CN117443380A - Biochar-supported iron catalyst and application thereof - Google Patents
Biochar-supported iron catalyst and application thereof Download PDFInfo
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- CN117443380A CN117443380A CN202311298943.2A CN202311298943A CN117443380A CN 117443380 A CN117443380 A CN 117443380A CN 202311298943 A CN202311298943 A CN 202311298943A CN 117443380 A CN117443380 A CN 117443380A
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- Prior art keywords
- catalyst
- biochar
- butanone
- iron
- reaction
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 59
- LVSQXDHWDCMMRJ-UHFFFAOYSA-N 4-hydroxybutan-2-one Chemical compound CC(=O)CCO LVSQXDHWDCMMRJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 241000001727 Tropicoporus linteus Species 0.000 claims abstract description 20
- 238000000197 pyrolysis Methods 0.000 claims abstract description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- -1 iron ions Chemical class 0.000 claims abstract description 14
- 238000005576 amination reaction Methods 0.000 claims abstract description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001448 anilines Chemical class 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000002504 physiological saline solution Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000002041 carbon nanotube Substances 0.000 abstract description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 6
- 238000007126 N-alkylation reaction Methods 0.000 abstract description 3
- 241000123107 Phellinus Species 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QVNNESUIUTZTAK-UHFFFAOYSA-N 4-anilinobutan-2-one Chemical compound CC(=O)CCNC1=CC=CC=C1 QVNNESUIUTZTAK-UHFFFAOYSA-N 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 230000004075 alteration Effects 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 2
- DHYHYLGCQVVLOQ-UHFFFAOYSA-N 3-bromoaniline Chemical compound NC1=CC=CC(Br)=C1 DHYHYLGCQVVLOQ-UHFFFAOYSA-N 0.000 description 2
- GQOSMJZUHKLRAX-UHFFFAOYSA-N 4-(2-chloroanilino)butan-2-one Chemical compound CC(=O)CCNc1ccccc1Cl GQOSMJZUHKLRAX-UHFFFAOYSA-N 0.000 description 2
- JXSODWSVGCOTCU-UHFFFAOYSA-N 4-(3-bromoanilino)butan-2-one Chemical compound CC(=O)CCNc1cccc(Br)c1 JXSODWSVGCOTCU-UHFFFAOYSA-N 0.000 description 2
- FQHXNEKYPIDUAA-UHFFFAOYSA-N 4-(3-methoxyanilino)butan-2-one Chemical compound COC1=CC=CC(NCCC(C)=O)=C1 FQHXNEKYPIDUAA-UHFFFAOYSA-N 0.000 description 2
- WRHSJXOYKXFEHT-UHFFFAOYSA-N 4-(4-fluoroanilino)butan-2-one Chemical compound CC(=O)CCNC1=CC=C(F)C=C1 WRHSJXOYKXFEHT-UHFFFAOYSA-N 0.000 description 2
- FUWGEYOVQGAXJM-UHFFFAOYSA-N 4-(4-nitroanilino)butan-2-one Chemical compound CC(=O)CCNC1=CC=C([N+]([O-])=O)C=C1 FUWGEYOVQGAXJM-UHFFFAOYSA-N 0.000 description 2
- HATXVLGYOYFJEA-UHFFFAOYSA-N 4-[4-(trifluoromethyl)anilino]butan-2-one Chemical compound CC(=O)CCNc1ccc(cc1)C(F)(F)F HATXVLGYOYFJEA-UHFFFAOYSA-N 0.000 description 2
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-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
- ODGIMMLDVSWADK-UHFFFAOYSA-N 4-trifluoromethylaniline Chemical compound NC1=CC=C(C(F)(F)F)C=C1 ODGIMMLDVSWADK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WWJFFVUVFNBJTN-UIBIZFFUSA-N (2S)-2-[[(2S,3S,4S)-2-amino-4-hydroxy-4-(5-hydroxypyridin-2-yl)-3-methylbutanoyl]amino]-2-[(2R,3S,4S,5R)-5-(2,4-dioxopyrimidin-1-yl)-3,4-dihydroxyoxolan-2-yl]acetic acid Chemical class C[C@@H]([C@H](N)C(=O)N[C@@H]([C@H]1O[C@H]([C@@H](O)[C@@H]1O)n1ccc(=O)[nH]c1=O)C(O)=O)[C@H](O)c1ccc(O)cn1 WWJFFVUVFNBJTN-UIBIZFFUSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 229930184499 Nikkomycin Natural products 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000005966 aza-Michael addition reaction Methods 0.000 description 1
