CN113750992A - Photoactive halloysite-based closed boron cluster M2BxHxPreparation method and application of nano noble metal catalyst - Google Patents
Photoactive halloysite-based closed boron cluster M2BxHxPreparation method and application of nano noble metal catalyst Download PDFInfo
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- CN113750992A CN113750992A CN202110732906.2A CN202110732906A CN113750992A CN 113750992 A CN113750992 A CN 113750992A CN 202110732906 A CN202110732906 A CN 202110732906A CN 113750992 A CN113750992 A CN 113750992A
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- halloysite
- noble metal
- boron cluster
- nano
- catalyst
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 194
- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 51
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 111
- 238000003756 stirring Methods 0.000 claims abstract description 83
- 238000001914 filtration Methods 0.000 claims abstract description 71
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000005406 washing Methods 0.000 claims abstract description 59
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 8
- 150000001638 boron Chemical class 0.000 claims abstract description 5
- 150000003841 chloride salts Chemical class 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 134
- 239000011734 sodium Substances 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- RESTWAHJFMZUIZ-UHFFFAOYSA-N 1-ethyl-4-nitrobenzene Chemical compound CCC1=CC=C([N+]([O-])=O)C=C1 RESTWAHJFMZUIZ-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 10
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 claims description 7
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002828 nitro derivatives Chemical class 0.000 claims description 4
- AEBJDOTVYMITIA-UHFFFAOYSA-N 1,3,5-trichloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=C(Cl)C=C(Cl)C=C1Cl AEBJDOTVYMITIA-UHFFFAOYSA-N 0.000 claims description 3
- WMASLRCNNKMRFP-UHFFFAOYSA-N 1-fluoro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(F)=C1 WMASLRCNNKMRFP-UHFFFAOYSA-N 0.000 claims description 3
- SCCCFNJTCDSLCY-UHFFFAOYSA-N 1-iodo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1 SCCCFNJTCDSLCY-UHFFFAOYSA-N 0.000 claims description 3
- DPHCXXYPSYMICK-UHFFFAOYSA-N 2-chloro-1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C(Cl)=C1 DPHCXXYPSYMICK-UHFFFAOYSA-N 0.000 claims description 3
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 claims description 3
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 22
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 abstract description 2
- 229940005991 chloric acid Drugs 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 description 113
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 57
- 239000000741 silica gel Substances 0.000 description 57
- 229910002027 silica gel Inorganic materials 0.000 description 57
- 238000001291 vacuum drying Methods 0.000 description 49
- 150000001298 alcohols Chemical class 0.000 description 40
- 239000012065 filter cake Substances 0.000 description 26
- 239000000706 filtrate Substances 0.000 description 26
- 230000001678 irradiating effect Effects 0.000 description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 25
- 229910052763 palladium Inorganic materials 0.000 description 17
- 238000004064 recycling Methods 0.000 description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 239000010931 gold Substances 0.000 description 11
- NKJIFDNZPGLLSH-UHFFFAOYSA-N 4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1 NKJIFDNZPGLLSH-UHFFFAOYSA-N 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- CBBOPZBGHQVCGA-UHFFFAOYSA-N 4-[(4-cyanophenyl)diazenyl]benzonitrile Chemical compound C1=CC(C#N)=CC=C1N=NC1=CC=C(C#N)C=C1 CBBOPZBGHQVCGA-UHFFFAOYSA-N 0.000 description 9
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 9
- 229910052707 ruthenium Inorganic materials 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- -1 azobenzene compound Chemical class 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- AXKGIPZJYUNAIW-UHFFFAOYSA-N (4-aminophenyl)methanol Chemical compound NC1=CC=C(CO)C=C1 AXKGIPZJYUNAIW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- WNVWWDKUMKBZQV-UHFFFAOYSA-N bis(4-methylphenyl)diazene Chemical compound C1=CC(C)=CC=C1N=NC1=CC=C(C)C=C1 WNVWWDKUMKBZQV-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- NATVSFWWYVJTAZ-UHFFFAOYSA-N 2,4,6-trichloroaniline Chemical compound NC1=C(Cl)C=C(Cl)C=C1Cl NATVSFWWYVJTAZ-UHFFFAOYSA-N 0.000 description 1
- XJCVRTZCHMZPBD-UHFFFAOYSA-N 3-nitroaniline Chemical compound NC1=CC=CC([N+]([O-])=O)=C1 XJCVRTZCHMZPBD-UHFFFAOYSA-N 0.000 description 1
- KQIKKETXZQDHGE-FOCLMDBBSA-N 4,4'-diaminoazobenzene Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=C(N)C=C1 KQIKKETXZQDHGE-FOCLMDBBSA-N 0.000 description 1
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 1
- 229910002710 Au-Pd Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FIQUJBRQBIUISO-UHFFFAOYSA-N bis(2-chlorophenyl)diazene Chemical compound ClC1=CC=CC=C1N=NC1=CC=CC=C1Cl FIQUJBRQBIUISO-UHFFFAOYSA-N 0.000 description 1
- XGZUVWDFPZDZAQ-UHFFFAOYSA-N bis(3-fluorophenyl)diazene Chemical compound FC1=CC=CC(N=NC=2C=C(F)C=CC=2)=C1 XGZUVWDFPZDZAQ-UHFFFAOYSA-N 0.000 description 1
- HPSZIXYLILUGIP-UHFFFAOYSA-N bis(3-methylphenyl)diazene Chemical compound CC1=CC=CC(N=NC=2C=C(C)C=CC=2)=C1 HPSZIXYLILUGIP-UHFFFAOYSA-N 0.000 description 1
- RYPGBMPNCYRHKZ-UHFFFAOYSA-N bis(4-ethylphenyl)diazene Chemical compound C1=CC(CC)=CC=C1N=NC1=CC=C(CC)C=C1 RYPGBMPNCYRHKZ-UHFFFAOYSA-N 0.000 description 1
- FHSRQGXDVXFRHU-UHFFFAOYSA-N bis(4-iodophenyl)diazene Chemical compound C1=CC(I)=CC=C1N=NC1=CC=C(I)C=C1 FHSRQGXDVXFRHU-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N ortho-methyl aniline Natural products CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a natural ore material supported catalyst technology, in particular to a light-active halloysite-based closed boron cluster M2BxHxThe preparation method and the application of the nano noble metal catalyst comprise the following steps: dispersing natural halloysite in water, adding closed boron cluster M2BxHxStirring at 80-100 ℃ until the reaction is complete, and filtering, washing and drying after the reaction is finished to obtain halloysite-based boron clusters; and dispersing the halloysite-based boron cluster in water, stirring and reacting noble metal chloric acid or noble metal chloride salt at 20-50 ℃ under the irradiation of ultraviolet light until the reaction is complete, and filtering, washing and drying after the reaction is finished to obtain the halloysite-based closed boron cluster nano noble metal catalyst. The invention uses halloysite solid-supported closed boron cluster M for the first time2BxHxThe preparation method is simple and easy to regulate and control; the p-nitrobenzene compounds are subjected to azoreduction, so that the conversion rate is high, and aniline or azobenzene can be selectively obtained by regulating and controlling conditions.
Description
Technical Field
The invention relates to a natural ore material supported catalyst technology, in particular to a light-active halloysite-based closed boron cluster M2A preparation method and application of a BxHx nano noble metal catalyst.
