CN106914255B - Non-alloy metal compound and preparation method and application thereof - Google Patents
Non-alloy metal compound and preparation method and application thereof Download PDFInfo
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- CN106914255B CN106914255B CN201710196454.4A CN201710196454A CN106914255B CN 106914255 B CN106914255 B CN 106914255B CN 201710196454 A CN201710196454 A CN 201710196454A CN 106914255 B CN106914255 B CN 106914255B
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- copper
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- 229910002065 alloy metal Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 150000002736 metal compounds Chemical class 0.000 title abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 138
- 239000002184 metal Substances 0.000 claims abstract description 137
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 117
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 51
- 239000002905 metal composite material Substances 0.000 claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 29
- 239000010941 cobalt Substances 0.000 claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 29
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 26
- 239000010948 rhodium Substances 0.000 claims abstract description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 24
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 24
- 239000004332 silver Substances 0.000 claims abstract description 24
- 230000009467 reduction Effects 0.000 claims abstract description 21
- 239000012876 carrier material Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 16
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 14
- 150000005181 nitrobenzenes Chemical class 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims abstract description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 91
- 239000003054 catalyst Substances 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000000084 colloidal system Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000002105 nanoparticle Substances 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 29
- 239000002244 precipitate Substances 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000001307 helium Substances 0.000 claims description 17
- 229910052734 helium Inorganic materials 0.000 claims description 17
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 15
- 150000004692 metal hydroxides Chemical class 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 8
- 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 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 7
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- JXMZUNPWVXQADG-UHFFFAOYSA-N 1-iodo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1I JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910001295 No alloy Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 150000002739 metals Chemical class 0.000 abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- 239000004408 titanium dioxide Substances 0.000 abstract description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 2
- 150000001448 anilines Chemical class 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 6
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical compound [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 4
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 3
- MSLQKIPIYZNMEP-UHFFFAOYSA-N [Cu].[Pt].[Ru] Chemical class [Cu].[Pt].[Ru] MSLQKIPIYZNMEP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- WRWZNPYXEXPBAY-UHFFFAOYSA-N azane cobalt Chemical compound N.[Co] WRWZNPYXEXPBAY-UHFFFAOYSA-N 0.000 description 3
- SUCYXRASDBOYGB-UHFFFAOYSA-N cobalt rhodium Chemical compound [Co].[Rh] SUCYXRASDBOYGB-UHFFFAOYSA-N 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000005653 Brownian motion process Effects 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910018883 Pt—Cu Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- KMPWYEUPVWOPIM-KODHJQJWSA-N cinchonidine Chemical compound C1=CC=C2C([C@H]([C@H]3[N@]4CC[C@H]([C@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-KODHJQJWSA-N 0.000 description 1
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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Abstract
The invention relates to a non-alloy metal composite and a preparation method and application thereof, wherein the non-alloy metal composite is loaded on a carrier material in a mutually contact manner by at least one of platinum, rhodium, ruthenium or iridium and at least one of copper, cobalt, nickel or silver, and the carrier material is any one of activated carbon, silicon dioxide, titanium dioxide, montmorillonite, a molecular sieve, a carbon nano tube or graphene. The non-alloy metal compound prepared by the invention has a novel structure, is loaded on a carrier material in a metal-metal mutual contact mode, can effectively adjust the catalytic performance by changing the proportion of metals, and has the advantages of simplicity, flexibility and strong adjustability. The non-alloy metal compound has extremely high catalytic efficiency in the reaction of preparing halogenated aniline by catalyzing the selective reduction of halogenated nitrobenzene, the selectivity of the halogenated aniline is higher than 95 percent and can reach more than 99 percent, and the non-alloy metal compound has good application prospect.
Description
Technical Field
The invention relates to the field of preparation and application of nano materials, in particular to a non-alloy metal compound and a preparation method and application thereof.
Background
The platinum group elements have very wide application prospects in the field of catalysis, including catalytic cracking, catalytic hydrogenation, electrocatalysis and the like. However, the catalytic properties of the platinum group elements are too single to meet all the requirements of catalytic reactions, especially those involving selective catalysis. For example, platinum is a catalyst for the selective reduction of halogenated nitrobenzene to halogenated aniline, and not only catalyzes hydrogen to reduce nitro functional groups to amine groups, but also catalyzes the side reaction of dehalogenation of halogenated aniline. Other platinum group elements have catalytic properties similar to platinum, which is the case with platinum elements. It is difficult to obtain good selectivity in some selective catalytic reactions by using platinum group elements alone as catalysts. In order to solve the problem, organic or inorganic additives, such as cinchonidine, fluoride and the like, are added to improve the selectivity of some stereo-conformation selective reactions or functional group reduction selective reactions. However, the addition of the above-mentioned additives makes the separation of the product difficult, and the additives are also difficult to recycle.
Modification or modification of the structure of the catalyst is a viable approach. Taking a platinum-based catalyst as an example, one approach is to select a suitable support, and the catalytic performance of platinum can be adjusted by selecting different metal oxides as the support for platinum particles, such as titanium oxide, aluminum oxide, silicon oxide, iron oxide, and the like. However, the use of these carriers for conditioning the catalytic performance of platinum is relatively limited because the type of carrier is fixed and its effect on the load is substantially fixed, making it difficult to achieve a large degree of improvement. Another approach is to use inert metal elements to adjust the performance of platinum-based catalysts, such as copper, cobalt, tin, etc. and platinum to make metal composite catalysts. However, the metal composite catalyst synthesized at present is mainly of an alloy or core-shell structure, and when the ratio between metal and metal is adjusted, the geometric morphology of the alloy surface changes due to different alloy ratios, so that the surface structure is greatly different, and the catalytic performance is influenced; meanwhile, the Fermi levels of different metals are different, so that charge transfer effect can occur, the charge transfer degree is different when the proportion is different, and the effect of metal-metal electrons can be changed along with the charge transfer effect, so that the catalytic performance is difficult to effectively regulate and control. The core-shell structure also has similar problems, and when the ratio of the core metal to the shell metal is adjusted, the surface structure is changed, so that the adjustment of the catalytic performance is difficult.
In order to effectively adjust the catalytic performance of the platinum group catalyst by independently adjusting the metal-metal ratio without changing the surface structure of the metal composite, it is necessary to develop a metal composite having a novel structure.