- 150000001576 beta-amino acids Chemical class 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a biochar-supported iron monoatomic catalyst and application thereof, wherein Phellinus linteus mycelium is used as a biochar pyrolysis precursor, iron ions are complexed on the surface of the biochar pyrolysis precursor, and the biochar-supported iron monoatomic catalyst is obtained by pyrolysis in an inert gas atmosphere. 4-hydroxy-2-butanone and different aniline compounds are used as reaction substrates, a biochar-supported iron single-atom catalyst is used, acetone or butanone is used as a solvent, and the N-alkylation product is obtained by reaction at room temperature in a nitrogen atmosphere. The invention uses Phellinus as a pyrolysis precursor of a carbon carrier for the first time to prepare the monoatomic catalyst. The biochar single-atom catalyst prepared by the invention has the appearance similar to that of a carbon nano tube. The invention uses the iron monoatomic catalyst for catalyzing the alcohol amination reaction of aniline and 4-hydroxy-2-butanone for the first time.
Description
Technical Field
The invention relates to an iron monoatomic catalyst loaded by biochar, an aniline compound and alcohol amination reaction of 4-hydroxy-2-butanone.
Background
The C-N bond exists as an important structural fragment in a large number of bioactive molecules and pharmaceutical molecules, and is widely used in the fields of fine chemistry and medicine, such as synthesis of beta-amino acids, beta-amino alcohols, 1, 3-diaminoalkanes, lactams, nikkomycins, and the like. Methods for synthesizing C-N bonds are numerous, such as halogenSubstituted hydrocarbon substitution reaction, aza-Michael addition reaction, aromatic halohydrocarbon coupling reaction, mannich reaction, high enol or allyl alcohol oxidative amination reaction, and the like. The direct substitution of the alcoholic hydroxyl group by the amine is one of important methods for preparing the C-N bond, the raw materials are easy to obtain, and the byproduct is H 2 O, green and environment-friendly and has high atom economy. However, neither thermodynamic nor kinetic, hydroxyl is a good leaving group and requires prior conversion to halogenated hydrocarbons, p-toluenesulfonates, sulfonates, and the like. The direct substitution reaction of the alcoholic hydroxyl group is carried out The medicine round table conference is selected as one of ten green chemical key research fields.
In 1981, grigg and Watanabe reported almost simultaneously that rhodium, iridium and ruthenium catalyzed the reaction of amine directly substituted alcoholic hydroxyl groups, and opened the study of amine directly substituted alcoholic hydroxyl groups. Thereafter, various methods for catalyzing the direct substitution of an alcoholic hydroxyl group by an amine have been reported, and catalysts involving metal salts or complexes of silver, gold, iridium, palladium, rhenium, ruthenium, cobalt, copper, iron, manganese, nickel, and the like, bimetallic catalytic systems and nonmetallic catalytic systems (enzymes, aldehydes, ketones, iodine, carbon materials, and organophosphines) have also been reported.
The invention uses the iron single-atom catalyst loaded by the biochar for catalyzing the alcohol amination reaction of 4-hydroxy-2-butanone and aniline compounds for the first time. The method provided by the invention is quick, simple, convenient, environment-friendly, low in cost and easy to industrialize, and the prepared biochar loaded iron monoatomic catalyst is good in stability and has a good application prospect in the field of alcohol amination reaction.
Disclosure of Invention
The invention discloses a biochar-supported iron monoatomic catalyst and an application thereof in catalyzing alcohol amination reaction of 4-hydroxy-2-butanone and aniline compounds.