Background
There are a large number of clay minerals on the earth's surface, many of which have nanostructures, nanoclays being a cheap nanomaterial in nature. Halloysite belongs to the kaolin group of clay minerals and is widely referred to as halloysite nanotubes because of its hollow nanotube-like structure. Halloysite is a clay mineral composed of aluminum octahedrons and silicon oxygen octahedrons in a 1:1 layered structure (Liuming sago, Lonice girth, Girdminn, etc.. halloysite nanotubes and their composites [ M ] 2019 ]. Halloysite has a special structure with a negative charge on its surface and a positive charge on its central internal diameter. Halloysite ores are distributed in all parts of the world basically, and the annual output is estimated to be more than ten thousand tons, so that halloysite is an inorganic nano material with good application prospect.
Nano-metal materials are an important component of nano-materials, and nano-scale metals can exhibit some unique properties such as electricity, light, magnetism, etc. compared with common metal materials, besides, nano-metal materials have larger specific surface area, more surface active atoms and higher surface energy compared with macroscopic metal materials. Nanomaterials therefore have better activity in many chemical reactions. Compared with other nano metal materials, nano noble metals have higher activity, better stability and certain specific catalytic activity, but the content of the noble metals in the earth is very limited, so that how to maximize the utilization rate of the noble metals becomes a research hotspot of researchers. Currently, the nano noble metal material needs to solve the following problems: the preparation is harsh, the particle size is not uniform, the repeated utilization rate is low, and the like, and the problems seriously hinder the development of the nano noble metal material. In 1912, Alfred Stock et al first proposed the concept of "borane", which was studied extensively since borane chemistry [ Stock A. hydrates of Boron and Silicon [ M ]].Cornell University Press,1933.]. The borane complexes are also called boron clusters, and have the general formula [ B ]nHn]2-Widely used in the field of supramolecular assembly, Boron Neutron Capture Therapy (BNCT for short) [ Johnson L S, Yanch J C, Shortkroff S, Sledge C B.in: Cancer Neutron Capture Therapy [ M],p.183.Plenum,New York 1996]Meanwhile, the boron cluster also has the characteristic of mild reducibility, and can reduce most noble metals (patent No. ZL 201610955661.9, patent No. ZL 201610959726.7)]。
The nitrobenzene compounds are active in chemical property and are important industrial raw materials for organic synthesis intermediates and production of aniline and azobenzene. The azobenzene compound can be used for dye synthesis, rubber accelerators and the like, has extremely high economic value, and is mainly obtained by dissolving nitrobenzene in hot methanol sodium hydroxide solution and adding Zn powder in the prior method for industrially preparing azobenzene. The conversion process is complicated and the cost is high.
Disclosure of Invention
An object of the present invention is to providePhotoactive halloysite-based closed boron cluster M2The preparation method of the BxHx nano noble metal catalyst has simple preparation process and easy regulation.
The second purpose of the invention is to provide a light active halloysite-based closed boron cluster M2The application of the BxHx nano noble metal catalyst can reduce azo on nitrobenzene compounds, has the advantages of mild reaction, short reaction time, easy operation, good environment, high repeated utilization rate and the like, and is beneficial to the industrial production of converting the nitrobenzene compounds into azobenzene.
The scheme adopted by the invention for realizing one of the purposes is as follows: photoactive halloysite-based closed boron cluster M2BxHxThe preparation method of the nano noble metal catalyst comprises the following steps:
(1) dispersing natural halloysite in water, adding closed boron cluster M2BxHxStirring at 80-100 ℃ until the reaction is complete, and filtering, washing and drying after the reaction is finished to obtain halloysite-based boron cluster M2BxHx;
(2) Grouping the halloysite-based boron clusters M2BxHxDispersing in water, stirring and reacting noble metal chloric acid or noble metal chloride under the irradiation of ultraviolet light at 20-50 ℃ until the reaction is complete, filtering, washing and drying after the reaction is finished to obtain the halloysite-based closed boron cluster M2BxHxA nano noble metal catalyst.
Preferably, in the step (1), the closed boron cluster M2BxHxThe M metal in the compound is any one of alkali metal elements Li, Na, K, Rb and Cs, and X is one of 6, 7, 8, 9, 10, 11 and 12.
Preferably, in the step (1), the halloysite and the closed boron cluster M2BxHxThe mass ratio of (A) to (B) is 1-5: 1.
Preferably, in the step (2), the soluble compound of the noble metal is at least one of chloroauric acid, chloroplatinic acid, chloropalladic acid, chlororuthenic acid, chloroaurate, chloroplatinate, chloroplatinite, chloropalladate, chlororuthenate, silver ammonia solution, gold chloride and greening platinum.
Preferably, in the step (2), the halloysite-based closed boron cluster M2BxHxThe mass ratio of the ultraviolet light to the noble metal chloride acid or the noble metal chloride salt is 10-50: 1, and the wavelength range of the ultraviolet light is 200-400 nm.
The catalyst can be single noble metal Au, Pd, Ag, Ru, etc., or two or more than two multi-metal nano materials, such as Au-Pd, Au-Ag, Au-Pd-Ag, etc.
The second scheme adopted by the invention for achieving the purpose is as follows: the optically active halloysite-based closed boron cluster M2BxHxPhotoactive halloysite-based closed boron cluster M prepared by preparation method of nano noble metal catalyst2BxHxThe application of the nano noble metal catalyst is applied to the selective reduction reaction of nitrobenzene compounds, and the specific operation is as follows: nitrobenzene compounds and halloysite-based closed boron cluster M2BxHxAdding the nano noble metal catalyst and the cocatalyst into the alcohol solution, mixing uniformly, and continuously filling N2And controlling the reaction temperature to be 10-30 ℃, and reacting completely under the irradiation of ultraviolet light to obtain azobenzene compounds and aniline compounds.
Preferably, the nitro compound and the halloysite-based closed boron cluster M2BxHxThe mass ratio of the nano noble metal catalyst to the cocatalyst is 3-5: 0.1-0.5: 0.5-1.
Preferably, the nitro compound is at least one of nitrobenzene, paranitrotoluene, m-nitrotoluene, p-nitrotoluene, 4-iodo-1-nitrobenzene, 3-fluoro-1-nitrobenzene, 1-fluoro-2-chloro-4-nitrobenzene, 4-ethyl nitrobenzene, 2,4, 6-trichloronitrobenzene, paranitrophenol, m-nitrophenol, p-nitrophenol and p-nitrobenzyl alcohol.
Preferably, the alcohol solution is any one of methanol, ethanol, isopropanol and n-butanol.
Preferably, the promoter is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
The invention has the following advantages and beneficial effects:
(1) the invention uses halloysite solid-supported closed boron cluster M for the first time2BxHxThe preparation method is simple and easy to regulate and control;
(2) the invention adopts halloysite-based closed boron cluster M2BxHxThe nanometer noble metal is used as a catalyst to reduce azo on nitrobenzene compounds, so that the conversion rate is high, and aniline or azobenzene can be selectively obtained by regulating and controlling conditions;
(3) the invention adopts halloysite-based closed boron cluster M2BxHxThe nanometer noble metal is used as a catalyst to reduce azo of nitrobenzene compounds, has the advantages of mild reaction, short reaction time, easy operation, good environment, high repeated utilization rate and the like, and is beneficial to the industrial production of converting the nitrobenzene compounds into azobenzene.