Disclosure of Invention
In view of the problems of the prior art, the object of the present invention is to provide an unalloyed metal composite, a method for preparing the same and an application thereof, which can obtain a metal composite loaded on a carrier material in a metal-metal mutual contact manner, wherein the metal composite has a novel mutual contact structure and does not form an alloy; the method can effectively adjust the catalytic performance by changing the ratio of metals, has the advantages of simplicity, flexibility and strong adjustability, has extremely high catalytic efficiency in the reaction of preparing halogenated aniline by catalyzing the selective reduction of halogenated nitrobenzene, has the selectivity of the halogenated aniline of more than 99 percent, and has good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a non-alloy metal composite, which is composed of a metal a, a metal B and a support material, wherein the metal a and the metal B are supported on the support material in a mutually contacting manner, the metal a is at least one of platinum, rhodium, ruthenium or iridium, and the metal B is at least one of copper, cobalt, nickel or silver.
In the obtained non-alloy metal composite, the nano particles of the metal A and the nano particles of the metal B are loaded on a carrier material in a mutually contacted mode. The form of mutual contact means: the two are in contact with each other in a physical contact mode, and no alloy is formed between the two.
The surface structure of the existing bimetallic catalyst with an alloy or core-shell structure can generate great difference along with the change of the proportion between metals, simultaneously, the degree of electron transfer between the metals is changed, and the effective regulation of the catalytic performance is difficult to realize. The non-alloy metal composite prepared by the invention has a novel structure, and is loaded on a carrier material in a metal-metal mutual contact mode (non-alloy), when the ratio between metals is adjusted, the structure of an active material cannot be changed, and the electron transfer degree between metals is controllable; therefore, when the catalyst is used as a catalyst, the catalytic performance can be effectively adjusted by changing the ratio of the metals, and the catalyst has the advantages of simplicity, flexibility and strong adjustability. The non-alloy metal compound has excellent catalytic performance, and the catalytic efficiency in the reaction of catalyzing the selective reduction of the halogenated nitrobenzene to prepare the halogenated aniline can reach more than 99 percent.
According to the invention, the metal a is at least one of platinum, rhodium, ruthenium or iridium, and may be any one of platinum, rhodium, ruthenium or iridium, for example, and typical but non-limiting combinations are as follows: platinum and rhodium; platinum and ruthenium; platinum and iridium; rhodium and ruthenium; rhodium and iridium; ruthenium and iridium; platinum, rhodium and ruthenium; platinum, rhodium and iridium; platinum, ruthenium and iridium; rhodium, ruthenium and iridium; platinum, rhodium, ruthenium and iridium.
According to the invention, the metal B is at least one of copper, cobalt, nickel or silver, and may be any one of copper, cobalt, nickel or silver, for example, and a typical but non-limiting combination is: copper and cobalt; copper and nickel; copper and silver; cobalt and nickel; cobalt and silver; nickel and silver; copper, cobalt and nickel; copper, cobalt and silver; copper, nickel and silver; cobalt, nickel and silver; copper, cobalt, nickel and silver.
According to the invention, the carrier material is any one of activated carbon, silicon dioxide, titanium dioxide, montmorillonite, molecular sieve, carbon nano tube or graphene.
According to the invention, the content of metal a in the non-alloyed metal composite is 0.1-20 wt.%, which may be, for example, 0.1 wt.%, 0.5 wt.%, 1 wt.%, 3 wt.%, 5 wt.%, 7 wt.%, 10 wt.%, 12 wt.%, 14 wt.%, 16 wt.%, 18 wt.% or 20 wt.%, and the particular values between the above-mentioned values are not exhaustive for reasons of brevity and brevity.
The content of the metal A in the non-alloyed metal composite according to the invention is preferably 1 to 5 wt.%.
According to the invention, the content of metal B in the non-alloyed metal composite is between 0.5 and 30 wt.%, and may be, for example, 0.5 wt.%, 1 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.% or 30 wt.%, and the particular values between the above values, which are limited by space and for reasons of brevity, are not exhaustive and are not included in the recited ranges.
The content of the metal B in the non-alloy metal composite of the present invention is preferably 1 to 10%.
According to the invention, the metal a is preferably platinum and/or ruthenium, most preferably platinum.
According to the invention, the metal B is preferably copper and/or cobalt, most preferably copper.
In a second aspect, the present invention provides a method of making a non-alloy metal composite as defined in the first aspect, the method comprising the steps of:
(1) preparing a supported metal catalyst of metal B;
(2) preparing a nanoparticle colloid of metal A;
(3) and (3) mixing the nanoparticle colloid obtained in the step (2) with the supported metal catalyst obtained in the step (1) in a protective atmosphere, and stirring until the colloid is completely adsorbed to obtain the non-alloy metal composite.
The nano-sized active metal particles are frequently used for preparing metal composites because of their excellent properties in the fields of catalysis and adsorption. When metal salt is used as a starting material to prepare metal nanoparticles, particularly bimetallic nanoparticles, a higher preparation temperature is generally required. However, the melting point of the nano-sized metal particles is low, and two or more kinds of metal nanoparticles may cause alloy formation when they are brought into contact at a high temperature, so that it is difficult to obtain a metal-metal mutual contact structure (non-alloy) by a conventional synthesis method. The preparation method is designed, so that metal B is firstly loaded on a carrier, and metal A nano particles which can move freely collide with metal B under the action similar to Brownian motion and are fixed on the metal B under the normal temperature condition, so that a metal-metal mutual contact structure is formed.
According to the invention, the metal B in step (1) is any one or a combination of at least two of copper, cobalt, nickel or silver, for example, any one of copper, cobalt, nickel or silver, and a typical but non-limiting combination is: copper and cobalt; copper and nickel; copper and silver; cobalt and nickel; cobalt and silver; nickel and silver; copper, cobalt and nickel; copper, cobalt and silver; copper, nickel and silver; cobalt, nickel and silver; copper, cobalt, nickel and silver.
According to the invention, the metal a in step (2) is any one or a combination of at least two of platinum, rhodium, ruthenium or iridium, for example, any one of platinum, rhodium, ruthenium or iridium, and a typical but non-limiting combination is: platinum and rhodium; platinum and ruthenium; platinum and iridium; rhodium and ruthenium; rhodium and iridium; ruthenium and iridium; platinum, rhodium and ruthenium; platinum, rhodium and iridium; platinum, ruthenium and iridium; rhodium, ruthenium and iridium; platinum, rhodium, ruthenium and iridium.