4-hydroxy-2-butanone and different aniline compounds are used as reaction substrates, a biochar-supported iron single-atom catalyst is used, acetone or butanone is used as a solvent, and the N-alkylation product is obtained by reaction at room temperature in a nitrogen atmosphere. The invention uses Phellinus as a pyrolysis precursor of a carbon carrier for the first time to prepare the monoatomic catalyst. The biochar single-atom catalyst prepared by the invention has the appearance similar to that of a carbon nano tube. The invention uses the iron monoatomic catalyst for catalyzing the alcohol amination reaction of aniline and 4-hydroxy-2-butanone for the first time.
In the technical scheme, 2-5g (preferably 3-4 g) of Phellinus linteus mycelium is firstly dispersed in 150mL of physiological saline by ultrasonic, then 2-6mmol (preferably 5-5.5 mmol) of soluble ferric salt is added into the dispersion liquid, and the ferric ion is surface-complexed under the condition of 60-100 ℃ (preferably 80-90 ℃).
In the technical scheme, the ultrasonic dispersion pretreatment time is 20-50min, preferably 30-40min; the ultrasonic treatment power is 40-100kw; the time for complexing the iron ions on the surface is 12-24 hours; after complexing iron ions on the surface of Phellinus linteus mycelium, cooling to room temperature, centrifuging, collecting Phellinus linteus mycelium, washing with water, and freeze drying.
In the technical scheme, the soluble manganese salt is one of ferric chloride, ferric nitrate or ferric sulfate.
In the technical scheme, the pyrolysis temperature of the Phellinus linteus mycelium is 600-1000 ℃ (preferably 700-800 ℃) for 1-4 hours (preferably 1-2 hours).
In the technical scheme, the inert atmosphere is one of nitrogen or argon; 1g of dried Phellinus linteus mycelium is introduced into an inert atmosphere at an air flow rate of 10-30mL/min; the heating rate from room temperature to pyrolysis temperature is 2-5 ℃/min; the temperature reduction rate from the pyrolysis temperature to 40 ℃ after pyrolysis is 2-5 ℃/min; the prepared biochar-supported iron single-atom catalyst has a morphology similar to that of a carbon nano tube. Iron is dispersed on the biochar carrier in the form of single atoms.
In the technical scheme, in the nitrogen atmosphere, the biochar-supported iron single-atom catalyst catalyzes 4-hydroxy-2-butanone and different aniline compounds to perform an alcohol amination reaction to prepare 4- (N-phenyl) -2-butanone compounds.
In the technical proposal, the different aniline compounds are aniline, 2-chloroaniline, 3-bromoaniline, 4-fluoroaniline, 2-methylaniline, 3-methoxyaniline, 4-nitroaniline and 4-trifluoromethyl aniline
In the technical scheme, the concentration of the 4-hydroxy-2-butanone in the solvent is 0.5-1mol/L, preferably 0.5mol/L; the concentration of the aniline compound in the solvent is 0.5-1mol/L, preferably 0.5mol/L. The molar ratio of the 4-hydroxy-2-butanone to the aniline compound is 1:2-2:1, and the preferable molar ratio is 1:1. The amount of the biochar-supported iron single-atom catalyst is 10-30mg, preferably 20mg. The reaction time is 4 to 12 hours, preferably 8 hours.
Due to the application of the scheme, compared with the prior art, the invention has the following advantages:
1. according to the preparation method, phellinus linteus mycelium is used as a pyrolyzing precursor of a carbon carrier for the first time to prepare the biochar-supported iron single-atom catalyst, a non-renewable carbon source, an expensive template agent, an activating agent and a hetero-atom source are not required to be used, and the biochar-supported iron single-atom catalyst can be recycled;
2. the reaction does not need to add an alkaline additive additionally;
3. the reaction is carried out at room temperature without heating;
4. the reaction has good selectivity and no other byproducts.
Drawings
FIG. 1A scanning electron microscope spectrogram of a catalyst (Cat-700);
FIG. 2A transmission electron microscope spectrum of the catalyst (Cat-700) for spherical aberration correction.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples.