Drawings
FIG. 1 is a halloysite-based boron cluster Na prepared in example 12B12H12Fourier transform infrared spectroscopy (FTIR) pictures;
FIG. 2 is halloysite-based boron cluster Cs prepared in example 62B10H10X-ray photoelectron spectroscopy (XPS) images of the nano-palladium catalyst;
FIG. 3 is the halloysite-based boron cluster Rb prepared in example 92B12H12X-ray photoelectron spectroscopy (XPS) pictures of nano-Ag;
FIG. 4 is the halloysite-based boron cluster Na prepared in example 72B6H6Transmission Electron Microscopy (TEM) of nano Pd;
halloysite-based boron cluster Rb prepared in example 12 at FIG. 52B8H8Transmission Electron Microscopy (TEM) of nano Au.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1:
(1) 1.0012g of natural halloysite are dispersed in 50mL water, 0.2003g Na was added2B12H12Continuously stirring and reacting at 80 ℃;
(2) filtering after 12h, washing the filter cake with water and ethanol for 3 times in sequence, and vacuum drying the washed precipitate at room temperature for 12h to obtain 1.1924g of halloysite-based Na2B12H12The material is characterized by Fourier transform infrared spectroscopy (FT-IR), and as shown in figure 1, the successful combination of boron clusters and halloysite is proved;
(3) 1.1852g of halloysite-based Na2B12H12Dispersed in 20mL of water; rapidly adding 0.0251g of sodium chloroaurate with purity of 99%;
(4) stirring under 365nm ultraviolet lamp at 20 deg.C for 5min, and filtering to obtain dark purple precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 6 times, and vacuum drying the washed precipitate at room temperature for 18 hr to obtain 1.1911g halloysite Na2B12H12A nano-gold catalyst;
(6) 1.375g nitrobenzene, 20.13mL isopropanol, 0.1233g halloysite Na2B12H12Nanogold catalyst, 0.2855g NaOH, was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 3 hr, centrifuging to obtain filtrate, and separating with silica gel column chromatography to obtain azobenzene with yield of 89.5%.
Example 2:
(1) 1.0045g of natural halloysite was dispersed in 50mL of water and 0.4035g K was added2B12H12Continuously stirring and reacting at 100 ℃;
(2) filtering after 48h, washing a filter cake for 3 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 8h to obtain 1.3907g of halloysite K2B12H12;
(3) 1.3852g of halloysite base K2B12H12Dispersed in 20mL of water; 0.1574g of sodium chloropalladate with the purity of 99 percent is rapidly added;
(4) stirring under 395nm ultraviolet lamp at 40 deg.C for 10min, and filtering to obtain black precipitate;
(5) washing the precipitate with water and ethanol for 4 times, vacuum drying the washed precipitate at room temperature for 12 hr to obtain 1.3977g halloysite K2B12H12A nano-palladium catalyst;
(6) 2.759g of paranitrotoluene, 20.07mL of isopropanol, 0.4877g of halloysite K2B12H12Nano-Palladium catalyst, 0.2490g NaOH, was charged to a 50mL flask, N2Continuously stirring under protection, irradiating with 400nm ultraviolet lamp for 5h, centrifuging to obtain filtrate, and separating with chromatography silica gel column to obtain the product with yield of ortho-methyl azobenzene of 77.4%; the yield of the orthomethylaniline was 12.3%.
Example 3:
(1) 2.1566g of natural halloysite was dispersed in 50mL of water, 1.0608g of Cs was added2B12H12Continuously stirring at 90 ℃ for reaction;
(2) filtering after 48h, washing a filter cake for 3 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 24h to obtain 3.1754g of halloysite-based Cs2B12H12;
(3) 3.1750g of halloysite-based Cs2B12H12Dispersed in 50mL of water; 0.1439g of chloroplatinic acid with a purity of 99% were rapidly added;
(4) stirring under 365nm ultraviolet lamp at 50 deg.C for 30min, and filtering to obtain black precipitate;
(5) washing the precipitate with water and ethanol for 4 times, vacuum drying the washed precipitate at room temperature for 20 hr to obtain 3.2128g halloysite-based Cs2B12H12A nano platinum catalyst;
(6) 7.5044g of nitrobenzene, 20.54mL of isopropanol, 0.7519g of halloysite-based Cs2B12H12Nano platinum catalyst, 0.5704g KOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 200nm ultraviolet lamp for 6 hr, centrifuging to obtain filtrate, and separating with silica gel column chromatography to obtain azobenzene with yield of 87.1%.
Example 4:
(1) 5.083 will be mixed0g of natural halloysite dispersed in 50mL of water was added 5.0731g of Na2B12H12Continuously stirring and reacting at 100 ℃;
(2) filtering after 48h, washing the filter cake with water and ethanol for 5 times in turn, and vacuum drying the washed precipitate at room temperature for 24h to obtain 9.8851g of halloysite-based Na2B12H12;
(3) 9.4018g of halloysite-based Na2B12H12Dispersed in 20mL of water; 0.4810g of chloroauric acid with a purity of 99% were rapidly added;
(4) stirring under 395nm ultraviolet lamp at 25 deg.C for 30min, and filtering to obtain dark purple precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 5 times, vacuum drying the washed precipitate at room temperature for 12 hr to obtain 9.4866g halloysite Na2B12H12A nano-gold catalyst;
(6) 10.2086g of 4-iodo-1-nitrobenzene, 20.04mL of ethanol, 2.0074g of halloysite Na2B12H12Nanogold catalyst, 2.0105g LiOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 6 hr, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain 4,4' -diiodoazobenzene with yield of 70.5%. The yield of 4-iodo-1-aniline was 18.1%.
Example 5:
(1) 1.0012g of natural halloysite were dispersed in 50mL of water, 0.2003g of Na was added2B12H12Continuously stirring and reacting at 80 ℃;
(2) filtering after 12h, washing the filter cake with water and ethanol for 3 times in sequence, and vacuum drying the washed precipitate at room temperature for 12h to obtain 1.1924g of halloysite-based Na2B12H12;
(3) 1.1852g of halloysite-based Na2B12H12Dispersed in 20mL of water; rapidly adding 0.0251g of sodium chloroaurate with purity of 99%;
(4) stirring under 365nm ultraviolet lamp at 20 deg.C for 5min, and filtering to obtain dark purple precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 6 times, and vacuum drying the washed precipitate at room temperature for 18 hr to obtain 1.1911g halloysite Na2B12H12A nano-gold catalyst;
(6) 1.375g of nitrobenzene, 20.1743g of isopropanol, 0.1233g of halloysite Na2B12H12Nanogold catalyst, 0.2855g NaOH, was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 3 hr, centrifuging to obtain filtrate, and separating with silica gel column chromatography to obtain azobenzene with yield of 89.5%.
Example 6:
(1) 2.4617g of natural halloysite was dispersed in 50mL of water, 1.9684g of Cs was added2B10H10Continuously stirring and reacting at 85 ℃;
(2) filtering after 48h, washing a filter cake for 5 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 24h to obtain 3.9881g of halloysite-based Cs2B10H10;
(3) 3.9880g of halloysite-based Cs2B10H10Dispersed in 20mL of water; 0.0996g of chloropalladic acid with a purity of 99% was added rapidly;
(4) stirring under 365nm ultraviolet lamp at 20 deg.C for 5min, and filtering to obtain dark black precipitate;
(5) washing the precipitate with water and ethanol for 4 times, vacuum drying the washed precipitate at room temperature for 12 hr to obtain 4.0742g halloysite-based Cs2B10H10A nano palladium catalyst. Prepared halloysite-based Cs2B10H10The nano-palladium catalyst was characterized by X-ray photoelectron spectroscopy (XPS), as shown in fig. 2, from which palladium nanoparticles having a valence of 0 could be seen;
(6) 2.4975g of nitrobenzene, 20.08mL of n-butanol, 0.2501g of halloysite-based Cs2B10H10Nano-palladium catalyst, 0.2475g LiOH was added to a 50mL flask, N2Stirring continuously under protection, irradiating with 395nm ultraviolet lamp for 5 hr, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain anilineThe ratio was 79.8%.
