd nano-cluster and the γ-Fe that is in the partial reduction state
2O
3Catalyst (Pd:0.5wt.%) that constitutes and catalytic performance test thereof
One, Preparation of Catalyst
Compound concentration is 2.82 * 10
-2The aqueous solution of mol/L palladium bichloride.
γ-Fe
2O
3Available from Alfa Aesar.Tem study shows, this γ-Fe
2O
3The primary particle average grain diameter be 25nm, particle diameter is distributed as 5-50nm.
Get the palladium chloride aqueous solution of the above-mentioned preparation of 8.4ml, under stirring fast, it is added drop-wise to the Fe that 50ml is dispersed with the above-mentioned preparation of 5.0g
3O
4In the ethanol of nano structural material, at room temperature stir 1h after, to wherein adding the sodium bicarbonate aqueous solution that 20ml concentration is 0.5mol/L, after continuing to stir 2h, apply magnetic field with precipitate and separate, washing, and be scattered in again in the 50ml glycol water (glycol/water volume ratio=1: 1), be warming up to 373K and keep 3h, finish back cooling of reaction applies magnetic field and will precipitate from reaction system and separate, and washes, in 473K vacuum drying 20h, promptly make Pd/ γ-Fe
2O
3The load type metal nanocluster catalyst.Tem study shows, prepared Pd/ γ-Fe
2O
3The average grain diameter of Pd metal nanoparticle is 3nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 2-6nm, γ-Fe
2O
3The primary particle average grain diameter be 25nm, particle diameter is distributed as 5-50nm.
1.0g is pressed the Pd/ γ-Fe of said process preparation
2O
3Be scattered in the ethanol,, handle 1h in the 353K reduction to wherein adding the 10ml hydrazine hydrate.XPS and XRD analysis show that the gained catalyst is by Pd nano particle and the γ-Fe that is in the partial reduction state
2O
3Nano particle constitutes and (is designated as Pd/ γ-Fe
2O
3-PR).Tem study shows, prepared Pd/ γ-Fe
2O
3The average grain diameter of Pd metal nanoparticle is 3nm in the-PR catalyst, and particle diameter is distributed as 2-6nm, is in the γ-Fe of partial reduction state
2O
3(γ-Fe
2O
3-PR) average grain diameter of primary particle is 25nm, particle diameter is distributed as 5-50nm.Icp analysis shows that the content of Pd in the prepared catalyst is 0.5wt.%, and O/Fe is 1.40 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 44m
2/ g.
Two, catalyst m-chloronitrobenzene hydrogenation
Pd/ γ-the Fe that in autoclave, adds the step 1 preparation of 0.1g embodiment 5
2O
3-PR catalyst to wherein adding the methanol solution contain 1mmol m-chloronitrobenzene, under agitation, is 2.0MPa in Hydrogen Vapor Pressure, and temperature is to implement catalytic hydrogenation under the condition of 303K, and the product gas chromatographic analysis behind the 40min is answered in negate.
Pd/ γ-Fe under the above-mentioned reaction condition
2O
3-PR catalytic activity and catalytic selectivity result are as shown in table 6.
Table 6Pd/ γ-Fe
2O
3The hydrogenation of-PR load type metal nanocluster catalyst catalysis m-chloronitrobenzene
Reaction condition: methanol solvate, 20ml; Temperature, 303K; Pressure, 2.0MPa; The m-chloronitrobenzene, 1mmol.
The above results shows that this catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Embodiment 6: preparation is by Pd-Pt bimetal nano bunch (wherein Pd: Pt (mol ratio)=3: 1) and the Fe that is in the partial reduction state
3O
4Catalyst (Pd-Pt:1wt.%) that constitutes and catalytic performance test thereof
One, Preparation of Catalyst
Prepare the aqueous solution (1.90 * 10 of palladium bichloride respectively
-2Mol/L) and the ethylene glycol solution (1.90 * 10 of chloroplatinic acid
-2Mol/L), and be to mix at 3: 1 by volume, be mixed with palladium bichloride-chloroplatinic acid glycol water it.
Fe
3O
4Nano structural material is pressed (J.H.Fendler described in the document, et al., Preparation of particulatemono-and multilayers from surfactant-stabilized, nanosized magnetite crystallites.J.Phys.Chem.1994,98,4506-4510) method preparation.3g Iron dichloride tetrahydrate and 6g six Ferric Chloride Hydrateds are dissolved in the 30ml water, under stirring fast,, generate black precipitate to wherein adding 12.5ml concentrated ammonia liquor (14.8mol/L), centrifugation, precipitation in the 423K vacuum drying, is cooled to room temperature after washing, promptly make Fe
3O
4Nano structural material.Tem study shows, this Fe
3O
4The primary particle average grain diameter of material is 13nm, and particle diameter is distributed as 5-20nm.
Get the palladium bichloride-chloroplatinic acid glycol water of the above-mentioned preparation of 8.2ml, under stirring fast, it is added drop-wise to the Fe that 50ml is dispersed with the above-mentioned preparation of 2.0g
3O
4In the ethylene glycol of nano structural material, after at room temperature continuing to stir 0.5h, to wherein adding the NaOH aqueous solution that 37ml concentration is 0.5M, after continuing stirring reaction 2h, apply magnetic field sediment is separated, washing, in hydrogen atmosphere, handle 6h, promptly make Pd-Pt/Fe in the 373K reduction
3O
4The load type double-metal nanocluster catalyst.Tem study shows, prepared Pd-Pt/Fe
3O
4The average grain diameter of Pd-Pt bimetal nano particle is 4nm in the load type double-metal nanocluster catalyst, and particle diameter is distributed as 1-7nm, Fe
3O
4The primary particle average grain diameter be 13nm, particle diameter is distributed as 5-20nm.