Examples
Example 1 preparation method of biochar-supported iron monatomic catalyst
In a 250mL round bottom flask, a magnetic stirrer rotor, 3g Phellinus linteus mycelium and 150mL physiological saline were added and sonicated (power 40kw for 30 min). At room temperature, 5mmol of ferric chloride was slowly added and stirring was continued for 30min. Then stirred at 80℃for 12h. Cooling to room temperature, centrifuging (10000 r/min,10 min), collecting Phellinus linteus mycelium, washing with deionized water for 3 times, and freeze drying. 1g of the freeze-dried material prepared in the above step was taken in a quartz boat, and the quartz boat was placed in a tube furnace, and nitrogen gas was introduced at room temperature for 30 minutes (gas flow rate: 10 mL/min). Then, the nitrogen flow rate was kept unchanged, and the temperature was raised to 700 ℃ (the temperature raising rate from room temperature to pyrolysis temperature was 5 ℃/min). The nitrogen flow rate is kept unchanged, and after pyrolysis is kept at 700 ℃ for 1h, the temperature is slowly reduced to 30 ℃ (the temperature reduction rate is 5 ℃/min).
The black solid in the quartz boat was ground into powder in an agate mortar to obtain a biochar-supported iron monoatomic catalyst (labeled Cat-700) in a mass yield of 27% (relative to Phellinus linteus mycelium).
The preparation methods of Cat-800 and Cat-900 are identical to the preparation process of Cat-700 described above, except that the pyrolysis temperatures are different. The pyrolysis temperatures of Cat-800 and Cat-900 were 800℃and 900℃respectively, and the yields were 28% and 27%, respectively.
The elemental composition and atomic percentage content of the biochar-supported iron monoatomic catalyst surface were analyzed using X-ray photoelectron spectroscopy techniques. The surface of the biochar-supported iron single-atom catalyst consists of carbon, nitrogen, oxygen, phosphorus and iron, wherein the content of carbon element is maximum and exceeds 84at%; secondly, nitrogen element with the content of 6.35 to 7.07at percent; the content of oxygen element is 5.61-6.15at%; the content of the phosphorus element is 1.32 to 1.71at%; the content of iron element is minimum (0.77-0.96 at%). The element content of the surface of the biochar-supported iron monoatomic catalyst prepared at different pyrolysis temperatures is different.
TABLE 1 surface element content of biochar Supported iron monatomic catalyst
Cat-700 scanning electron microscope (FIG. 1) shows that the morphology of the biochar-supported iron single-atom catalyst is very similar to that of the carbon nanotubes. The spherical aberration correction transmission electron microscope spectrogram (figure 2) shows that the iron element is uniformly distributed on the biochar carrier, and uniformly dispersed bright spots can be observed, which shows the atomic-level distribution of the iron element.
Scanning electron microscope spectrograms of Cat-800 and Cat-900 show that the morphology of the biochar-supported iron single-atom catalyst is very similar to that of the carbon nano tube. The spherical aberration correction transmission electron microscope spectrogram shows that the iron element is uniformly distributed on the biochar carrier, and uniformly dispersed bright spots can be observed, so that the atomic-level distribution of the iron element is illustrated.
Preparation of other biochar-supported iron monoatomic catalysts: the preparation process adopted is identical to the preparation process of Cat-700, and is different from the preparation process in that the dosage of the metal ferric salt (2-6 mmol) is changed when the biochar-supported iron single-atom catalyst is prepared, namely, the adding quantity of the metal ferric salt is replaced by 5mmol respectively by 2mmol, 3mmol, 4mmol and 6mmol, and the biochar-supported iron single-atom catalyst can be prepared. The scanning electron microscope spectrogram shows that the appearance of the biochar-supported iron single-atom catalyst is very similar to that of a carbon nano tube. The spherical aberration correction transmission electron microscope spectrogram shows that the iron element is uniformly distributed on the biochar carrier, and uniformly dispersed bright spots can be observed, so that the atomic-level distribution of the iron element is illustrated.