Example 7:
(1) 3.8150g of natural halloysite were dispersed in 50mL of water, 0.9474g of Na was added2B6H6Continuously stirring for reaction at 95 ℃;
(2) filtering after 48h, washing the filter cake with water and ethanol for 5 times in sequence, and vacuum drying the washed precipitate at room temperature for 12h to obtain 4.7011g of halloysite-based Na2B6H6;
(3) 4.2816g of halloysite-based Na2B6H6Dispersed in 20mL of water; 0.1701g of sodium chloropalladate with the purity of 99 percent is rapidly added;
(4) stirring under 365nm ultraviolet lamp at 50 deg.C for 20min, and filtering to obtain black precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 4 times, vacuum drying the washed precipitate at room temperature for 24 hr to obtain 4.4010g halloysite Na2B6H6Nano palladium catalyst, prepared halloysite Na2B6H6The nano palladium catalyst is characterized by a Transmission Electron Microscope (TEM), as shown in FIG. 4, the reduced nano Pd has small particle size and uniform distribution;
(6) 5.6610g of 3-fluoro-1-nitrobenzene, 20.51mL of isopropanol, 0.5610g of halloysite Na2B6H6Nano-Palladium catalyst, 1.1184g NaOH, was charged to a 50mL flask, N2Continuously stirring under protection, irradiating with 395nm ultraviolet lamp for 3 hr, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain 3, 3' -difluoroazobenzene with yield of 39.5%; the yield of 3-fluoro-1-aniline was 47.1%.
Example 8:
(1) 1.4861g of natural halloysite were dispersed in 50mL of water, 0.5042g of Li were added2B10H10Continuously stirring and reacting at 80 ℃;
(2) filtering after 12h, washing filter cake for 3 times by water and ethanol in turn, placing washed precipitate at room temperature for vacuum drying for 12h to obtain 1.9174g halloysite-based Li2B10H10;
(3) 1.5003g of halloysite-based Na2B12H12Dispersed in 20mL of water; 0.0995g of sodium chloroplatinate with a purity of 99% was added rapidly;
(4) stirring under 395nm ultraviolet lamp at 50 deg.C for 25min, and filtering to obtain black precipitate;
(5) washing the precipitate with water and ethanol for 4 times, vacuum drying the washed precipitate at room temperature for 12 hr to obtain 1.5398g halloysite-based Li2B10H10A nano platinum catalyst;
(6) 2.6185g of 2,4, 6-trichloronitrobenzene, 20.03mL of isopropanol, 0.5233g of Li2B10H10Nano platinum catalyst, 0.2601g KOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 6 hr, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain 2,4, 6-trichloroaniline with yield of 85.0%.
Example 9:
(1) 1.0003g of natural halloysite was dispersed in 50mL of water and 0.1998g of Rb were added2B12H12Continuously stirring and reacting at 100 ℃;
(2) filtering after 48h, washing the filter cake with water and ethanol for 5 times in sequence, and vacuum drying the washed precipitate at room temperature for 8h to obtain 1.1976g of halloysite-based Rb2B12H12;
(3) 1.1801g of halloysite-based Rb2B12H12Dispersed in 20mL of water; rapidly adding 0.0236g of silver nitrate with the purity of 99 percent;
(4) stirring under 365nm ultraviolet lamp at 30 deg.C for 10min, and filtering to obtain light yellow precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 5 times, and vacuum drying the washed precipitate at room temperature for 18 hr to obtain 1.2193g of halloysite Rb2B12H12Nano silver catalyst, halloysite-based Rb prepared by using nano silver catalyst2B12H12The nanosilver catalyst was characterized by X-ray photoelectron spectroscopy (XPS), as shown in fig. 3, from which it can be seen that: the generation of 0-valent Ag is proved;
(6) 1.6881g of nitrobenzene, 20.13mL of isopropanol, 0.2812g of halloysite Rb2B12H12Nano silver catalyst, 0.2805g LiOH was added to a 50mL flask, N2Stirring continuously under protection, irradiating with 395nm ultraviolet lamp for 0.5 hr, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain azobenzene with yield of 49.5%.
Example 10:
(1) 5.5704g of natural halloysite were dispersed in 50mL of water, 1.1135g of Na was added2B12H12Continuously stirring and reacting at 80 ℃;
(2) filtering after 12h, washing the filter cake with water and ethanol for 3 times in sequence, and vacuum drying the washed precipitate at room temperature for 12h to obtain 6.6692g of halloysite-based Na2B12H12;
(3) 5.8260g of halloysite-based Na2B12H12Dispersed in 20mL of water; 0.5854g of a silver ammonia solution with a purity of 99% prepared from silver nitrate was added rapidly;
(4) stirring under 365nm ultraviolet lamp at 40 deg.C for 30min, and filtering to obtain brown yellow precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 5 times, vacuum drying the washed precipitate at room temperature for 24 hr to obtain 6.3011g halloysite Na2B12H12A nano-silver catalyst;
(6) 10.1849g of 4-ethyl-1-nitrobenzene, 20.04mL of isopropanol, 2.0603g of halloysite Na2B12H12Nano silver catalyst, 1.0281g LiOH was added to a 50mL flask, N2Stirring continuously under protection, irradiating with 365nm ultraviolet lamp for 5 hr, centrifuging to obtain filtrate, and separating with silica gel column chromatography to obtain 4,4' -diethyl azobenzene with yield of 81.1%.
Example 11:
(1) 1.8018g of natural halloysite was dispersed in 50mL of water, 0.9010g of Cs was added2B12H12Continuously stirring and reacting at 100 ℃;
(2) filtering after 12h, washing the filter cake with water and ethanol for 5 times in sequence, and placing the washed precipitate in a containerVacuum drying at room temperature for 24h to obtain 2.6814g halloysite-based Cs2B12H12;
(3) 2.4725g of halloysite-based Cs2B12H12Dispersed in 20mL of water; 0.1214g of chlororuthenic acid having a purity of 99% were rapidly added;
(4) stirring under 395nm ultraviolet lamp at 25 deg.C for 10min, and filtering to obtain black precipitate;
(5) washing the precipitate with water and ethanol for 4 times, and vacuum drying the washed precipitate at room temperature for 18 hr to obtain 2.5811g halloysite-based Cs2B12H12A nano ruthenium catalyst;
(6) 8.0012g of p-nitrobenzyl alcohol, 20.08mL of methanol, 1.0004g of halloysite-based Cs2B12H12Nano ruthenium catalyst, 1.9894g NaOH, was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 3 hr, centrifuging to obtain filtrate, and separating with chromatography silica gel column to obtain p-aminobenzyl alcohol with yield of 66.1%.
Example 12:
(1) 6.7150g of natural halloysite were dispersed in 50mL of water and 4.008g of Rb were added2B8H8Continuously stirring and reacting at 100 ℃;
(2) filtering after 8h, washing the filter cake for 3 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 24h to obtain 10.0017g of halloysite-based Rb2B8H8;
(3) 7.0416g of halloysite-based Rb2B8H8Dispersed in 20mL of water; 0.2007g of sodium chloroaurate with a purity of 99% were added rapidly;
(4) stirring under 365nm ultraviolet lamp at 45 deg.C for 5min, and filtering to obtain dark purple precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 5 times, and vacuum drying the washed precipitate at room temperature for 24 hr to obtain 7.2017g of halloysite Rb2B8H8Nano gold catalyst, prepared halloysite-based Rb2B8H8Transmission of nano-gold catalystThe characteristics of electron microscopy (TEM) are shown in FIG. 5, and it can be seen from the graph that the nano gold particles are uniformly distributed and have smaller particle size;
(6) 8.0006g of p-nitrobenzyl alcohol, 20.18mL of isopropanol, 2.6706g of halloysite Rb2B8H8Nanogold catalyst, 2.6614g NaOH, was added to a 50mL flask, N2Stirring under protection, irradiating with 395nm ultraviolet lamp for 3 hr, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain 4,4' -azobenzene benzyl ethanol with yield of 58.9% and p-aminobenzyl alcohol with yield of 19.5%.