0.4g is pressed the Pd-Pt/Fe of said process preparation
3O
4Be scattered in the methyl alcohol, place autoclave, at 313K, 1.0MPa Hydrogen Vapor Pressure reduction is down handled 3h.XPS and XRD analysis show that the gained catalyst is by Pd-Pt bimetal nano particle and the Fe that is in the partial reduction state
3O
4Nano particle constitutes and (is designated as Pd-Pt/Fe
3O
4-PR).Tem study shows, prepared Pd-Pt/Fe
3O
4The average grain diameter of Pd-Pt bimetal nano particle is 4nm in the-PR catalyst, and particle diameter is distributed as 1-7nm, is in the Fe of partial reduction state
3O
4(Fe
3O
4-PR) average grain diameter of primary particle is 13nm, particle diameter is distributed as 5-20nm.Icp analysis shows that the content of Pd-Pt in the prepared catalyst is 1wt.%, and O/Fe is 1.29 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 180m
2/ g.
Two, Pd-Pt/Fe
3O
4Load type double-metal nanocluster catalyst (wherein Pd: Pt (mol ratio)=3: 1, and Pd-Pt:1wt.%) catalysis 3, the performance test of 4-dichloro-hydrogenation of chloronitrobenzene
The Pd-Pt/Fe that in autoclave, adds the step 1 preparation of 0.06g embodiment 6
3O
4The load type double-metal nanocluster catalyst contains 1mmol 3, the methanol solution of 4-dichloro-nitrobenzene to wherein adding, under agitation, in Hydrogen Vapor Pressure is 0.5MPa, and temperature is to implement catalytic hydrogenation under the condition of 303K, and the product gas chromatographic analysis behind the 90min is answered in negate.
Pd-Pt/Fe under the above-mentioned reaction condition
3O
4Load type double-metal nanocluster catalyst catalytic activity and catalytic selectivity result are as shown in table 7.
Table 7Pd-Pt/Fe
3O
4Load type double-metal nanocluster catalyst catalysis 3, the hydrogenation of 4-dichloro-nitrobenzene
Reaction condition: methanol solvate, 20ml; Temperature, 303K; Pressure, 0.5MPa; 3,4-dichloro-nitrobenzene, 1mmol.
The above results shows that this catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Three, Pd-Pt/Fe
3O
4-PR catalyst 3, the performance test of 4-dichloro-hydrogenation of chloronitrobenzene
The Pd-Pt/Fe that in reactor, adds the step 1 preparation of 0.05g embodiment 6
3O
4-PR catalyst contains 1mmol 3 to wherein adding, and the methanol solution of 4-dichloro-nitrobenzene under agitation, is 1MPa in Hydrogen Vapor Pressure, and temperature is to implement catalytic hydrogenation under the condition of 303K, and the product gas chromatographic analysis behind the 60min is answered in negate.
Pd-Pt/Fe under the above-mentioned reaction condition
3O
4-PR load type double-metal nanocluster catalyst catalytic activity and catalytic selectivity result are as shown in table 8.
Table 8Pd-Pt/Fe
3O
4-PR load type double-metal nanocluster catalyst catalysis 3, the hydrogenation of 4-dichloro-nitrobenzene
Reaction condition: methanol solvate, 20ml; Temperature, 323K; Pressure, 1MPa; 3,4-dichloro-nitrobenzene, 1mmol.
The above results shows that this catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Embodiment 7: preparation is by Pd-Rh bimetal nano bunch (wherein Pd: Rh (mol ratio)=5: 1) and the γ-Fe that is in the partial reduction state
2O
3Catalyst (Pd-Rh:0.5wt.%) that constitutes and catalytic performance test thereof
One, Preparation of Catalyst
The aqueous solution (1.88 * 10 with palladium bichloride
-2Mol/L) and the aqueous solution (1.88 * 10 of radium chloride
-2Mol/L) be to mix at 5: 1 by volume.The potassium hydroxide aqueous solution of getting 5ml concentration and be 0.2mol/L joins under vigorous stirring in the aqueous solution of the palladium bichloride of 10ml and radium chloride fast, stir 1min and make palladium-rhodium bimetallic compound colloid under 353K, the content of Pd and Rh is 1.32g/L in the colloid.
γ-Fe
2O
3(L.J.Wan described in the nano structural material reference literature, et al., Self-assembled 3Dflowerlike iron oxide nanostructures and their application in water treatment.Adv.Mater.2006,18,2426-2431) method preparation.1.2g six Ferric Chloride Hydrateds, 2.7g urea and 7.2g TBAB are dissolved in the 180ml ethylene glycol; be warming up to 468K backflow 30min, be cooled to room temperature after, the precipitation that generates is centrifugal, ethanol washing four times; with its under nitrogen protection in 673K roasting 3h, make nanostructured Fe
3O
4Material is again with gained Fe
3O
4In air,, promptly make γ-Fe in 523K roasting 3h
2O
3Nano structural material.Tem study shows, this γ-Fe
2O
3The primary particle average grain diameter of material is 20nm, and particle diameter is distributed as 15-25nm.
Get the palladium-rhodium bimetallic compound colloid of the above-mentioned preparation of 7.6ml, under stirring fast, it is added drop-wise to γ-Fe that 50ml is dispersed with the above-mentioned preparation of 2.0g
2O
3In the ethanol of nano structural material, after at room temperature continuing to stir 5min,,, then system is warming up to 373K, continues to stop behind the reaction 5h the stirring reaction 5h under 303K of system elder generation to wherein adding 2ml oxalic acid aqueous solution (35%).Apply magnetic field and make precipitate and separate, washing in 333K vacuum drying 20h, promptly makes Pd-Rh/ γ-Fe
2O
3The load type double-metal nanocluster catalyst.Tem study shows, prepared Pd-Rh/ γ-Fe
2O
3The average grain diameter of Pd-Rh bimetal nano particle is 3nm in the load type double-metal nanocluster catalyst, and particle diameter is distributed as 2-6nm, γ-Fe
2O
3The primary particle average grain diameter be 20nm, particle diameter is distributed as 15-25nm.