According to the present invention, the method for preparing nanoparticle colloid of metal a in step (2) is polyol reduction method or sol-gel method.
According to the invention, the nano particle colloid and the supported metal catalyst in the step (3) are added in an amount that the content of the metal B in the obtained non-alloy metal composite is 0.5-30 wt% and the content of the metal A in the obtained non-alloy metal composite is 0.1-20 wt%.
According to the invention, the supported metal catalyst in the step (3) is dispersed in a solvent before being mixed with the colloid. The solvent is water and/or alcohol.
According to the invention, the alcohol is any one of methanol, ethanol or ethylene glycol or a combination of at least two of them, for example, any one of methanol, ethanol or ethylene glycol, and a typical but non-limiting combination is: methanol and ethanol; methanol and ethylene glycol; methanol, ethanol and ethylene glycol.
According to the present invention, the solid-to-liquid ratio of the supported metal catalyst and the solvent is 1 (2-200), and may be, for example, 1:2, 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 1:120, 1:140, 1:160, 1:180, or 1:200, and specific values therebetween are not exhaustive, and for reasons of brevity and conciseness, the present invention does not provide an exhaustive list of specific values included in the range.
The unit of the solid-to-liquid ratio of the supported metal catalyst and the solvent is g/ml.
According to the present invention, the protective atmosphere in step (3) is any one or a combination of at least two of nitrogen, argon or helium, for example, any one of nitrogen, argon or helium, and a typical but non-limiting combination is: nitrogen and argon; nitrogen and helium; argon and helium; nitrogen, argon and helium.
Preferably, after the stirred colloid is completely adsorbed in the step (3), centrifugal washing is carried out, and the obtained solid is freeze-dried to obtain the non-alloy metal composite.
In the present invention, the method for preparing the supported metal catalyst of metal B in step (1) and the method for preparing the nanoparticle colloid of metal a in step (2) are performed by methods known in the art, and are not particularly limited.
By way of example, but not limitation, the following is a specific procedure for preparing a supported metal catalyst of metal B as described in step (1):
(a) dissolving a metal salt corresponding to the metal B in a solvent, adding an alkaline solution to generate a hydroxide precipitate, and after solid-liquid separation, adding the precipitate into ammonia water to dissolve to obtain an ammonia coordination metal hydroxide solution;
(b) dispersing a carrier material in a solvent, then mixing the carrier material with the ammonia coordination metal hydroxide solution obtained in the step (a), and heating the mixture to completely volatilize ammonia and water to obtain a solid compound of the metal hydroxide and the carrier;
(c) dispersing the solid compound obtained in the step (b) in a solvent, adding a reducing agent under a protective atmosphere for reaction, carrying out solid-liquid separation after the reaction is finished, and carrying out vacuum freeze drying to obtain the supported metal catalyst.
According to the invention, when the metal B in step (a) is copper, the corresponding metal salt is any one of copper sulfate, copper nitrate or copper chloride or a combination of at least two of copper sulfate, copper nitrate or copper chloride, for example, any one of copper sulfate, copper nitrate or copper chloride, and a typical but non-limiting combination is: copper sulfate and copper nitrate; copper sulfate and copper chloride; copper nitrate and copper chloride; copper sulfate, copper nitrate and copper chloride.
According to the present invention, when the metal B in step (a) is cobalt, the corresponding metal salt is any one of cobalt sulfate, cobalt nitrate or cobalt chloride or a combination of at least two of them, for example, any one of cobalt sulfate, cobalt nitrate or cobalt chloride, and a typical but non-limiting combination is: cobalt sulfate and cobalt nitrate; cobalt sulfate and cobalt chloride; cobalt nitrate and cobalt chloride; cobalt sulfate, cobalt nitrate and cobalt chloride.
According to the invention, when the metal B in step (a) is nickel, the corresponding metal salt is any one of nickel sulfate, nickel nitrate or nickel chloride or a combination of at least two of nickel sulfate, nickel nitrate or nickel chloride, for example, any one of nickel sulfate, nickel nitrate or nickel chloride, and a typical but non-limiting combination is nickel sulfate and nickel nitrate; nickel sulfate and nickel chloride; nickel nitrate and nickel chloride; nickel sulfate, nickel nitrate and nickel chloride.
According to the invention, when the metal B in step (a) is silver, the corresponding metal salt is silver nitrate.
According to the present invention, the solvent in step (a), step (b) and step (c) is independently water or alcohol.
According to the invention, the alcohol is any one of methanol, ethanol or ethylene glycol or a combination of at least two of them, for example, any one of methanol, ethanol or ethylene glycol, and a typical but non-limiting combination is: methanol and ethanol; methanol and ethylene glycol; methanol, ethanol and ethylene glycol.
According to the invention, the solid-to-liquid ratio of the metal salt and the solvent in step (a) is 1 (20-500), and may be, for example, 1:20, 1:50, 1:100, 1:150, 1:200, 1:250, 1:300, 1:350, 1:400, 1:450 or 1:500, and specific values therebetween, and the invention is not exhaustive and for the sake of brevity only specific values included in the ranges are not intended. The solid-liquid ratio of the metal salt to the solvent is preferably 1 (50-150).
The unit of the solid-liquid ratio of the metal salt to the solvent is g/ml.
According to the invention, the alkaline solution of step (a) is a NaOH and/or KOH solution.
According to the invention, the alkaline solution is added in step (a) and then stirred.
According to the invention, the alkaline solution of step (a) is added in an amount such that at least the metal B is completely precipitated as a hydroxide, i.e. the metal B may be just completely precipitated as a hydroxide, or may be in excess.
According to the invention, the aqueous ammonia described in step (a) is added in an amount such that at least the hydroxide precipitate is completely dissolved, i.e. just as completely dissolved, or in excess.
According to the invention, the solid-to-liquid ratio of the carrier material to the solvent in step (b) is 1 (2-200), which may be, for example, 1:2, 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 1:120, 1:140, 1:160, 1:180, or 1:200, and the specific values between the above values are not exhaustive and are not intended to limit the invention to the specific values included in the ranges for brevity and conciseness.
The unit of the solid-liquid ratio of the carrier material to the solvent is g/ml.