Example 13:
(1) 1.5011g of natural halloysite were dispersed in 50mL of water, 0.6004g of Li were added2B12H12Continuously stirring at 90 ℃ for reaction;
(2) filtering after 24h, washing a filter cake for 5 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 24h to obtain 2.0015g of halloysite-based Li2B12H12;
(3) 1.4955g of halloysite-based Li2B12H12Dispersed in 20mL of water; 0.0992g of sodium chloropalladate with the purity of 99 percent is rapidly added;
(4) stirring under 365nm ultraviolet lamp at 20 deg.C for reaction for 15min, and filtering to obtain black precipitate;
(5) washing precipitate with water and ethanol for 5 times, vacuum drying at room temperature for 8 hr to obtain 1.5027g halloysite-based Li2B12H12A nano-palladium catalyst;
(6) 1.1506g of p-nitrophenol, 20.12mL of ethanol, 0.2610g of halloysite-based Li2B12H12Nano-palladium catalyst, 0.1301g LiOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 6 hr, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain p-aminophenol with yield of 70.6%.
Example 14:
(1) 2.5001g of natural halloysite was dispersed in 50mL of water, 1.9902g of Cs was added2B6H6,80℃Continuously stirring for reaction;
(2) filtering after 24h, washing a filter cake for 5 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 24h to obtain 4.3995g of halloysite-based Cs2B6H6;
(3) 4.0012g of halloysite-based Cs2B6H6Dispersed in 20mL of water; 0.1334g of ammonium chlororuthenate with a purity of 99% is rapidly added;
(4) stirring under 395nm ultraviolet lamp at 25 deg.C for 30min, and filtering to obtain black precipitate;
(5) washing the precipitate with water and ethanol for 5 times, vacuum drying the washed precipitate at room temperature for 24 hr to obtain 4.1004g halloysite-based Cs2B6H6A nano ruthenium catalyst;
(6) 5.0002g of 1-fluoro-2-chloro-4-nitrobenzene, 20.00mL of isopropanol, 0.4998g of halloysite-based Cs2B6H6Nano ruthenium catalyst, 1.0080g NaOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 395nm ultraviolet lamp for 5 hr, centrifuging to obtain filtrate, and separating with silica gel column chromatography to obtain 1,1 '-difluoro-2, 2' -dichloro-azobenzene with a yield of 25.2%; the yield of 1-fluoro-2-chloro-aniline was 69.9%.
Example 15:
(1) 6.0018g of natural halloysite were dispersed in 50mL of water, 1.9901g of Na was added2B10H10Continuously stirring and reacting at 100 ℃;
(2) filtering after 48h, washing the filter cake with water and ethanol for 5 times in sequence, and vacuum drying the washed precipitate at room temperature for 20h to obtain 7.9514g of halloysite-based Na2B10H10;
(3) 7.9510g of halloysite-based Na2B10H10Dispersed in 20mL of water; 0.3892g of sodium chloroplatinate with a purity of 99% was added rapidly;
(4) stirring under 365nm ultraviolet lamp at 50 deg.C for 30min, and filtering to obtain black precipitate;
(5) filtering the precipitate, washing with water and ethanol for 4 times, and washing the precipitateThe precipitate was dried under vacuum at room temperature for 24h to give 8.3018g of halloysite-based Na2B10H10A nano platinum catalyst;
(6) 5.6017g of p-nitrotoluene, 20.08mL of isopropanol, 0.1109g of halloysite Na2B10H10Nano platinum catalyst, 0.1129g NaOH was added to a 50mL flask, N2Stirring continuously under protection, irradiating with 365nm ultraviolet lamp for 1h, centrifuging to obtain filtrate, and separating with chromatography silica gel column to obtain 4,4' -azotoluene with yield of 85.2%.
Example 16:
(1) 2.4001g of natural halloysite was dispersed in 50mL of water and 0.5990g K was added2B8H8Continuously stirring for reaction at 95 ℃;
(2) filtering after 48h, washing a filter cake for 5 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 24h to obtain 2.8901g of halloysite K2B8H8;
(3) 2.8809g of halloysite base K2B8H8Dispersed in 20mL of water; 0.0570g of silver nitrate with a purity of 99% were added rapidly;
(4) stirring under 365nm ultraviolet lamp at 25 deg.C for 30min, and filtering to obtain brown yellow precipitate;
(5) washing the precipitate with water and ethanol for 4 times, vacuum drying the washed precipitate at room temperature for 18 hr to obtain 2.9112g halloysite K2B8H8A nano-silver catalyst;
(6) 5.0041g of chloronitrobenzene, 20.03mL of n-butanol, 1.0000g of halloysite K2B8H8Nano silver catalyst, 0.9992g NaOH, was added to a 50mL flask, N2Stirring continuously under protection, irradiating with 365nm ultraviolet lamp for 5 hr, centrifuging to obtain filtrate, and separating with silica gel column chromatography to obtain 2, 2' -dichloroazobenzene with yield of 95.4%.
Example 17:
(1) 1.0008g of natural halloysite dispersed in 50mL of water was added 0.2005g K2B12H12Continuously stirring and reacting at 80 ℃;
(2) filtering after 12h, washing a filter cake for 5 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 24h to obtain 1.1988g of halloysite K2B12H12;
(3) 1.1800g of halloysite base K2B12H12Dispersed in 20mL of water; 0.0301g of sodium chloropalladate with the purity of 99 percent is rapidly added;
(4) stirring under 365nm ultraviolet lamp at 20 deg.C for 5min, and filtering to obtain black precipitate;
(5) washing the precipitate with water and ethanol for 3 times, vacuum drying at room temperature for 12 hr to obtain 1.1992g halloysite K2B12H12A nano-palladium catalyst;
(6) 7.0322g of nitrobenzene, 20.02mL of isopropanol, 1.1694g of halloysite K2B12H12Nano-palladium catalyst, 2.3370g KOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 0.5h, centrifuging to obtain filtrate, and separating with chromatography silica gel column to obtain azobenzene with yield of 97.0%.
Example 18:
(1) 3.0008g of natural halloysite were dispersed in 50mL of water, 2.0012g of Na was added2B6H6Continuously stirring and reacting at 100 ℃;
(2) filtering after 24h, washing a filter cake for 5 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 8h to obtain 4.9980g of halloysite-based Na2B6H6;
(3) 3.5003g of halloysite-based Na2B6H6Dispersed in 20mL of water; rapidly adding 0.1005g of chloroplatinic acid with the purity of 99 percent;
(4) stirring under 365nm ultraviolet lamp at 45 deg.C for 30min, and filtering to obtain black precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 5 times, vacuum drying the washed precipitate at room temperature for 24 hr to obtain 3.5090g halloysite Na2B6H6A nano platinum catalyst;
(6) 1.0008g of p-nitroaniline, 20.00mL of methanol, 0.1997g of halloysite Na2B6H6Nano platinum catalyst, 0.9991g KOH was added to a 50mL flask, N2Stirring continuously under protection, irradiating with 365nm ultraviolet lamp for 5 hr, centrifuging to obtain filtrate, and separating with silica gel column chromatography to obtain 4,4' -diaminoazobenzene with yield of 81.1%.