0.5g is pressed the Pd-Rh/ γ-Fe of said process preparation
2O
3Be scattered in the water, to wherein adding the KBH that 20ml concentration is 0.2M
4The aqueous solution, 3h is handled in reduction under 323K.XPS and XRD analysis show that the gained catalyst is by Pd-Rh bimetal nano particle and the γ-Fe that is in the partial reduction state
2O
3Nano particle constitutes and (is designated as Pd-Rh/ γ-Fe
2O
3-PR).Tem study shows, prepared Pd-Rh/ γ-Fe
2O
3The average grain diameter of Pd-Rh bimetal nano particle is 3nm in the-PR catalyst, and particle diameter is distributed as 2-6nm, is in the γ-Fe of partial reduction state
2O
3(γ-Fe
2O
3-PR) average grain diameter of primary particle is 20nm, particle diameter is distributed as 15-25nm.Icp analysis shows that the content of Pd-Rh in the prepared catalyst is 0.5wt.%, and O/Fe is 1.47 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 45m
2/ g.
Two, catalyst 2,4-dinitro-chlorine benzene hydrogenation
Pd-Rh/ γ-the Fe that in reactor, adds the step 1 preparation of 0.06g embodiment 7
2O
3-PR catalyst contains 0.5mmol 2 to wherein adding, and the methanol solution of 4-dinitrofluorobenzene under agitation, is 0.1MPa in Hydrogen Vapor Pressure, and temperature is to implement catalytic hydrogenation under the condition of 303K, and the product gas chromatographic analysis behind the 60min is answered in negate.
Pd-Rh/ γ-Fe under the above-mentioned reaction condition
2O
3-PR load type double-metal nanocluster catalyst catalytic activity and catalytic selectivity result are as shown in table 9
Table 9Pd-Rh/ γ-Fe
2O
3-PR load type double-metal nanocluster catalyst catalysis 2,4-dinitro-chlorine benzene hydrogenation performance
Reaction condition: methanol solvate, 20ml; Temperature, 303K; Pressure, 0.1MPa; 2,4-dinitrofluorobenzene, 0.5mmol.
The above results shows that this catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Embodiment 8: preparation is by Pd-Ru bimetal nano bunch (wherein Pd: Ru (mol ratio)=1: 1) and the α-Fe that is in the partial reduction state
2O
3The catalyst (Pd-Ru:2wt.%) that constitutes
The aqueous solution (2.82 * 10 with palladium bichloride
-2Mol/L) and the ethylene glycol solution (2.82 * 10 of ruthenic chloride
-2Mol/L) be to mix and be cooled to 243K at 1: 1 by volume.Get the lithium hydroxide ethylene glycol solution (0.5mol/L) that 10ml also is cooled to 243K, under agitation join in the glycol water of the palladium bichloride of 20ml and ruthenic chloride, system is warming up to 270K and continues to stir 20min, obtain palladium-ruthenium bimetallic compound colloid, the content of Pd and Ru is 2.92g/L in the colloid.
α-Fe
2O
3(X.Cao, et al., Preparation of amorphousFe described in the nano structural material reference literature
2O
3Powder with different particle sizes.J.Mater.Chem.1997,7,2447-2451) method preparation.With Fe (CO)
5Decahydronaphthalenes solution (0.25M) be that 273K, pressure are violent ultrasonic processing 3h in the air atmosphere of 0.15MPa in temperature, after the gained sediment was fully washed with pentane, vacuum drying 3h under 403K promptly made α-Fe
2O
3Nano structural material.Tem study shows, this α-Fe
2O
3The primary particle average grain diameter of material is 14nm, and particle diameter is distributed as 8-20nm.
The above-mentioned freshly prepd palladium of 14.0ml-ruthenium bimetallic compound colloid drops is added to α-Fe that 50ml is dispersed with the above-mentioned preparation of 2.0g
2O
3In the water of nano structural material, after at room temperature continuing to stir 5min,,, then system is warming up to 373K, continues to stop behind the reaction 5h the stirring reaction 5h under 303K of system elder generation to wherein adding 10ml ethylene glycol.With precipitation and centrifugal separation, washing is handled 6h in 323K in hydrogen atmosphere, promptly make Pd-Ru/ α-Fe
2O
3The load type double-metal nanocluster catalyst.Tem study shows, prepared Pd-Ru/ α-Fe
2O
3The average grain diameter of Pd-Ru bimetal nano particle is 5nm in the load type double-metal nanocluster catalyst, and particle diameter is distributed as 3-10nm, carrier α-Fe
2O
3The primary particle average grain diameter is 14nm, and particle diameter is distributed as 8-20nm.
0.5g is pressed the Pd-Ru/ α-Fe of said process preparation
2O
3Place tube furnace, in the mist (volume ratio is 1: 1) of hydrogen and nitrogen, 3h is handled in reduction under 313K.XPS and XRD analysis show that the gained catalyst is by Pd-Ru bimetal nano particle and the α-Fe that is in the partial reduction state
2O
3Nano particle constitutes and (is designated as Pd-Ru/ α-Fe
2O
3-PR).Tem study shows, prepared Pd-Ru/ α-Fe
2O
3The average grain diameter of Pd-Ru bimetal nano particle is 5nm in the-PR catalyst, and particle diameter is distributed as 3-10nm, is in the α-Fe of partial reduction state
2O
3(α-Fe
2O
3-PR) average grain diameter of primary particle is 14nm, particle diameter is distributed as 8-20nm.Icp analysis shows that the content of Pd-Ru in the prepared catalyst is 2wt.%, and O/Fe is 1.46 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 210m
2/ g.
This catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Two, Pd-Ru/ α-Fe
2O
3Load type double-metal nanocluster catalyst (wherein Pd: Ru (mol ratio), and Pd-Ru: 2wt.%=1: 1) catalysis m-chloronitrobenzene hydrogenation performance test
Pd-Ru/ α-the Fe that in reactor, adds the step 1 preparation of 0.02g embodiment 8
2O
3Catalyst to wherein adding the methanol solution contain the 1mmolm-chloronitrobenzene, under agitation, is 0.1MPa in Hydrogen Vapor Pressure, and temperature is to implement catalytic hydrogenation under the condition of 323K, and the product gas chromatographic analysis behind the 120min is answered in negate.
Pd-Ru/ α-Fe under the above-mentioned reaction condition
2O
3Load type double-metal nanocluster catalyst catalytic activity and catalytic selectivity result are as shown in table 10.
Table 10Pd-Ru/ α-Fe
2O
3The hydrogenation of load type double-metal nanocluster catalyst catalysis m-chloronitrobenzene
Reaction condition: methanol solvate, 20ml; Temperature, 323K; Pressure, 0.1MPa; The m-chloronitrobenzene, 1mmol.
This catalyst shows good catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Embodiment 9: preparation is by Pd-Ir bimetal nano bunch (wherein Pd: Ir (mol ratio)=4: 1) and the Fe that is in the partial reduction state
3O
4The catalyst (Pd-Ir:0.1wt.%) that constitutes
Ethylene glycol solution (1.13 * 10 with palladium bichloride
-2Mol/L) and the ethylene glycol solution (1.13 * 10 of iridium chloride
-2Mol/L) be to mix and be cooled to 250K at 4: 1 by volume, get the Ca (OH) that 4ml also is cooled to 250K
2The aqueous solution (0.05mol/L) under agitation joins in the ethylene glycol solution of 5ml palladium bichloride and iridium chloride, system is warming up to 280K and continues stir 70min, obtains palladium-iridium bimetallic compound colloid, and the content of Pd and Ir is 0.77g/L in the colloid.
Fe
3O
4Nano structural material prepares by the following method.The configuration quality percent concentration is 10% ammoniacal liquor and 4% iron chloride (0.25mol/L) aqueous solution respectively, gets proper ammonia solution and slowly is added drop-wise in the 100ml ferric chloride solution, finally controls pH about 7.5, aging 5min.The ferric hydroxide precipitate that generates is filtered, washed to there not being Cl
-Ion detects, and filter cake after the 353K drying, in 523-673K temperature programming heat treatment 3h, is cooled to room temperature in hydrogen gas stream, promptly obtains Fe
3O
4Nano structural material.Tem study shows, this Fe
3O
4The primary particle average grain diameter of material is 35nm, and particle diameter is distributed as 15-200nm.
Get the palladium-iridium bimetallic compound colloid of the above-mentioned preparation of 2.6ml, under stirring fast, it is added drop-wise to the Fe that 50ml is dispersed with the above-mentioned preparation of 2.0g
3O
4In the water of nano structural material, after continue stirring 1h under the 280K temperature, put it into the stirred in water bath reaction 5h of 303K, then with warming-in-water to 313K, continue to stop behind the reaction 1h.Utilize the magnetic field of magnet to make sediment is separated from dispersion, washing in the dry 12h of 353K, promptly makes Pd-Ir/Fe in air
3O
4The load type double-metal nanocluster catalyst.Tem study shows, prepared Pd-Ir/Fe
3O
4The average grain diameter of Pd-Ir bimetal nano particle is 2nm in the load type double-metal nanocluster catalyst, and particle diameter is distributed as 1-3nm, carrier Fe
3O
4The primary particle average grain diameter be 35nm, particle diameter is distributed as 15-200nm.
1.0g is pressed the Pd-Ir/Fe of said process preparation
3O
4Place tube furnace, under hydrogen and argon gas mixed atmosphere (volume ratio is 1: 3), 4h is handled in reduction under 473K.XPS and XRD analysis show that the gained catalyst is by Pd-Ir bimetal nano particle and the Fe that is in the partial reduction state
3O
4Nano particle constitutes and (is designated as Pd-Ir/Fe
3O
4-PR).Tem study shows, prepared Pd-Ir/Fe
3O
4The average grain diameter of Pd-Ir bimetal nano particle is 2nm in the-PR catalyst, and particle diameter is distributed as 1-3nm, is in the Fe of partial reduction state
3O
4-(Fe
3O
4-PR) average grain diameter of primary particle is 35nm, particle diameter is distributed as 15-200nm.Icp analysis shows that the content of Pd-Ir in the prepared catalyst is 0.1wt.%, and O/Fe is 1.31 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 23m
2/ g.
This catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Embodiment 10: preparation is by Pd-Os bimetal nano bunch (wherein Pd: Os (mol ratio)=9: 1) and the γ-Fe that is in the partial reduction state
2O
3The catalyst (Pd-Os:10wt.%) that constitutes
The aqueous solution (2.82 * 10 with palladium bichloride
-2Mol/L) and the aqueous solution (2.82 * 10 of osmium chloride
-2Mol/L) be to mix at 9: 1 by volume.The sodium hydrate aqueous solution of getting 32ml concentration and be 0.5mol/L joins under vigorous stirring in the aqueous solution of 80ml palladium bichloride and osmium chloride fast, stirs 1min under the room temperature and makes palladium-osmium bimetallic compound colloid, and the content of Pd and Os is 2.30g/L in the colloid.
Prepare the ammonia spirit of 12.5% (mass percent concentration) and the ferric sulfate aqueous solution of 0.5mol/L respectively, get proper ammonia solution and under agitation be added drop-wise in the 25ml ferrum sulfuricum oxydatum solutum, finally control pH about 7.5, aging 5min.With the ferric hydroxide precipitate that generates filter, washing, filter cake pulled an oar in 30ml 1.5% iron chloride and under 323K the low-grade fever slurries, make ferric hydroxide colloid, it is standby to be cooled to room temperature.