Example 2 4- (phenylamino) -2-butanone
The magneton, 20mg of charcoal-supported iron monoatomic catalyst (Cat-700), 1mmol of 4-hydroxy-2-butanone, 1mmol of aniline (R is hydrogen) and 2mL of acetone are sequentially added into a 25mL reaction bottle, the reaction system is stirred at room temperature under nitrogen atmosphere for reaction for 8h, the reaction solution is decompressed and desolventized, and the residue is subjected to column chromatography (eluent, ethyl acetate/petroleum ether=1:4, volume ratio) to obtain the 4- (phenylamino) -2-butanone, wherein the yield is 83% (135.5 mg) and yellow oil. 1 H NMR(400MHz,CDCl 3 )δ7.17(t,J＝7.8Hz,2H),6.73(t,J＝7.3Hz,1H),6.63(d,J＝8.2Hz,2H),3.40(t,J＝6.1Hz,2H),2.74(t,J＝6.1Hz,2H),2.14(s,3H)； 13 C NMR(101MHz,CDCl 3 )δ208.16,147.83,129.45,117.74,113.15,42.73,38.48,30.38.HRMS(ESI)for C 10 H 13 NO,calcd:163.0993,found:163.0984.
Example 2'
The procedure was as in example 2 above, except that 2mL of butanone (instead of 2mL of acetone) was used as the solvent, and the yield of 4- (phenylamino) -2-butanone was 81%.
The procedure was as in example 2 above, except that the reaction times were 4h,6h,10h, and 12h, and the yields of 4- (phenylamino) -2-butanone were 60%, 71%, 83%, and 87%, respectively.
The procedure was as in example 2 above, except that when the amount of the biochar-supported iron single-atom catalyst was 10mg or 30mg, the yields of 4- (phenylamino) -2-butanone were 51% and 84%, respectively;
example 3 4- ((2-chlorophenyl) amino) -2-butanone
The magneton, 20mg of charcoal-supported iron monoatomic catalyst (Cat-800), 0.5mmol of 4-hydroxy-2-butanone, 1mmol of 2-chloroaniline and 2mL of butanone are sequentially added into a 25mL reaction bottle, the reaction system is stirred at room temperature under nitrogen atmosphere for reaction for 9h, the reaction solution is decompressed and desolventized, and the residue is subjected to column chromatography (eluent, ethyl acetate/petroleum ether=1:4, volume ratio) to obtain 4- ((2-chlorophenyl) amino) -2-butanone as yellow oil, wherein the yield is 80% (79.1 mg). 1 H NMR(400MHz,CDCl 3 )δ7.14(d,J＝7.8Hz,1H),7.06(t,J＝8.3Hz,1H),6.55(dd,J＝15.8,7.9Hz,2H),4.44(s,1H),3.35(s,2H),2.67(t,J＝6.3Hz,2H),2.09(s,3H)； 13 C NMR(101MHz,CDCl 3 )δ207.57,143.63,129.38,127.90,119.54,117.51,111.17,42.66,38.15,30.42.HRMS(ESI)for C 10 H 12 ClNO,calcd:197.0610,found:197.0612.
Example 4 4- ((3-bromophenyl) amino) -2-butanone
Sequentially adding magneton, 20mg of biochar-supported iron monoatomic catalyst (Cat-900), 1mmol of 4-hydroxy-2-butanone, 0.5mmol of 3-bromoaniline and 2mL of acetone into a 25mL reaction bottle, stirring the reaction system at room temperature under nitrogen atmosphere for reacting for 12h, decompressing and desolventizing the reaction solution, and performing column chromatography treatment on residues (eluent)Ethyl acetate/petroleum ether=1:4, volume ratio) to give 4- ((3-bromophenyl) amino) -2-butanone as a yellow oil in 77% (93.2 mg) yield. 1 H NMR(400MHz,CDCl 3 )δ6.97(t,J＝8.0Hz,1H),6.76(d,J＝8.0Hz,1H),6.68(s,1H),6.47(d,J＝8.2Hz,1H),4.16(s,1H),3.32(t,J＝6.1Hz,2H),2.69(t,J＝6.1Hz,2H),2.12(s,3H)； 13 C NMR(101MHz,CDCl 3 )δ207.91,149.13,130.54,123.22,120.07,115.19,111.68,42.24,38.03,30.21.HRMS(ESI)for C 10 H 12 BrNO,calcd:241.0103,found:241.0108.