Example 19:
(1) 5.6118g of natural halloysite were dispersed in 50mL of water, 4.2080g of Na was added2B10H10Continuously stirring and reacting at 85 ℃;
(2) filtering after 24h, washing the filter cake with water and ethanol for 5 times in sequence, and vacuum drying the washed precipitate at room temperature for 24h to obtain 9.8001g of halloysite-based Na2B10H10;
(3) 8.1034g of halloysite-based Na2B10H10Dispersed in 20mL of water; rapidly adding 0.1618g of sodium chloroaurate with purity of 99%;
(4) stirring and reacting for 5min at 20 ℃ under a 370nm ultraviolet lamp, and filtering to obtain a purple precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 5 times, vacuum drying the washed precipitate at room temperature for 24 hr to obtain 8.1595g halloysite Na2B10H10A nano-gold catalyst;
(6) 9.0005g of p-nitrotoluene, 20.03mL of isopropanol, 2.9995g of halloysite Na2B10H10Nanogold catalyst, 1.5002g NaOH, was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 4 hr, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain 4,4' -azotoluene with yield of 90.6%.
Example 20:
(1) 1.0005g of natural halloysite was dispersed in 50mL of water and 0.39982g K was added2B6H6Continuously stirring and reacting at 100 ℃;
(2) filtering after 24h, washing the filter cake with water and ethanol for 5 times in sequence, and placing the washed precipitate at room temperatureVacuum drying for 18h to obtain 1.3522g halloysite-based K2B6H6;
(3) 1.0014g of halloysite-based K2B6H6Dispersed in 20mL of water; rapidly adding 0.0288g of silver ammonia solution prepared by silver nitrate with the purity of 99 percent;
(4) stirring under 365nm ultraviolet lamp at 20 deg.C for 15min, and filtering to obtain light yellow precipitate;
(5) washing the precipitate with water and ethanol for 3 times, vacuum drying the washed precipitate at room temperature for 10 hr to obtain 1.0214g halloysite K2B6H6A nano-silver catalyst;
(6) 5.5012g of p-nitroacetophenone, 20.02mL of methanol, 0.5501g of halloysite K2B6H6Nano silver catalyst, 1.0914g KOH, was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 5h, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain 4,4' -ethanolazobenzene with a yield of 55.1%; the yield of p-aminoacetophenone was 45.5%.
Example 21:
(1) 4.0831g of natural halloysite was dispersed in 50mL of water and 2.3890g K was added2B12H12Continuously stirring and reacting at 100 ℃;
(2) filtering after 24h, washing a filter cake for 3 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 24h to obtain 6.4511g of halloysite K2B12H12;
(3) 6.4510g of halloysite-based Cs2B12H12Dispersed in 20mL of water; 0.8051g of sodium chloroplatinate with a purity of 99% was added rapidly;
(4) stirring under 395nm ultraviolet lamp at 40 deg.C for 25min, and filtering to obtain black precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 5 times, and vacuum drying the washed precipitate at room temperature for 24 hr to obtain 7.1099g halloysite K2B12H12A nano platinum catalyst;
(6) 5.0004g of paranitrophenol, 20.28mL of ethanol, 0.6218g of halloysite K2B12H12Nano platinum catalyst, 0.6203g NaOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with an ultraviolet lamp of 370nm for 5h, centrifuging to obtain filtrate, and separating with silica gel column chromatography to obtain paranitroaniline with yield of 83.2%.
Example 22:
(1) 9.8112g of natural halloysite was dispersed in 50mL of water and 2.4510g K was added2B8H8Continuously stirring and reacting at 85 ℃;
(2) filtering after 12h, washing filter cake with water and ethanol for 4 times in sequence, and vacuum drying the washed precipitate at room temperature for 24h to obtain 12.2049g halloysite K2B8H8;
(3) 12.2001g of halloysite base K2B8H8Dispersed in 20mL of water; rapidly adding 0.2438g of chloroplatinic acid with the purity of 99%;
(4) stirring under 375nm ultraviolet lamp at 40 deg.C for 30min, and filtering to obtain black precipitate;
(5) washing the precipitate with water and ethanol for 3 times, vacuum drying at room temperature for 20 hr to obtain 12.4031g halloysite K2B8H8A nano platinum catalyst;
(6) 5.0007g of m-nitrophenol, 20.00mL of isopropanol, 1.6674g of halloysite K2B8H8Nano platinum catalyst, 0.8334g CsOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 5h, centrifuging to obtain filtrate, and separating with chromatography silica gel column to obtain m-nitroaniline with yield of 77.6%.
Example 23:
(1) 3.0005g of natural halloysite was dispersed in 50mL of water and 1.9958g of Rb were added2B12H12Continuously stirring and reacting at 100 ℃;
(2) filtering after 24h, washing a filter cake for 5 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 12h to obtain 4.8952g of halloysite-based Rb2B12H12;
(3) 4.0005g of halloysite-based Rb2B12H12Dispersed in 20mL of water; 0.3979g of sodium chloroaurate with a purity of 99% were added rapidly;
(4) stirring under 365nm ultraviolet lamp at 20 deg.C for 5min, and filtering to obtain dark purple precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 4 times, and vacuum drying the washed precipitate at room temperature for 12 hr to obtain 4.3074g of halloysite Rb2B12H12A nano-gold catalyst;
(6) 0.5419g of p-nitrobenzonitrile, 20.10mL of n-butanol, 0.1052g of halloysite Rb2B12H12Nanogold catalyst, 0.0498g NaOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 4h, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain 4,4' -azobisbenzonitrile with a yield of 80.6%.
Example 24:
(1) 9.0095g of natural halloysite were dispersed in 50mL of water, 3.0010g of Li were added2B6H6Continuously stirring and reacting at 80 ℃;
(2) filtering after 12h, washing a filter cake for 5 times by using water and ethanol in sequence, and placing the washed precipitate at room temperature for vacuum drying for 8h to obtain 12.0010g of halloysite-based Li2B6H6;
(3) 12.0001g of halloysite-based Li2B6H6Dispersed in 20mL of water; 0.2659g of ammonium chlororuthenate with a purity of 99% is rapidly added;
(4) stirring under 390nm ultraviolet lamp at 25 deg.C for 15min, and filtering to obtain black precipitate;
(5) washing the precipitate with water and ethanol for 4 times, and vacuum drying the washed precipitate at room temperature for 18 hr to obtain 2.5811g halloysite-based Li2B6H6A nano ruthenium catalyst;
(6) 5.0045g of p-nitrobenzonitrile, 20.08mL of isopropanol, 0.4995g of halloysite-based Li2B6H6Nano ruthenium catalyst, 0.5001g NaOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 4h, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain 4,4' -azodibenzoyl nitrile with yield of 28.8%; the yield of p-aminobenzonitrile was 69.3%.
Example 25:
(1) 5.9860g of natural halloysite was dispersed in 50mL of water and 4.4889g K was added2B8H8Continuously stirring and reacting at 85 ℃;
(2) filtering after 12h, washing filter cake with water and ethanol for 4 times in sequence, and vacuum drying the washed precipitate at room temperature for 15h to obtain 10.0117g halloysite K2B8H8;
(3) 10.0005g of halloysite base K2B8H8Dispersed in 20mL of water; rapidly adding 0.5001g of ammonium chlororuthenate with the purity of 99 percent;
(4) stirring under 365nm ultraviolet lamp at 35 deg.C for 15min, and filtering to obtain black precipitate;
(5) washing the precipitate with water and ethanol for 4 times, vacuum drying the washed precipitate at room temperature for 20 hr to obtain 10.4517g halloysite K2B8H8A nano ruthenium catalyst;
(6) 0.8810g of nitrobenzene, 20.03mL of isopropanol, 0.1093g of halloysite K2B8H8Nano ruthenium catalyst, 0.1081g NaOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 3h, centrifuging to obtain filtrate, and separating with chromatographic silica gel column to obtain azobenzene with yield of 76.0%.