The above-mentioned freshly prepd palladium of 96.6ml-osmium bimetallic compound colloid under agitation is added drop-wise to above-mentioned Fe (OH)
3In the colloid, obtain the rufous complex sol, behind the stirring 0.5h, 100ml ethylene glycol is injected above-mentioned complex sol, continue to stir 0.5h, at N
2Protection down is heated to backflow with system, behind the backflow 2h to wherein adding 2mlNaOOCCH
2The OH aqueous solution (0.5g/ml) continues backflow 30h, the black precipitate that generates separated with externally-applied magnetic field, and washing, oxidation drying 20h in the 353K air promptly makes Pd-Os/ γ-Fe
2O
3The load type double-metal nanocluster catalyst.Tem study shows, prepared Pd-Os/ γ-Fe
2O
3The average grain diameter of Pd-Os bimetal nano particle is 13nm in the load type double-metal nanocluster catalyst, and particle diameter is distributed as 3-25nm, carrier γ-Fe
2O
3The average grain diameter of primary particle is 15nm, and particle diameter is distributed as 8-25nm.
0.3g is pressed the Pd-Os/ γ-Fe of said process preparation
2O
3Be scattered in the methyl alcohol, place autoclave, at 303K, 1.0MPa Hydrogen Vapor Pressure reduction is down handled 3h.XPS and XRD analysis show that the gained catalyst is by Pd-Os bimetal nano particle and the γ-Fe that is in the partial reduction state
2O
3Nano particle constitutes and (is designated as Pd-Os/ γ-Fe
2O
3-PR).Tem study shows, prepared Pd-Os/ γ-Fe
2O
3The average grain diameter of Pd-Os bimetal nano particle is 13nm in the-PR catalyst, and particle diameter is distributed as 3-25nm, is in the γ-Fe of partial reduction state
2O
3(γ-Fe
2O
3-PR) average grain diameter of primary particle is 15nm, particle diameter is distributed as 8-25nm.Icp analysis shows that the content of Pd-Os in the prepared catalyst is 10wt.%, and O/Fe is 1.45 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 105m
2/ g.
This catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Embodiment 11: preparation is by Pd-Ru-Ir tri-metal nano bunch (wherein Pd: Ru: Ir (mol ratio)=3: 1: 1) and the Fe that is in the partial reduction state
3O
4The catalyst (Pd-Ru-Ir:1wt.%) that constitutes
Ethylene glycol solution (1.88 * 10 with palladium bichloride
-2Mol/L), the ethylene glycol solution (1.88 * 10 of ruthenic chloride
-2Mol/L) and the ethylene glycol solution (1.88 * 10 of iridium chloride
-2Mol/L) be to mix at 3: 1: 1 by volume, be put in and cool off 60min in the ice-water bath, get the NaOH aqueous solution (0.25mol/L) that 6ml also fully cools off in ice-water bath, under agitation join in the ethylene glycol solution of 12ml palladium bichloride, ruthenic chloride and iridium chloride, 30min is stirred in continuation in ice-water bath, obtain palladium-ruthenium-iridium three metallic compound colloids, wherein the concentration of Pd-Ru-Ir is 1.53g/L.
Fe
3O
4Nano structural material is pressed the method preparation of step 1 among the embodiment 2.
Get the palladium-ruthenium-iridium three metallic compound colloids of the above-mentioned preparation of 13.2ml, under stirring fast, it is added drop-wise to the Fe that 50ml is dispersed with the above-mentioned preparation of 2.0g
3O
4In the ethylene glycol of nano structural material, after at room temperature continuing to stir 1h, put it into the stirred in water bath reaction 5h of 303K, then it is warming up to 433K under nitrogen protection, continue to stop behind the reaction 3h, be cooled to room temperature.Apply magnetic field and make precipitate and separate, washing in the dry 12h of 353K, promptly makes Pd-Ru-Ir/Fe in air
3O
4Support type tri-metal nano cluster catalyst.Tem study shows, prepared Pd-Ru-Ir/Fe
3O
4The average grain diameter of Pd-Ru-Ir tri-metal nano particle is 4nm in the support type tri-metal nano cluster catalyst, and particle diameter is distributed as 2-8nm, Fe
3O
4The primary particle average grain diameter be 27nm, particle diameter is distributed as 10-55nm.
0.45g is pressed the Pd-Ru-Ir/Fe of said process preparation
3O
4Be scattered in the ethanol, place autoclave, at 353K, 1.0MPa Hydrogen Vapor Pressure reduction is down handled 5h.XPS and XRD analysis show that the gained catalyst is by Pd-Ru-Ir/ tri-metal nano particle and the Fe that is in the partial reduction state
3O
4Nano particle constitutes and (is designated as Pd-Ru-Ir/Fe
3O
4-PR).Tem study shows, prepared Pd-Ru-Ir/Fe
3O
4The average grain diameter of Pd-Ru-Ir tri-metal nano particle is 4nm in the-PR catalyst, and particle diameter is distributed as 2-8nm, is in the Fe of partial reduction state
3O
4(Fe
3O
4-PR) average grain diameter of primary particle is 27nm, particle diameter is distributed as 10-55nm.Icp analysis shows that the content of Pd-Ru-Ir in the prepared catalyst is 1wt.%, and O/Fe is 1.31 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 39m
2/ g.
This catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Embodiment 12: preparation is by Pd-Re bimetal nano bunch (wherein Pd: Re (mol ratio)=6: 1) and the Fe that is in the partial reduction state
3O
4The catalyst (Pd-Re:3wt.%) that constitutes
Ethylene glycol solution (3.77 * 10 with palladium bichloride
-2Mol/L) and the aqueous solution (3.77 * 10 of chlorination rhenium
-2Mol/L) be to mix and be cooled to 260K at 6: 1 by volume, get the NaOH aqueous solution (0.4mol/L) that 12ml also is cooled to 260K, under agitation join in the glycol water of the palladium bichloride of 20ml and chlorination rhenium, system is warming up to 273K and continue stirs 30min make palladium-rhenium bimetallic compound colloid, the content of Pd and Re is 2.77g/L in the colloid.