Example 5 4- ((4-fluorophenyl) amino) -2-butanone
To a 25mL reaction flask, a magneton, 20mg of a charcoal-supported iron monoatomic catalyst (Cat-700), 1mmol of 4-hydroxy-2-butanone, 1mmol of 4-fluoroaniline and 2mL of acetone were sequentially added, the reaction system was stirred at room temperature under nitrogen atmosphere for reaction for 9 hours, the reaction solution was desolventized under reduced pressure, and the residue was subjected to column chromatography (eluent, ethyl acetate/petroleum ether=1:4, volume ratio) to obtain 4- ((4-fluorophenyl) amino) -2-butanone as a yellow oil in 77% yield (139.5 mg). 1 H NMR(400MHz,CDCl 3 )δ7.13(d,J＝8.7Hz,2H),6.32(d,J＝8.7Hz,2H),3.96(s,1H),3.14(t,J＝6.1Hz,2H),2.61(t,J＝6.1Hz,2H),2.05(s,3H)； 13 C NMR(101MHz,CDCl 3 )δ207.03,146.45,131.07,113.35,108.08,42.24,38.12,30.21.HRMS(ESI)for C 10 H 12 FNO,calcd:181.0905,found:181.0907.
Example 6 4- (ortho-toluidine) -2-butanone
The magneton, 20mg of charcoal-supported iron monoatomic catalyst (Cat-900), 1mmol of 4-hydroxy-2-butanone, 1mmol of o-toluidine and 2mL of acetone are sequentially added into a 25mL reaction bottle, the reaction system is stirred and reacted for 9h in a nitrogen atmosphere at room temperature, the reaction liquid is decompressed and desolventized, and the residue is subjected to column chromatography (eluent, ethyl acetate/petroleum ether=1:4, volume ratio) to obtain the 4- (o-toluidine) -2-butanone, yellow oil, and the yield is 71% (125.9 mg). 1 H NMR(400MHz,CDCl 3 )δ7.15(t,J＝7.7Hz,1H),7.09(d,J＝7.2Hz,1H),6.73(t,J＝7.3Hz,1H),6.66(d,J＝8.0Hz,1H),3.90(s,1H),3.49(t,J＝6.1Hz,2H),2.81(t,J＝6.1Hz,2H),2.19(s,3H),2.14(s,3H)； 13 C NMR(101MHz,CDCl 3 )δ208.27,145.76,130.33,127.16,122.58,117.20,109.67,42.60,38.38,30.33,17.49.HRMS(ESI)for C 11 H 15 NO,calcd:177.1155,found:177.1153.
Example 7 4- ((3-methoxyphenyl) amino) -2-butanone
To a 25mL reaction flask, a magneton, 20mg of a charcoal-supported iron monoatomic catalyst (Cat-800), 1mmol of 4-hydroxy-2-butanone, 1mmol of m-methoxyaniline and 2mL of butanone were sequentially added, the reaction system was stirred at room temperature under nitrogen atmosphere for reaction for 8 hours, the reaction solution was desolventized under reduced pressure, and the residue was subjected to column chromatography (eluent, ethyl acetate/petroleum ether=1:4, volume ratio) to obtain 4- ((3-methoxyphenyl) amino) -2-butanone as a yellow oil, with a yield of 89% (172.0 mg). 1 H NMR(400MHz,CDCl 3 )δ7.08(t,J＝8.1Hz,1H),6.27(d,J＝8.1Hz,1H),6.24(d,J＝8.1Hz,1H),6.15(s,1H),3.77(s,3H),3.38(t,J＝6.1Hz,2H),2.72(t,J＝6.1Hz,2H),2.14(s,3H)； 13 C NMR(101MHz,CDCl 3 )δ208.19,160.95,149.20,130.12,106.19,102.72,99.01,55.13,42.61,38.38,30.32.HRMS(ESI)for C 11 H 15 NO 2 ,calcd:193.1101,found:193.1117.