According to the invention, the heating temperature in step (b) is 50-130 ℃, for example 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or 130 ℃, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
According to the present invention, the solid-to-liquid ratio of the solid complex and the solvent in step (c) is 1 (2-200), and may be, for example, 1:2, 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 1:120, 1:140, 1:160, 1:180, or 1:200, and specific values therebetween are not exhaustive, and for brevity and clarity, the present invention is not intended to include the specific values included in the range.
The unit of the solid-liquid ratio of the solid compound to the solvent is g/ml.
According to the present invention, the protective atmosphere in step (c) is any one or a combination of at least two of nitrogen, argon or helium, for example, any one of nitrogen, argon or helium, and typical but non-limiting combinations are: nitrogen and argon; nitrogen and helium; argon and helium; nitrogen, argon and helium.
According to the present invention, the reducing agent in step (c) is any one or a combination of at least two of sodium borohydride, hydrazine hydrate, lithium aluminum hydride, ascorbic acid, sodium hypophosphite, hydrogen iodide, sulfur or hydrogen sulfide, for example, any one of sodium borohydride, hydrazine hydrate, lithium aluminum hydride, ascorbic acid, sodium hypophosphite, hydrogen iodide, sulfur or hydrogen sulfide, and a typical but non-limiting combination is: sodium borohydride and hydrazine hydrate; lithium aluminum hydride and ascorbic acid; sodium hypophosphite and hydrogen iodide; sulfur and hydrogen sulfide; sodium borohydride and lithium aluminum hydride; ascorbic acid and hydrogen iodide; sodium borohydride, hydrazine hydrate and lithium aluminum hydride; ascorbic acid, sodium hypophosphite and hydrogen sulfide; sodium borohydride, hydrazine hydrate, lithium aluminum hydride, ascorbic acid, and the like, are not exhaustive for purposes of space and simplicity.
According to the present invention, the reducing agent in step (c) is added in an amount at least to completely reduce the metal hydroxide in the solid composite, i.e. the metal hydroxide in the solid composite may be just completely reduced, or may be in excess.
Taking the preparation of platinum nanoparticle colloid as an example, the polyol reduction method is selected to prepare platinum nanoparticle colloid, and the preparation method is exemplarily as follows, but not limited thereto:
dissolving chloroplatinic acid in an ethylene glycol solution, then dropping alkali liquor (dissolved in ethylene glycol), adjusting the pH value to be more than 10, and reacting for 3h at the temperature of 180 ℃ under the protection of protective gas (nitrogen, argon or helium) to obtain the platinum nano particle colloid.
As a preferred technical scheme, the preparation method of the non-alloy metal oxide comprises the following steps:
(1) dissolving a metal salt corresponding to the metal B in a solvent, adding an alkaline solution to generate a hydroxide precipitate, and after solid-liquid separation, adding the precipitate into ammonia water to dissolve to obtain an ammonia coordination metal hydroxide solution; dispersing a carrier material in a solvent, then mixing the carrier material with an ammonia coordination metal hydroxide solution, heating to completely volatilize ammonia and water to obtain a solid compound of metal hydroxide and a carrier, dispersing the obtained solid compound in the solvent, adding a reducing agent under a protective atmosphere to react, carrying out solid-liquid separation after the reaction is finished, and carrying out vacuum freeze drying to obtain a supported metal catalyst;
(2) preparing nanoparticle colloid of the metal A by using a polyol reduction method or a sol-gel method;
(3) dispersing the supported metal catalyst obtained in the step (a) in a solvent, mixing the dispersed supported metal catalyst with the nano particle colloid obtained in the step (b) in a protective atmosphere, stirring until the colloid is completely adsorbed, centrifuging, washing with water, and freeze-drying the obtained solid to obtain the non-alloy metal composite.
In a third aspect, the present invention provides the use of a non-alloyed metal complex as described in the first aspect as a catalyst for the selective reduction of halogenated nitrobenzene to produce halogenated aniline.
The non-alloy metal compound prepared by the invention has extremely high catalytic efficiency in the reaction of preparing halogenated aniline by catalyzing the selective reduction of halogenated nitrobenzene, can obviously inhibit the occurrence of dehalogenation side reaction, and improves the selectivity of halogenated aniline, wherein the selectivity of halogenated aniline is higher than 95% and can reach more than 99%.
According to the invention, the halogenated nitrobenzene is any one or combination of at least two of chloronitrobenzene, bromonitrobenzene or iodonitrobenzene, for example, the halogenated nitrobenzene can be any one of chloronitrobenzene, bromonitrobenzene or iodonitrobenzene, and typical but non-limiting combinations are as follows: chloronitrobenzene and bromonitrobenzene; bromonitrobenzene and iodonitrobenzene; chloronitrobenzene and iodonitrobenzene; chloronitrobenzene, bromonitrobenzene and iodonitrobenzene.
The following are illustrative, but not limiting, of the specific operation of the non-alloyed metal composite prepared according to the present invention as a catalyst for the selective reduction of halogenated nitrobenzene to halogenated aniline:
the non-alloy metal compound prepared by the invention is mixed with halogenated nitrobenzene in a reaction kettle, hydrogen is introduced as a reducing agent, the pressure is controlled to be 1-20MPa, and the temperature is controlled to be-20-200 ℃, so that the halogenated aniline can be obtained.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the non-alloy metal composite prepared by the invention has a novel structure, is loaded on a carrier material in a metal-metal mutual contact mode (non-alloy), can effectively adjust the catalytic performance by changing the ratio of metals, and has the advantages of simplicity, flexibility and strong adjustability.
(2) The non-alloy metal compound prepared by the invention has extremely high catalytic efficiency in the reaction of preparing halogenated aniline by catalyzing the selective reduction of halogenated nitrobenzene, and the selectivity of the halogenated aniline is higher than 95 percent and can reach more than 99 percent.
Drawings
FIG. 1 is a TEM photograph of a platinum-copper/activated carbon catalyst obtained in example 1 of the present invention, wherein the loading amount of platinum is 2 wt% and the loading amount of copper is 5 wt%;
FIG. 2 is a high resolution TEM photograph of a Pt-Cu/C catalyst obtained in example 1 of the present invention, wherein the loading of Pt is 2 wt% and the loading of Cu is 5 wt%;
FIG. 3(a) is a STEM photograph of a platinum-copper/activated carbon catalyst obtained in example 1 of the present invention;
FIG. 3(b) is a photograph of a line scan of the platinum-copper/activated carbon catalyst obtained in example 1 of the present invention, which corresponds to FIG. 3 (a).