Example 26:
(1) 1.8155g of natural halloysite were dispersed in 50mL of water, 1.2101g of Na was added2B12H12Continuously stirring at 90 ℃ for reaction;
(2) filtering after 12h, washing the filter cake with water and ethanol for 3 times in sequence, and vacuum drying the washed precipitate at room temperature for 18h to obtain 2.9150g of halloysite-based Na2B12H12;
(3) 2.2144g of halloysite-based Na2B12H12Dispersed in 20mL of water; 0.1469g of silver nitrate with a purity of 99% were added rapidly;
(4) stirring under 365nm ultraviolet lamp at 20 deg.C for 5min, and filtering to obtain brown yellow precipitate;
(5) filtering the precipitate, washing the precipitate with water and ethanol for 3 times, vacuum drying the washed precipitate at room temperature for 12 hr to obtain 2.3091g halloysite Na2B12H12A nano-silver catalyst;
(6) 1.8460g of m-nitrotoluene, 20.06mL of isopropanol, 0.1837g of halloysite Na2B12H12Nano silver catalyst, 0.3592g KOH was added to a 50mL flask, N2Continuously stirring under protection, irradiating with 365nm ultraviolet lamp for 3 hr, centrifuging to obtain filtrate, and separating with silica gel column chromatography to obtain 3, 3' -dimethyl azobenzene with yield of 64.8%.
Example 27:
this example prepares halloysite-based Na2B12H12The method of the nano gold catalyst is the same as that of example 1, except that the catalyst is recycled for the second time, nitrobenzene, alcohols, the catalyst, the cocatalyst and the like are added according to the same proportion, and the yield of azobenzene obtained by separating through a chromatographic silica gel column is 88.3%. The azobenzene is recycled for the third time, nitrobenzene, alcohols, a catalyst, a cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 87.1 percent. The azobenzene is recycled for the fourth time, nitrobenzene, alcohols, catalyst, cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 85.0 percent. The azobenzene is recycled for the fifth time, nitrobenzene, alcohols, catalyst, cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 81.1 percent. And recycling for the sixth time, adding nitrobenzene, alcohols, a catalyst, a cocatalyst and the like according to the same proportion, and separating by a chromatographic silica gel column to obtain the azobenzene with the yield of 80.7 percent. The eighth time of recycling, nitrobenzene, alcohols, catalyst, cocatalyst and the like are added according to the same proportion,the azobenzene yield by column chromatography on silica gel was 78.1%. And the azobenzene is recycled for the ninth time, nitrobenzene, alcohols, a catalyst, a cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 75.6 percent. The product is reused for the tenth time, nitrobenzene, alcohols, catalyst, cocatalyst and the like are added according to the same proportion, and the yield of azobenzene obtained by separating through a chromatographic silica gel column is 71.4 percent.
Example 28:
this example prepares halloysite-based Cs2B10H10The method of the nano palladium catalyst is the same as that of example 6, except that the catalyst is recycled for the second time, nitrobenzene, alcohols, the catalyst, the cocatalyst and the like are added according to the same proportion, and the yield of aniline obtained by separating through a chromatographic silica gel column is 79.0%. The third time of recycling, and adding nitrobenzene, alcohols, catalyst, cocatalyst and the like according to the same proportion, and the yield of azobenzene obtained by separating through a chromatographic silica gel column is 78.3%. The azobenzene is recycled for the fourth time, nitrobenzene, alcohols, catalyst, cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 78.0 percent. The azobenzene is recycled for the fifth time, nitrobenzene, alcohols, catalyst, cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 76.9 percent. And recycling for the sixth time, adding nitrobenzene, alcohols, a catalyst, a cocatalyst and the like according to the same proportion, and separating by a chromatographic silica gel column to obtain the azobenzene with the yield of 76.1 percent. And the azobenzene is recycled for the eighth time, nitrobenzene, alcohols, a catalyst, a cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 72.2 percent. And the azobenzene is recycled for the ninth time, nitrobenzene, alcohols, a catalyst, a cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 70.6 percent. The product is reused for the tenth time, nitrobenzene, alcohols, catalyst, cocatalyst and the like are added according to the same proportion, and the yield of azobenzene obtained by separating through a chromatographic silica gel column is 67.6 percent.
Example 29:
this example prepares a halloysite base K2B12H12The method of the nano palladium catalyst was the same as that of example 17 except that the catalyst was reused for the second time, nitrobenzene, alcohols, catalyst, co-catalyst and the like were added in the same ratio, and the yield of azobenzene obtained by separation with a column chromatography silica gel was 64.1%. The third time of recycling, and adding 4-ethyl nitrobenzene, alcohols, catalyst, cocatalyst and the like according to the same proportion, and obtaining the azobenzene yield of 63.7% by separating through a chromatographic silica gel column. The azobenzene is recycled for the fourth time, 4-ethyl nitrobenzene, alcohols, a catalyst, a cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 62.1 percent. The fifth time of recycling, and add 4-ethyl nitrobenzene, alcohols, catalyst, cocatalyst, etc. according to the same proportion, the azobenzene yield obtained by the separation of the chromatographic silica gel column is 60.4%. And recycling for the sixth time, adding 4-ethyl nitrobenzene, alcohols, a catalyst, a cocatalyst and the like according to the same proportion, and separating by a chromatographic silica gel column to obtain the azobenzene with the yield of 59.7 percent. And the azobenzene is recycled for the eighth time, 4-ethyl nitrobenzene, alcohols, a catalyst, a cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 58.4 percent. And the azobenzene is recycled for the ninth time, 4-ethyl nitrobenzene, alcohols, a catalyst, a cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 56.1 percent. The product is reused for the tenth time, 4-ethyl nitrobenzene, alcohols, catalyst, cocatalyst and the like are added according to the same proportion, and the yield of azobenzene obtained by separating through a chromatographic silica gel column is 55.3 percent.
Example 30:
this example prepares a halloysite base K2B12H12The process of the nanogold catalyst was the same as in example 17, except that the catalyst was reused for the second time, nitrobenzene, alcohols, catalyst, promoter and the like were added in the same ratio, and the yield of azobenzene obtained by separation with a column chromatography silica gel was 88.6%. The nitrobenzene, the alcohols, the catalyst and the cocatalyst are added according to the same proportion for the third time of recyclingReagent, etc. and the azobenzene yield obtained by separating the mixture through a chromatographic silica gel column is 80.1 percent; the yield of aniline was 7.1%. The fourth time of recycling, nitrobenzene, alcohols, catalyst, cocatalyst and the like are added according to the same proportion, and the yield of azobenzene obtained by separating through a chromatographic silica gel column is 71.8 percent; the yield of aniline was 10.5%. The azobenzene is recycled for the fifth time, nitrobenzene, alcohols, a catalyst, a cocatalyst and the like are added according to the same proportion, and the yield of the azobenzene obtained by separating through a chromatographic silica gel column is 65.3 percent; the yield of aniline was 19.1%. Recycling for the sixth time, adding nitrobenzene, alcohols, a catalyst, a cocatalyst and the like according to the same proportion, and separating through a chromatographic silica gel column to obtain the azobenzene with the yield of 58.1 percent; the yield of aniline was 30.1%. Recycling for the eighth time, adding nitrobenzene, alcohols, a catalyst, a cocatalyst and the like according to the same proportion, and separating through a chromatographic silica gel column to obtain azobenzene with the yield of 45.1%; the yield of aniline was 40.4%. The ninth time is recycled, nitrobenzene, alcohols, catalyst, cocatalyst and the like are added according to the same proportion, and the yield of azobenzene obtained by separating through a chromatographic silica gel column is 44.7 percent; the yield of aniline was 40.5%. Recycling for the tenth time, adding nitrobenzene, alcohols, a catalyst, a cocatalyst and the like according to the same proportion, and separating through a chromatographic silica gel column to obtain the azobenzene with the yield of 44.5 percent; the yield of aniline was 40.7%.