Example 8 4- ((4-nitrophenyl) amino) -2-butanone
The magneton, 20mg of charcoal-supported iron monoatomic catalyst (Cat-800), 1mmol of 4-hydroxy-2-butanone, 1mmol of p-nitroaniline and 2mL of butanone are sequentially added into a 25mL reaction bottle, the reaction system is stirred and reacted for 12h in a nitrogen atmosphere at room temperature, the reaction liquid is decompressed and desolventized, and the residue is subjected to column chromatography (eluent, ethyl acetate/petroleum ether=1:4, volume ratio) to obtain 4- ((4-nitrophenyl) amino) -2-butanone as a yellow solid, the melting point is 89-91 ℃, and the yield is 50% (104.1 mg). 1 H NMR(400MHz,CDCl 3 )δ8.03(d,J＝9.0Hz,2H),6.45(d,J＝9.2Hz,2H),5.12(s,1H),3.46(q,J＝5.9Hz,2H),2.78(t,J＝6.0Hz,2H),2.18(s,3H)； 13 C NMR(101MHz,CDCl 3 )δ207.59,153.22,137.74,126.50,111.09,42.14,37.67,30.32.HRMS(ESI)for C 10 H 12 N 2 O 3 ,calcd:208.0844,found:208.0839.
Example 9 4- ((4-trifluoromethylphenyl) amino) -2-butanone
The magneton, 20mg of charcoal-supported iron monoatomic catalyst (Cat-700), 1mmol of 4-hydroxy-2-butanone, 1mmol of para-trifluoromethylaniline and 2mL of acetone are sequentially added into a 25mL reaction bottle, the reaction system is stirred at room temperature under nitrogen atmosphere for reaction for 12h, the reaction solution is decompressed and desolventized, and the residue is subjected to column chromatography (eluent, ethyl acetate/petroleum ether=1:4, volume ratio) to obtain 4- ((4-trifluoromethylphenyl) amino) -2-butanone as a yellow solid, the melting point is 89-91 ℃, and the yield is 49% (113.3 mg). 1 H NMR(400MHz,CDCl 3 )δ7.38(d,J＝8.5Hz,2H),6.57(d,J＝8.5Hz,2H),4.36(s,1H),3.46(s,2H),2.76(t,J＝6.0Hz,2H),2.19(s,3H)； 13 C NMR(101MHz,CDCl 3 )δ207.87,150.34,126.84,126.45,123.75,118.97,112.09,42.41,37.94,30.46.HRMS(ESI)for C 11 H 12 F 3 NO,calcd:231.0872,found:231.0869.
Comparative example
1. Compared with other solvents, the acetone or butanone solvents used in the invention have obvious advantages, the yield of the product is obviously higher than that of the other solvents, and specific data are shown in Table 2 (except that the solvents are different (the dosage is 2mL respectively), and other processes and conditions are the same as in example 2).
Table 24 isolation yields of- (phenylamino) -2-butanone in different solvents
2. The same reaction procedure and conditions as in example 2 were used, except that no catalyst was used in the reaction procedure; compared with the reaction result without using the catalyst, the biochar-supported iron monoatomic catalyst used in the invention has obvious advantages, and specific data are shown in Table 3 (the same as in example 2 except that the biochar-supported iron monoatomic catalyst is not added).
Table 3 4 isolation yields of- (phenylamino) -2-butanone in different solvents
3. In contrast to palladium-catalyzed oxidative amination of homoenols (chem. Commun.2017,53, 10422-10425) or allylic alcohols (J. Org. Chem.2018,83, 3941-3951), the present invention has the following advantages:
(1) The reaction uses an iron single-atom catalyst loaded by biochar, and an expensive palladium catalyst is not needed;
(2) The reaction does not require an oxidant;
(3) The reaction was carried out at room temperature without heating.
We have verified experimentally: palladium catalysts do not catalyze the reaction of 4-hydroxy-2-butanone with aromatic amines to beta-aminoketones under the conditions of the present reaction (the procedure is as in example 1 except for the catalyst).
4. In contrast to the iodine-catalyzed nucleophilic substitution reaction of benzyl alcohol (Synlett 2008,7,1045-1049;Tetrahedron Lett.2007,48,8120-8124), the present invention has the following advantages: the nucleophilic substitution reaction of benzyl alcohol catalyzed by iodine (Synlett 2008,7,1045-1049;Tetrahedron Lett.2007,48,8120-8124) can only be the reaction of benzyl alcohol with other alcohols to form ethers, which we have experimentally verified that iodine catalysis cannot catalyze the reaction of benzyl alcohol with amines. The invention relates to an iron monoatomic catalyst loaded by biochar for catalyzing aniline and 4-hydroxy-2-butanone to generate an alcohol amination reaction, which is obviously different from the prior art.