Preparing mass percent concentration respectively is 10% tetramethyl ammonium hydroxide and 4% iron chloride (0.25mol/L) aqueous solution, gets an amount of tetramethyl ammonium hydroxide solution and slowly is added drop-wise in the 50ml ferric chloride solution, finally controls pH about 8, aging 8min.The ferric hydroxide precipitate that generates is filtered, washed to there not being Cl
-Ion, filter cake pulled an oar in the 15ml4% ferric chloride solution and under 323K the low-grade fever slurries, make ferric hydroxide colloid, it is standby to be cooled to room temperature.
The above-mentioned freshly prepd palladium of 14.7ml-rhenium bimetallic compound colloid drops is added in the above-mentioned ferric hydroxide colloid, and again to wherein injecting 15ml 1, ammediol is put into then and is had the teflon-lined autoclave and handle treatment temperature 353K, time 72h.With the sedimentation and filtration that generates, washing to there not being Cl
-Ion, vacuum drying 48h under 353K promptly makes Pd-Re/Fe
3O
4The load type double-metal nanocluster catalyst.Tem study shows, prepared Pd-Re/Fe
3O
4The average grain diameter of Pd-Re bimetal nano particle is 11nm in the load type double-metal nanocluster catalyst, and particle diameter is distributed as 3-20nm, carrier Fe
3O
4The primary particle average grain diameter is 18nm, and particle diameter is distributed as 8-23nm.
0.3g is pressed the Pd-Re/Fe of said process preparation
3O
4Be scattered in the methyl alcohol, place autoclave, at 303K, 1.0MPa Hydrogen Vapor Pressure reduction is down handled 3h.XPS and XRD analysis show that the gained catalyst is by Pd-Re bimetal nano particle and the Fe that is in the partial reduction state
3O
4Nano particle constitutes and (is designated as Pd-Re/Fe
3O
4-PR).Tem study shows, prepared Pd-Re/Fe
3O
4The average grain diameter of Pd-Re bimetal nano particle is 11nm in the-PR catalyst, and particle diameter is distributed as 3-20nm, is in the Fe of partial reduction state
3O
4(Fe
3O
4-PR) average grain diameter of primary particle is 18nm, particle diameter is distributed as 8-23nm.Icp analysis shows that the content of Pd-Re in the prepared catalyst is 3wt.%, and O/Fe is 1.32 than (x/y).The BET characterization result shows that this specific surface area of catalyst is 122m
2/ g.
This catalyst shows excellent catalytic performance in the reaction of the synthetic chloro arylamine of chloro aromatic nitro compound selective hydration.
Claims (20)
1. a class loading type Pd base metal nanometer cluster catalyst is by the Pd metal nanoparticle or contain the bimetallic of Pd or multi-metal nanoparticles and be Fe as the general formula of carrier
yO
xFerric oxide nano particles constitute;
Wherein, the bimetallic of the described Pd of containing or other metal in the multi-metal nanoparticles are selected from any one or a few among Pt, Rh, Ru, Os, Ir and the Re;
When metal nanoparticle is the Pd nano particle, 1＜x/y＜4/3 or 4/3＜x/y＜3/2;
When metal nanoparticle is described bimetallic that contains Pd or multi-metal nanoparticles, 1＜x/y≤3/2.
2. catalyst according to claim 1 is characterized in that: described loading type Pd base metal nanometer cluster catalyst be by the Pd metal nanoparticle be Fe as the general formula of carrier
yO
xFerric oxide nano particles constitute;
Wherein, 1＜x/y＜4/3 or 4/3＜x/y＜3/2.
3. catalyst according to claim 1 is characterized in that: described loading type Pd base metal nanometer cluster catalyst is to be Fe by the bimetallic that contains Pd or multi-metal nanoparticles and as the general formula of carrier
yO
xFerric oxide nano particles constitute;
Wherein, the bimetallic of the described Pd of containing or other metal in the multi-metal nanoparticles are selected from any one or a few among Pt, Rh, Ru, Os, Ir and the Re;
Described Fe
yO
xIn, 1＜x/y≤3/2.
4. according to the arbitrary described catalyst of claim 1-3, it is characterized in that: described Pd metal nanoparticle or contain the bimetallic of Pd or the particle diameter of multi-metal nanoparticles is 1-25nm, described general formula as carrier is Fe
yO
xThe particle diameter of primary particle of ferric oxide nano particles be 5-200nm.
5. according to the arbitrary described catalyst of claim 1-3, it is characterized in that: described Pd metal nanoparticle or contain the bimetallic of Pd or the quality percentage composition of multi-metal nanoparticles is 0.1-15%.
6. a method for preparing the described loading type Pd base metal nanometer cluster catalyst of claim 1 comprises the steps:
1) with Pd based metallization compound colloid and ferric hydroxide colloid mixing, heat-treat behind the adding reducing agent, sediment separate out, washing, drying or oxidation obtain with Fe
3O
4Or γ-Fe
2O
3Loading type Pd base metal nanometer cluster catalyst for carrier;
2) described step 1) is prepared with γ-Fe
2O
3And Fe
3O
4For the loading type Pd base metal nanometer cluster catalyst of carrier reduces processing, obtain described loading type Pd base metal nanometer cluster catalyst.