Example 31:
this example prepares halloysite-based Li2B6H6The method of the nano ruthenium catalyst is the same as that in example 24, except that the catalyst is recycled for the second time, and p-nitrobenzonitrile, alcohols, a catalyst, a cocatalyst and the like are added according to the same proportion, and the yield of the 4,4' -azodibenzonitrile obtained by the separation of the chromatographic silica gel column is 25.1%; the yield of p-aminobenzonitrile was 67.0%. The third time of recycling, adding p-nitrobenzonitrile, alcohols, a catalyst, a cocatalyst and the like according to the same proportion, and obtaining the 4,4' -azodibenzonitrile with the yield of 24.7 percent through the separation of a chromatographic silica gel column; the yield of p-aminobenzonitrile was 66.3%. The fourth time of recycling, and adding p-nitrobenzonitrile, alcohols, methanol, ethanol, methanol, ethanol, methanol, ethanol, methanol, ethanol, methanol, ethanol, water and the like,The yield of the catalyst, the cocatalyst and the like, which are separated by a chromatographic silica gel column, of the 4,4' -azodibenzonitrile is 21.3 percent; the yield of p-aminobenzonitrile was 64.7%. The fifth time of recycling, and adding p-nitrobenzonitrile, alcohols, a catalyst, a cocatalyst and the like according to the same proportion, and separating through a chromatographic silica gel column to obtain 4,4' -azodibenzonitrile with the yield of 19.9%; the yield of p-aminobenzonitrile was 64.1%. The product is recycled for the sixth time, the p-nitrobenzonitrile, the alcohols, the catalyst, the cocatalyst and the like are added according to the same proportion, and the yield of the 4,4' -azodibenzonitrile obtained by the separation of the chromatographic silica gel column is 19.4 percent; the yield of p-aminobenzonitrile was 63.7%. The eighth time of recycling, adding the p-nitrobenzonitrile, the alcohols, the catalyst, the cocatalyst and the like according to the same proportion, and obtaining the 4,4' -azodibenzonitrile with the yield of 19.1 percent through the separation of a chromatographic silica gel column; the yield of p-aminobenzonitrile was 63.2%. The ninth time is recycled, the p-nitrobenzonitrile, the alcohols, the catalyst, the cocatalyst and the like are added according to the same proportion, and the yield of the 4,4' -azodibenzonitrile obtained by the separation of the chromatographic silica gel column is 18.3 percent; the yield of p-aminobenzonitrile was 60.7%. The mixture is recycled for the tenth time, p-nitrobenzonitrile, alcohols, a catalyst, a cocatalyst and the like are added according to the same proportion, and the yield of the 4,4' -azodibenzonitrile obtained by the separation of a chromatographic silica gel column is 17.7 percent; the yield of p-aminobenzonitrile was 59.8%.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. Photoactive halloysite-based closed boron cluster M2BxHxThe preparation method of the nano noble metal catalyst is characterized by comprising the following steps:
(1) dispersing natural halloysite in water, adding closed boron cluster M2BxHx,80~10Stirring at 0 ℃ until the reaction is complete, filtering, washing and drying after the reaction is finished to obtain the halloysite boron cluster M2BxHx;
(2) Grouping the halloysite-based boron clusters M2BxHxDispersing in water, adding a soluble compound of noble metal, stirring and reacting under ultraviolet irradiation at 20-50 ℃ until the reaction is complete, filtering, washing and drying after the reaction is finished to obtain the halloysite-based closed boron cluster M2BxHxA nano noble metal catalyst.
2. The photoactive halloysite-based closed boron cluster M of claim 12BxHxThe preparation method of the nano noble metal catalyst is characterized by comprising the following steps: in the step (1), the closed boron cluster M2BxHxThe M metal in the compound is any one of alkali metal elements Li, Na, K, Rb and Cs, and X is one of 6, 7, 8, 9, 10, 11 and 12.
3. The photoactive halloysite-based closed boron cluster M of claim 12BxHxThe preparation method of the nano noble metal catalyst is characterized by comprising the following steps: in the step (1), halloysite and a closed boron cluster M2BxHxThe mass ratio of (A) to (B) is 1-5: 1.
4. The photoactive halloysite-based closed boron cluster M of claim 12BxHxThe preparation method of the nano noble metal catalyst is characterized by comprising the following steps: in the step (2), the soluble compound of the noble metal is at least one of chloroauric acid, chloroplatinic acid, chloropalladite, chlororuthenic acid, chloroaurate, chloroplatinate, chloroplatinite, chloropalladate, chlororuthenate, silver ammonia solution, gold chloride and greening platinum.
5. The photoactive halloysite-based closed boron cluster M of claim 12BxHxThe preparation method of the nano noble metal catalyst is characterized by comprising the following steps: in the step (2)Closed boron cluster M based on halloysite2BxHxThe mass ratio of the ultraviolet light to the noble metal chloride acid or the noble metal chloride salt is 10-50: 1, and the wavelength range of the ultraviolet light is 200-400 nm.
6. The photoactive halloysite-based closed boron cluster M of any one of claims 1-52BxHxPhotoactive halloysite-based closed boron cluster M prepared by preparation method of nano noble metal catalyst2BxHxThe application of the nano noble metal catalyst is characterized in that: the method is applied to the selective reduction reaction of nitrobenzene compounds, and comprises the following specific operations: nitrobenzene compounds and halloysite-based closed boron cluster M2BxHxAdding the nano noble metal catalyst and the cocatalyst into the alcohol solution, mixing uniformly, and continuously filling N2And controlling the reaction temperature to be 10-30 ℃, and reacting completely under the irradiation of ultraviolet light to obtain azobenzene compounds and aniline compounds.
7. The photoactive halloysite-based closed boron cluster M of claim 62BxHxThe application of the nano noble metal catalyst is characterized in that: the nitro compound and the halloysite-based closed boron cluster M2BxHxThe mass ratio of the nano noble metal catalyst to the cocatalyst is 3-5: 0.1-0.5: 0.5-1.
8. The photoactive halloysite-based closed boron cluster M of claim 62BxHxThe application of the nano noble metal catalyst is characterized in that: the nitro compound is at least one of nitrobenzene, paranitrotoluene, m-nitrotoluene, p-nitrotoluene, 4-iodo-1-nitrobenzene, 3-fluoro-1-nitrobenzene, 1-fluoro-2-chloro-4-nitrobenzene, 4-ethyl nitrobenzene, 2,4, 6-trichloronitrobenzene, paranitrophenol, m-nitrophenol, p-nitrophenol and p-nitrobenzyl alcohol.
9. The photoactive halloysite-based closed boron cluster M of claim 62BxHxThe application of the nano noble metal catalyst is characterized in that: the alcoholic solution is any one of methanol, ethanol, isopropanol and n-butanol.
10. The photoactive halloysite-based closed boron cluster M of claim 62BxHxThe application of the nano noble metal catalyst is characterized in that: the cocatalyst is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
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