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
Preparation of platinum copper/activated carbon composite:
(1) dissolving 0.32g of anhydrous copper chloride in 30ml of water, adding 50ml of 0.1M NaOH solution to generate a precipitate, stirring until the precipitate is completely precipitated, washing the precipitate by centrifugal water, and adding the precipitate into 50ml of 28 wt% ammonia water solution to obtain a copper ammonia solution; dispersing 3g of activated carbon into 150ml of ethanol, then dropwise adding a copper ammonia solution, stirring until the reaction is complete, and heating to 60 ℃ to completely volatilize ammonia and water to obtain a solid compound; dispersing the solid compound in 100ml of water, dropwise adding 50ml of 0.27M sodium borohydride solution under the protection of nitrogen, after complete reaction, centrifugally washing, and carrying out vacuum freeze drying to obtain a copper/activated carbon catalyst;
(2) dissolving 1g of chloroplatinic acid (Pt is more than or equal to 37.0%) into 50ml of ethylene glycol, mixing with 50ml of 0.25M NaOH ethylene glycol solution under the condition of stirring at room temperature, continuously stirring for 30min, heating to 160 ℃ under the protection of nitrogen, keeping the temperature for 3h, and cooling to obtain a platinum nanoparticle colloid with the mass fraction of 0.32%;
(3) and (2) dispersing the copper/activated carbon catalyst obtained in the step (1) in 100ml of ethylene glycol, dropwise adding 18.75g of platinum nanoparticle colloid obtained in the step (2) under the protection of nitrogen, stirring for 1h, adding 200ml of water, continuously stirring until the colloid is completely adsorbed, centrifugally washing, and freeze-drying to obtain the platinum-copper/activated carbon composite.
The platinum copper/activated carbon composite prepared in this example was subjected to electron microscopy characterization using a transmission electron microscope (TECnai F20, FEI usa), and platinum elements (bright spots) were supported on the activated carbon (dark portions) as shown in fig. 1. As shown in fig. 2, the large-area wavy substance is carrier activated carbon, and the obliquely striped substance is platinum particles; the lower right hand graph is an enlarged view of the obliquely striped particle in the graph, which is measured to have interplanar spacings of
Corresponding to the (111) crystal plane of Pt, (each crystal has a specific interplanar spacing, the interplanar spacing will change after forming the alloy, and the standard interplanar spacing of the Pt (111) crystal plane is
) Therefore, it was confirmed that the diagonal stripes were Pt particles and no alloy was formed. As shown in fig. 3(a) and 3(b), platinum element and copper element are present at the same time at the position of the platinum particle. As can be seen from fig. 2, 3(a) and 3(b), platinum and copper are in contact with each other, and do not form an alloy.
The platinum-copper/activated carbon composite prepared in the embodiment is used as a catalyst in the preparation of chloroaniline by the selective reduction of chloronitrobenzene:
0.1857g of the platinum-copper/activated carbon composite (Pt mass fraction is 2%) prepared in the embodiment is dispersed in 60ml of methanol, the mixture is placed in an autoclave, 1MPa of hydrogen is introduced, the mixture is slowly discharged, the air exchange is repeatedly carried out for 5 times, the pressure in the autoclave is kept at 1MPa, the mixture is heated to 60 ℃, the mixture is kept for 1h, the air release is slowly carried out, 0.3g of p-chloronitrobenzene is added, the 1MPa of hydrogen is introduced, the air exchange is repeatedly carried out for 5 times, the pressure in the autoclave is kept at 1MPa, the mixture is heated to 60 ℃ and reacts for 20min, and the p-chloroaniline.
After the reaction is finished, gas chromatography measurement shows that the conversion rate of the p-chloronitrobenzene is 100%, the selectivity of the p-chloroaniline is 99.5%, and the selectivity of the aniline is 0.5%.
Example 2
Preparing a platinum nickel/carbon nanotube composite:
(1) dissolving 0.31g of anhydrous nickel chloride in 30ml of water, adding 50ml of 0.1M NaOH solution to generate a precipitate, stirring until the precipitate is completely precipitated, washing the precipitate by centrifugal water, and adding the precipitate into 100ml of 30 wt% ammonia water solution to obtain a nickel-ammonia solution; dispersing 3g of carbon nano tube into 150ml of ethanol, then dropwise adding a nickel-ammonia solution, stirring until the nickel-ammonia solution completely reacts, and heating to 80 ℃ to completely volatilize ammonia and water to obtain a solid compound; dispersing the solid compound in 100ml of water, dropwise adding 50ml of 0.27M sodium borohydride solution under the protection of argon gas, centrifugally washing after complete reaction, and carrying out vacuum freeze drying to obtain a nickel/carbon nanotube catalyst;
(2) dissolving 1g of chloroplatinic acid (Pt is more than or equal to 37.0%) into 50ml of ethylene glycol, mixing with 50ml of 0.25M NaOH ethylene glycol solution under the condition of stirring at room temperature, continuously stirring for 30min, heating to 160 ℃ under the protection of helium gas, keeping for 3h, and cooling to obtain a platinum nanoparticle colloid with the mass fraction of 0.32%;
(3) and (2) dispersing the nickel/carbon nanotube catalyst obtained in the step (1) in 100ml of ethylene glycol, dropwise adding 18.75g of platinum nanoparticle colloid obtained in the step (2) under the protection of helium, stirring for 1h, adding 200ml of water, continuously stirring until the colloid is completely adsorbed, centrifugally washing, and freeze-drying to obtain the platinum nickel/carbon nanotube composite.
The platinum nickel/carbon nanotube composite prepared in the embodiment is used as a catalyst in the preparation of bromoaniline through selective reduction of bromonitrobenzene:
0.1857g of the platinum-nickel/carbon nanotube composite (Pt mass fraction is 2%) prepared in the embodiment is dispersed in 60ml of methanol, the mixture is placed in an autoclave, 1MPa of hydrogen is introduced, the mixture is slowly discharged, the air exchange is repeatedly carried out for 5 times, the pressure in the autoclave is kept at 1MPa, the mixture is heated to 60 ℃, the mixture is kept for 1h, the air release is slowly carried out, 0.3g of o-bromonitrobenzene is added, the 1MPa of hydrogen is introduced, the air exchange is repeatedly carried out for 5 times, the pressure in the autoclave is kept at 1MPa, the mixture is heated to 60 ℃ and reacts for 30min, and o-bromoaniline and.