7. method according to claim 6 is characterized in that: in the described step 1), the metal in the Pd based metallization compound colloid is selected from Pd and/or the following metal any one or a few: Pt, Rh, Ru, Os, Ir and Re;
Described Pd based metallization compound colloid is selected from any one or a few in Pd Base Metal oxide, hydroxide or the basic salt compound;
In the described Pd based metallization compound colloid in Pd based metallization compound and the ferric hydroxide colloid mass ratio of iron hydroxide be 1: 6-1250; The concentration of described ferric hydroxide colloid is 1-300g/L;
Described reducing agent is selected from H
2, the carbon atom number is in monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, formaldehyde, glycolic acid, hydroxy acid sodium, glyoxal and the oxalic acid of 1-4 any one or a few;
Described heat treatment method comprises solvent heat treatment, heating reflow treatment or microwave heating treatment;
Described heat treatment temperature is 303-473K, and heat treatment time is 1-200h, and baking temperature is 278-523K;
The temperature of described oxidation step is 313-523K, and oxidizing atmosphere is the mist of air or oxygen and inert gas;
Described step 2) in, the used reducing agent of reduction treatment step is selected from H
2, NaBH
4, KBH
4With in the hydrazine hydrate any one or a few;
Used medium is selected from organic solvent, water, H in the described reduction treatment step
2And H
2With in the mixed atmosphere of inert gas any one or a few;
The temperature that described reduction is handled is 300-523K, and the time that reduction is handled is 1 minute-100 hours.
8. according to claim 6 or 7 described methods, it is characterized in that: in the described step 1), Pd based metallization compound colloid is prepared as follows:
The soluble-salt of Pd or the soluble-salt or the acid of acid or Pd and at least a other transition metal are dissolved in alcohol, water or the alcohol-water mixture, are mixed with transistion metal compound solution; Wherein, the soluble-salt of described other transition metal or the transition metal in the acid are selected from any one or a few among Pt, Rh, Ru, Ir, Os or the Re.
Alcoholic solution, the aqueous solution or the alcohol-water mixture of solubility hydroxide, carbonate or the bicarbonate of alkali metal or alkaline-earth metal are mixed under the 243-373K temperature with described transistion metal compound solution, obtain described Pd based metallization compound colloid.
9. method according to claim 8 is characterized in that: described alcohol is the mixture of any one or its arbitrary proportion in monohydric alcohol, dihydroxylic alcohols or the trihydroxylic alcohol of 1-4 for the carbon atom number;
The concentration of described transistion metal compound solution is 0.01-100g/L;
Solubility hydroxide, carbonate or the bicarbonate of described alkali metal or alkaline-earth metal and the mol ratio of described transistion metal compound are 1-20: 1.
10. according to claim 6 or 7 described methods, it is characterized in that: in the described step 1), ferric hydroxide colloid is prepared as follows:
In the aqueous solution of molysite, add aqueous slkali, regulate the pH value, generate ferric hydroxide precipitate, then ferric hydroxide precipitate is joined peptization in the peptizing agent, obtain described ferric hydroxide colloid to 4-12.
11. method according to claim 10, it is characterized in that: described molysite is any one or a few in iron chloride, ferric nitrate or the ferric sulfate, described aqueous slkali is that mass percent concentration is the aqueous solution of ammoniacal liquor, potassium hydroxide, NaOH, lithium hydroxide or the tetramethyl ammonium hydroxide of 1-25%, and described peptizing agent is the solution or the hydrochloric acid of described molysite.
12. a method for preparing the described loading type Pd base metal nanometer cluster catalyst of claim 1 comprises the steps:
1) iron oxide is scattered in the mixed liquor of the water-soluble organic solvent of water or energy or described organic solvent and water, stirs or ultrasonic dispersion, obtain iron oxide carrier suspension;
2) the iron oxide carrier suspension mixing that Pd based metallization compound colloid and described step 1) are prepared is heat-treated after adding reducing agent, sediment separate out, and washing, drying, obtaining with the iron oxide is the loading type Pd base metal nanometer cluster catalyst of carrier;
3) with described step 2) what prepare is that the loading type Pd base metal nanometer cluster catalyst of carrier reduces processing with the iron oxide, obtains described loading type Pd base metal nanometer cluster catalyst.
13. method according to claim 12 is characterized in that: in the described step 1), described iron oxide comprises magnetic oxide and α-Fe
2O
3Described magnetic oxide is Fe
3O
4, γ-Fe
2O
3And Fe
yO
xIn any one or arbitrarily several mixture that mixes with arbitrary proportion, wherein, Fe
yO
xIn, 1＜x/y＜1.5;
The specific area of described iron oxide is 20-210m
2/ g; The quality of the iron oxide that disperses in every liter of iron oxide carrier suspension is 0.1-1000g;
The water-soluble organic solvent of described energy is monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, acetone, oxolane or the N of 1-4 for the carbon atom number, any one in the dinethylformamide or several arbitrarily mixture that mixes with arbitrary proportion;
Described reducing agent is H
2, the carbon atom number is any one or a few mixture that mixes with arbitrary proportion in monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, formaldehyde, glycolic acid, hydroxy acid sodium, glyoxal or the oxalic acid of 1-4;
Described step 2) in, the metal in the Pd based metallization compound colloid is selected from Pd and/or the following metal any one or a few: Pt, Rh, Ru, Os, Ir and Re;
Described Pd based metallization compound colloid is selected from any one or a few in Pd Base Metal oxide, hydroxide or the basic salt compound;
In the Pd based metallization compound colloid in Pd based metallization compound and the described iron oxide carrier suspension mass ratio of iron oxide carrier be 1: 5-900;
Described heat treatment method comprises solvent heat treatment, heating reflow treatment or microwave heating treatment;
Described heat treatment temperature is 303-473K, and heat treatment time is 1-200h, and baking temperature is 278-523K;
In the described step 3), the used reducing agent of reduction treatment step is selected from H
2, NaBH
4, KBH
4Or in the hydrazine hydrate any one or a few;
The used medium of described reduction treatment step is selected from organic solvent, water, H
2And H
2With in the mixed atmosphere of inert gas any one or a few;
The temperature that described reduction is handled is 300-523K, and the time that reduction is handled is 1 minute-100 hours.