After the reaction is finished, gas chromatography measurement shows that the conversion rate of o-bromonitrobenzene reaches 100%, the selectivity of o-bromoaniline is 96.3%, and the selectivity of aniline is 2.9%.
Example 3
Preparing a rhodium cobalt/carbon nanotube composite:
(1) dissolving 0.285g of anhydrous cobalt chloride in 30ml of water, adding 50ml of 0.1M KOH solution to generate a precipitate, stirring until the precipitate is completely precipitated, washing the precipitate by centrifugal water, and adding the precipitate into 100ml of 25 wt% ammonia water solution to obtain a cobalt-ammonia solution; dispersing 3g of carbon nano tube into 150ml of ethanol, then dropwise adding a cobalt ammonia solution, stirring until the cobalt ammonia solution completely reacts, and heating to 80 ℃ to completely volatilize ammonia and water to obtain a solid compound; dispersing the solid compound in 100ml of water, dropwise adding 50ml of 0.27M hydrazine hydrate solution under the protection of argon gas, centrifugally washing after the reaction is finished, and carrying out vacuum freeze drying to obtain a cobalt/carbon nano tube catalyst;
(2) dissolving 1g of chlororhodizonic acid amine (Rh is more than or equal to 27.5%) into 50ml of glycol, mixing with 50ml of 0.25M NaOH glycol solution under the condition of stirring at room temperature, continuously stirring for 30min, heating to 160 ℃ under the protection of argon gas, keeping for 3h, and cooling to obtain rhodium nanoparticle colloid with the mass fraction of 0.24%;
(3) and (2) dispersing the cobalt/carbon nanotube catalyst obtained in the step (1) in 100ml of ethylene glycol, dropwise adding 25.0g of rhodium nanoparticle colloid obtained in the step (2) under the protection of argon, stirring for 1h, adding 200ml of water, continuously stirring until the colloid is completely adsorbed, centrifugally washing, and freeze-drying to obtain the rhodium-cobalt/activated carbon composite.
The rhodium cobalt/activated carbon composite prepared in the embodiment is used as a catalyst in the preparation of chloroaniline by selective reduction of chloronitrobenzene, and except for the catalyst, the preparation conditions are completely the same as those in the embodiment 1.
After the reaction is finished, gas chromatography measurement shows that the conversion rate of p-chloronitrobenzene is 100%, the selectivity of p-chloroaniline is 95%, and the selectivity of aniline is 5%.
Examples4
Preparation of ruthenium platinum copper/silica complexes:
(1) dissolving 0.32g of anhydrous copper chloride in 30ml of water, adding 50ml of 0.1M NaOH solution to generate a precipitate, stirring until the precipitate is completely precipitated, washing the precipitate by centrifugal water, and adding the precipitate into 50ml of 28 wt% ammonia water solution to obtain a copper ammonia solution; dispersing 3g of silicon dioxide into 150ml of ethanol, then dropwise adding a copper ammonia solution, stirring until the reaction is complete, and heating to 60 ℃ to completely volatilize ammonia and water to obtain a solid compound; dispersing the solid compound in 100ml of water, dropwise adding 50ml of 0.27M sodium borohydride solution under the protection of nitrogen, after complete reaction, centrifugally washing, and carrying out vacuum freeze drying to obtain a copper/silicon dioxide catalyst;
(2) dissolving 1g of chlororuthenamine (Ru is more than or equal to 31.0%) into 50ml of ethylene glycol, mixing with 50ml of 0.25M NaOH ethylene glycol solution under the condition of stirring at room temperature, continuing stirring for 30min, heating to 160 ℃ under the protection of nitrogen, keeping the temperature for 3h, and cooling to obtain a ruthenium nanoparticle colloid with the mass fraction of 0.27%;
dissolving 1g of chloroplatinic acid (Pt is more than or equal to 37.0%) into 50ml of ethylene glycol, mixing with 50ml of 0.25M NaOH ethylene glycol solution under the condition of stirring at room temperature, continuously stirring for 30min, heating to 160 ℃ under the protection of nitrogen, keeping the temperature for 3h, and cooling to obtain a platinum nanoparticle colloid with the mass fraction of 0.32%;
(3) and (2) dispersing the copper/silicon dioxide catalyst obtained in the step (1) in 100ml of ethylene glycol, dropwise adding 9.40g of platinum nanoparticle colloid obtained in the step (2) and 11.1g of ruthenium nanoparticle colloid under the protection of argon gas, stirring for 1h, adding 200ml of water, continuously stirring until the colloid is completely adsorbed, centrifugally washing, and freeze-drying to obtain the ruthenium-platinum-copper/silicon dioxide composite.
The ruthenium platinum copper/silica composite prepared in the example is used as a catalyst in the preparation of chloroaniline by the selective reduction of chloronitrobenzene, and the preparation conditions are completely the same as those in the example 1 except for the catalyst.
After the reaction is finished, gas chromatography measurement shows that the conversion rate of the p-chloronitrobenzene is 100%, the selectivity of the p-chloroaniline is 99% and the selectivity of the aniline is 1%.
Comparative example 1
A platinum-copper/activated carbon catalyst was prepared using the following method, wherein platinum-copper was supported on activated carbon in the form of an alloy, the loading of platinum was 2 wt%, and the loading of copper was 5 wt%.
Dissolving 0.1625g of chloroplatinic acid in 100ml of ethylene glycol, adding 0.32g of anhydrous copper chloride, stirring and dissolving, adding 2.34g of PVPk-30, stirring and dissolving, dropwise adding a 0.1M NaOH ethylene glycol solution, and adjusting the pH value to be 10; and under the protection of argon, heating to 170 ℃, preserving heat for 3h, naturally cooling to room temperature, adding 3.0g of activated carbon, stirring for 2h, adding 200ml of water, continuously stirring for 2h, centrifuging, washing with water, and freeze-drying to obtain the platinum-copper/activated carbon catalyst.
The platinum copper/active carbon catalyst prepared by the comparative example is used for preparing chloroaniline by selective reduction of chloronitrobenzene, and the preparation conditions are completely the same as those in example 1 except for the catalyst.
After the reaction is finished, gas chromatography measurement shows that the conversion rate of p-chloronitrobenzene is 100%, the selectivity of p-chloroaniline is 96% and the selectivity of aniline is 4%.
Comparative example 2
A platinum/activated carbon catalyst was prepared using the following procedure, wherein the platinum loading was about 2 wt%.
(1) Dissolving 1g of chloroplatinic acid (Pt is more than or equal to 37.0%) into 50ml of ethylene glycol, mixing with 50ml of 0.25M NaOH ethylene glycol solution under the condition of stirring at room temperature, continuously stirring for 30min, heating to 160 ℃ under the protection of helium gas, keeping for 3h, and cooling to obtain a platinum nanoparticle colloid with the mass fraction of 0.32%;
(2) dispersing 3g of activated carbon in 100ml of ethylene glycol, dropwise adding 18.75g of platinum nanoparticle colloid obtained in the step (1) under the protection of helium, stirring for 1h, adding 200ml of water, continuously stirring until the colloid is completely adsorbed, centrifugally washing, and freeze-drying to obtain the platinum/activated carbon catalyst.
The platinum/activated carbon catalyst prepared in the comparative example was used in the preparation of chloroaniline by selective reduction of chloronitrobenzene, and the preparation conditions were exactly the same as in example 1 except for the catalyst.
After the reaction is finished, gas chromatography measurement shows that the conversion rate of the p-chloronitrobenzene is 100%, the selectivity of the p-chloroaniline is 75.2%, and the selectivity of the aniline is 20.5%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (43)
1. A non-alloy metal composite consisting of a metal a, a metal B and a support material, the metal a and the metal B being supported on the support material in contact with each other, the metal a being at least one of platinum, rhodium, ruthenium or iridium, the metal B being at least one of copper, cobalt, nickel or silver;
the mutual contact form refers to that: the two are in mutual contact in a physical contact mode, and no alloy is formed between the two;
the non-alloy metal composite is prepared by adopting the following method, and the method comprises the following steps:
(1) preparing a supported metal catalyst of metal B;
(2) preparing a nanoparticle colloid of metal A;
(3) and (3) mixing the nanoparticle colloid obtained in the step (2) with the supported metal catalyst obtained in the step (1) in a protective atmosphere, and stirring until the colloid is completely adsorbed to obtain the non-alloy metal composite.
2. The non-alloy metal composite of claim 1, wherein the support material is any one of activated carbon, silica, titania, montmorillonite, molecular sieves, carbon nanotubes, or graphene.
3. The unalloyed metal composite of claim 1, wherein the amount of metal a in the unalloyed metal composite is in the range of 0.1 to 20 wt%.
4. The unalloyed metal composite of claim 1, wherein the amount of metal a in the unalloyed metal composite is in the range of 1 to 5 wt%.
5. The unalloyed metal composite of claim 1, wherein the amount of metal B in said unalloyed metal composite is in the range of 0.5 to 30 wt%.
6. The unalloyed metallic composite of claim 1, wherein the amount of metal B present in said unalloyed metallic composite is in the range of 1% to 10%.
7. The unalloyed metal composite of claim 1, wherein said metal a is platinum and/or ruthenium.
8. The non-alloy metal composite of claim 1, wherein the metal a is platinum.
9. The unalloyed metal composite of claim 1, wherein said metal B is copper and/or cobalt.
10. The unalloyed metal composite of claim 1, wherein said metal B is copper.
11. The method of making a non-alloy metal composite according to claim 1, comprising the steps of:
(1) preparing a supported metal catalyst of metal B;
(2) preparing a nanoparticle colloid of metal A;
(3) and (3) mixing the nanoparticle colloid obtained in the step (2) with the supported metal catalyst obtained in the step (1) in a protective atmosphere, and stirring until the colloid is completely adsorbed to obtain the non-alloy metal composite.
12. The method of claim 11, wherein the metal B in step (1) is any one or a combination of at least two of copper, cobalt, nickel or silver.
13. The method of claim 11, wherein the metal a in step (2) is any one of platinum, rhodium, ruthenium or iridium or a combination of at least two thereof.
14. The method of claim 11, wherein the method for preparing the metal a nanoparticle colloid in step (2) is a polyol reduction method or a sol-gel method.
15. The method of claim 11, wherein the nanoparticle colloid and the supported metal catalyst in step (3) are added in amounts such that the resultant non-alloy metal composite has a metal B content of 0.5 to 30 wt% and a metal a content of 0.1 to 20 wt%.
16. The method of claim 11, wherein the supported metal catalyst of step (3) is dispersed in a solvent prior to mixing with the colloid.
17. The method of claim 16, wherein the solvent is water or an alcohol.
18. The method of claim 17, wherein the alcohol is any one of methanol, ethanol, or ethylene glycol, or a combination of at least two thereof.
19. The method of claim 16, wherein the solid-to-liquid ratio of the supported metal catalyst to the solvent is 1 (2-200), and the solid-to-liquid ratio of the supported metal catalyst to the solvent is in g/mL.
20. The method of claim 11, wherein the protective atmosphere of step (3) is any one of nitrogen, argon or helium or a combination of at least two thereof.
21. The method of claim 11, wherein the stirring colloid in the step (3) is completely adsorbed, and then the centrifugal water washing is performed, and the obtained solid is freeze-dried to obtain the non-alloy metal composite.
22. The method of claim 11, wherein the step (1) of preparing the supported metal catalyst of metal B is performed by:
(a) dissolving a metal salt corresponding to the metal B in a solvent, adding an alkaline solution to generate a hydroxide precipitate, and after solid-liquid separation, adding the precipitate into ammonia water to dissolve to obtain an ammonia coordination metal hydroxide solution;
(b) dispersing a carrier material in a solvent, then mixing the carrier material with the ammonia coordination metal hydroxide solution obtained in the step (a), and heating the mixture to completely volatilize ammonia and water to obtain a solid compound of the metal hydroxide and the carrier;
(c) dispersing the solid compound obtained in the step (b) in a solvent, adding a reducing agent under a protective atmosphere for reaction, carrying out solid-liquid separation after the reaction is finished, and carrying out vacuum freeze drying to obtain the supported metal catalyst.