14. according to claim 12 or 13 described methods, it is characterized in that: described step 2), Pd based metallization compound colloid is prepared as follows:
The soluble-salt of Pd or the soluble-salt or the acid of acid or Pd and at least a other transition metal are dissolved in alcohol, water or the alcohol-water mixture, are mixed with transistion metal compound solution; Wherein, the soluble-salt of described other transition metal or the transition metal in the acid are selected from any one or a few among Pt, Rh, Ru, Ir, Os or the Re.
Alcoholic solution, the aqueous solution or the alcohol-water mixture of solubility hydroxide, carbonate or the bicarbonate of alkali metal or alkaline-earth metal are mixed under the 243-373K temperature with described transistion metal compound solution, obtain described Pd based metallization compound colloid.
15. method according to claim 14 is characterized in that: described alcohol is the mixture of any one or its arbitrary proportion in monohydric alcohol, dihydroxylic alcohols or the trihydroxylic alcohol of 1-4 for the carbon atom number;
The concentration of described transistion metal compound solution is 0.01-100g/L;
Solubility hydroxide, carbonate or the bicarbonate of described alkali metal or alkaline-earth metal and the mol ratio of described transistion metal compound are 1-20: 1.
16. a method for preparing the described loading type Pd base metal nanometer cluster catalyst of claim 1 comprises the steps:
1) soluble-salt of Pd or the soluble-salt or the acid of acid or Pd and at least a other transition metal are dissolved in alcohol, water or the alcohol-water mixture, obtain transistion metal compound solution; Wherein, the soluble-salt of described other transition metal or the transition metal in the acid are selected from any one or a few among Pt, Rh, Ru, Ir, Os or the Re;
2) iron oxide is scattered in the mixed liquor of the water-soluble organic solvent of water or energy or described organic solvent and water, stirs or ultrasonic dispersion, obtain iron oxide carrier suspension;
3) transistion metal compound solution that described step 1) is prepared and described step 2) the iron oxide carrier suspension mixing for preparing, add alkali metal or the solubility hydroxide of alkaline-earth metal or alcoholic solution or the aqueous solution or the pure water mixed solution of carbonate or bicarbonate, the gained mixture is heat-treated, sediment separate out, described sediment is scattered in the mixed liquor of water or organic solvent that can be water-soluble or described organic solvent and water, heat-treat after adding reducing agent, sediment separate out, washing, drying, obtaining with the iron oxide is the loading type Pd base metal nanometer cluster catalyst of carrier;
What 4) described step 3) is prepared is that the loading type Pd base metal nanometer cluster catalyst of carrier reduces processing with the iron oxide, obtains described loading type Pd base metal nanometer cluster catalyst.
17. method according to claim 16 is characterized in that: in the described step 1), the concentration of described transistion metal compound solution is 0.01-100g/L;
Described step 2) in, iron oxide is selected from γ-Fe
2O
3, α-Fe
2O
3And Fe
yO
xIn any one or arbitrarily several mixture that mixes with arbitrary proportion, wherein, Fe
yO
xIn, 1＜x/y＜1.5;
The specific area of described iron oxide is 20-210m
2/ g; The quality of the iron oxide that disperses in every liter of iron oxide carrier suspension is 0.1-1000g;
The water-soluble organic solvent of described energy is monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, acetone, oxolane or the N of 1-4 for the carbon atom number, any one in the dinethylformamide or several arbitrarily mixture that mixes with arbitrary proportion;
In the described step 3), the mass ratio of iron oxide carrier is 1 in transition metal in the transistion metal compound and the iron oxide carrier suspension: 5-1000;
The mol ratio of the transistion metal compound in the hydroxide of described alkali metal or alkaline-earth metal, carbonate or bicarbonate and the described transistion metal compound solution is 1-100: 1;
The water-soluble organic solvent of described energy is monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, acetone, oxolane or the N of 1-4 for the carbon atom number, any one in the dinethylformamide or several arbitrarily mixture that mixes with arbitrary proportion;
Described reducing agent is selected from H
2, the carbon atom number is in monohydric alcohol, dihydroxylic alcohols or trihydroxylic alcohol, formaldehyde, glycolic acid, hydroxy acid sodium, glyoxal and the oxalic acid of 1-4 any one;
In the step of heat treatment, heat treatment temperature is 273-473K behind the solubility hydroxide of described adding alkali metal or alkaline-earth metal or the alcoholic solution of carbonate or bicarbonate or the aqueous solution or the pure water mixed solution, and heat treatment time is 0-200h;
In the step of heat treatment, heat treatment method comprises solvent heat treatment, heating reflow treatment or microwave heating treatment behind the described adding reducing agent, and heat treatment temperature is 303-473K, and heat treatment time is 1-200h, and baking temperature is 278-523K;
In the described step 4), the used reducing agent of reduction treatment step is selected from H
2, NaBH
4, KBH
4Or in the hydrazine hydrate any one or a few;
The used medium of described reduction treatment step is selected from organic solvent, water, H
2And H
2With in the mixed atmosphere of inert gas any one or a few;
The temperature that described reduction is handled is 300-523K, and the time that described reduction is handled is 1 minute-100 hours.
18. the arbitrary described loading type Pd base metal nanometer cluster catalyst of claim 1-5 in the nitro selective hydrogenation of chloro aromatic nitro compound as Application of Catalyst.
19. application according to claim 18 is characterized in that: the general structure of described chloro aromatic nitro compound is suc as formula shown in the I:
In the described formula I general structure, X=H, R, COOR, RO, Cl, NO
2Or NH
2Wherein, R is the saturated alkane base of C1-C4.
20. application according to claim 18 is characterized in that: the general structure of described chloro aromatic nitro compound is suc as formula shown in the II:
Among the formula II, X, X ', Y=H, R, COOR, RO, Cl, Z=H, NO
2Or NH
2Wherein, R is the saturated alkane base of C1-C4.
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