23. The method of claim 22, wherein when the metal B in step (a) is copper, the corresponding metal salt is any one of copper sulfate, copper nitrate or copper chloride or a combination of at least two thereof.
24. The method of claim 22, wherein when the metal B in step (a) is cobalt, the corresponding metal salt is any one of cobalt sulfate, cobalt nitrate or cobalt chloride or a combination of at least two of them.
25. The method of claim 22, wherein when the metal B in step (a) is nickel, the corresponding metal salt is any one of nickel sulfate, nickel nitrate or nickel chloride or a combination of at least two thereof.
26. The method of claim 22, wherein when the metal B of step (a) is silver, the corresponding metal salt is silver nitrate.
27. The method of claim 22, wherein the solvent in step (a), step (b), and step (c) is independently water and/or an alcohol.
28. The method of claim 27, wherein the alcohol is any one of methanol, ethanol, or ethylene glycol, or a combination of at least two thereof.
29. The method of claim 22, wherein the solid-to-liquid ratio of the metal salt to the solvent in step (a) is 1 (20-500), and the solid-to-liquid ratio of the metal salt to the solvent is in g/mL.
30. The method of claim 22, wherein the solid-to-liquid ratio of the metal salt to the solvent in step (a) is 1 (50-150), and the solid-to-liquid ratio of the metal salt to the solvent is in g/mL.
31. The method of claim 22, wherein the alkaline solution of step (a) is a NaOH and/or KOH solution.
32. The method of claim 22, wherein the alkaline solution is added in step (a) followed by stirring.
33. The method of claim 22, wherein said alkaline solution of step (a) is added in an amount to at least completely precipitate metal B as hydroxide.
34. The method of claim 22, wherein the aqueous ammonia of step (a) is added in an amount to at least completely dissolve the hydroxide precipitate.
35. The method of claim 22, wherein the solid-to-liquid ratio of the carrier material to the solvent in step (b) is 1 (2-200), and the unit of the solid-to-liquid ratio of the carrier material to the solvent is g/mL.
36. The method of claim 22, wherein the temperature of said heating of step (b) is 50-130 ℃.
37. The method of claim 22, wherein the solid-to-liquid ratio of the solid-to-liquid composite and the solvent in step (c) is 1 (2-200), and the unit of the solid-to-liquid ratio of the solid-to-liquid composite and the solvent is g/mL.
38. The method of claim 22, wherein the protective atmosphere of step (c) is any one of nitrogen, argon or helium or a combination of at least two thereof.
39. The method of claim 22, wherein the reducing agent in step (c) is any one of sodium borohydride, hydrazine hydrate, lithium aluminum hydride, ascorbic acid, sodium hypophosphite, hydrogen iodide, sulfur or hydrogen sulfide or a combination of at least two thereof.
40. The method of claim 22, wherein the reducing agent in step (c) is added in an amount to at least completely reduce the metal hydroxide in the solid composite.
41. The method according to any of the claims 11, characterized in that the method comprises the steps of:
(1) dissolving a metal salt corresponding to the metal B in a solvent, adding an alkaline solution to generate a hydroxide precipitate, and after solid-liquid separation, adding the precipitate into ammonia water to dissolve to obtain an ammonia coordination metal hydroxide solution; dispersing a carrier material in a solvent, then mixing the carrier material with an ammonia coordination metal hydroxide solution, heating to completely volatilize ammonia and water to obtain a solid compound of metal hydroxide and a carrier, dispersing the obtained solid compound in the solvent, adding a reducing agent under a protective atmosphere to react, carrying out solid-liquid separation after the reaction is finished, and carrying out vacuum freeze drying to obtain a supported metal catalyst;
(2) preparing nanoparticle colloid of the metal A by using a polyol reduction method or a sol-gel method;
(3) dispersing the supported metal catalyst obtained in the step (a) in a solvent, mixing the dispersed supported metal catalyst with the nano particle colloid obtained in the step (b) in a protective atmosphere, stirring until the colloid is completely adsorbed, centrifuging, washing with water, and freeze-drying the obtained solid to obtain the non-alloy metal composite.
42. Use of the non-alloy metal composite according to any one of claims 1 to 10 as a catalyst in the selective reduction of halonitrobenzene to produce haloaniline.
43. Use of a non-alloy metal composite according to claim 42 wherein the halogenated nitrobenzene is any one or a combination of at least two of chloronitrobenzene, bromonitrobenzene or iodonitrobenzene.
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| CN109752411B (en) * | 2017-11-07 | 2021-09-17 | 国家纳米科学中心 | Composite gas-sensitive material and preparation method and application thereof |
| CN107986935B (en) * | 2017-11-27 | 2021-03-19 | 国家纳米科学中心 | Method for preparing styrene by catalyzing phenylacetylene with bimetallic catalyst |
| CN108212173A (en) * | 2018-01-19 | 2018-06-29 | 西安工业大学 | A kind of colloid production hydrogen catalyst and preparation method thereof |
| CN109301268B (en) * | 2018-09-29 | 2021-09-07 | 信阳师范学院 | Li-CO2Battery anode catalyst material, preparation method thereof, battery anode material and battery |
| CN109126823B (en) * | 2018-10-23 | 2021-08-17 | 江西理工大学 | Method for preparing aniline by selective hydrogenation of nitrobenzene under catalysis of catalyst |
| CN111821969B (en) * | 2019-04-23 | 2021-10-12 | 湖南大学 | Modified carbon black loaded nickel-gold bimetallic nano-catalyst and preparation method thereof |
| CN112694411A (en) * | 2020-12-29 | 2021-04-23 | 浙江工业大学 | Simple method for preparing p-aminophenol by reducing p-nitrophenol |
| CN114195648A (en) * | 2021-11-22 | 2022-03-18 | 台州学院 | Method for preparing parachloroaniline through selective hydrogenation of parachloronitrobenzene |
| CN114937782B (en) * | 2022-04-24 | 2024-03-08 | 中国科学院长春应用化学研究所 | Supported metal-based catalyst and preparation method thereof |
| CN115155615B (en) * | 2022-08-12 | 2023-09-05 | 台州学院 | Porous carbon material supported ruthenium catalyst and preparation method and application thereof |
| CN115945209A (en) * | 2022-12-05 | 2023-04-11 | 黑龙江省科学院石油化学研究院 | Ni @ Pd core-shell nano-catalyst for hydrogen storage of organic liquid and preparation method and application thereof |
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