Compared with the patent 'a method for catalyzing N-alkylation reaction by TEMPO and TBN (CN 201910743878.7)' or the patent 'a method for generating beta-aminoketone compound by iodine catalysis (CN201811374694. X)', the invention has the following obvious differences and advantages: the content of the invention is that the iron monoatomic catalyst loaded by biochar catalyzes aniline and 4-hydroxy-2-butanone to generate alcohol amination reaction, and the catalyst is obviously different from the prior art; the iron single-atom catalyst loaded by the biochar can be recycled, the catalytic activity is not obviously reduced after six times of continuous use, and neither TEMPO/TBN nor iodine catalyst can be recycled.
Claims (9)
1. A biochar-supported iron catalyst characterized by: the Phellinus linteus mycelium is used as a charcoal pyrolysis precursor, the Phellinus linteus mycelium is dispersed in normal saline, then soluble ferric salt is added into the dispersion liquid, and iron ions are complexed on the surface of the Phellinus linteus mycelium; and (3) solid-liquid separation is carried out to collect Phellinus linteus mycelium, washing is carried out, freeze drying is carried out, and then the Phellinus linteus mycelium is pyrolyzed in inert atmosphere to obtain the biochar-loaded iron monoatomic catalyst.
2. The catalyst of claim 1, wherein:
the specific process is that 2-5g (preferably 3-4 g) Phellinus linteus mycelium is firstly ultrasonically dispersed in 150mL physiological saline to obtain dispersion liquid; then, a soluble iron salt having a molar amount of iron ions of 2 to 6mmol (preferably 5 to 5.5 mmol) is added to the dispersion, and the iron ions are surface-complexed under conditions of 60 to 100 ℃ (preferably 80 to 90 ℃).
3. The catalyst according to claim 1 or 2, characterized in that:
the ultrasonic dispersion pretreatment time is 20-50min, preferably 30-40min; the ultrasonic treatment power is 40-100kw;
the time for complexing the iron ions on the surface is 12-24 hours;
after complexing iron ions on the surface of Phellinus linteus mycelium, cooling to room temperature, centrifuging, collecting Phellinus linteus mycelium, washing with water, and freeze drying.
4. The catalyst of claim 1, wherein:
the soluble manganese salt is one or more of ferric chloride, ferric nitrate or ferric sulfate.
5. The catalyst of claim 1, wherein:
the pyrolysis temperature of Phellinus linteus mycelium is 600-1000deg.C (preferably 700-800deg.C) for 1-4 hr (preferably 1-2 hr).
6. The catalyst according to claim 1 or 5, characterized in that:
the inert atmosphere is one or more than two of nitrogen and argon;
1g of dried Phellinus linteus mycelium is introduced into an inert atmosphere at an air flow rate of 10-30mL/min;
the heating rate from room temperature to pyrolysis temperature is 2-5 ℃/min; cooling to room temperature-40 ℃ after pyrolysis to obtain the catalyst, and cooling from the pyrolysis temperature to the room temperature-40 ℃ after pyrolysis at a cooling rate of 2-5 ℃/min.
7. Use of the biochar-supported catalyst of any one of claims 1-6 in an alcohol amination reaction of 4-hydroxy-2-butanone and aniline compounds.
8. The use according to claim 7, characterized in that: the method is characterized in that:
in a nitrogen atmosphere, catalyzing 4-hydroxy-2-butanone and different aniline compounds to perform an alcohol amination reaction by using an iron single-atom catalyst loaded by biochar to prepare 4- (N-phenyl) -2-butanone compounds;
r substituent groups in the formula 1 are one or more than two of hydrogen, halogen (one or more than two of F, cl and Br), methyl, methoxy, nitro and trifluoromethyl, and the number is 1-5.
9. Use according to claim 7 or 8, characterized in that:
the concentration of 4-hydroxy-2-butanone in the solvent is 0.25-1mol/L, preferably 0.5mol/L; the concentration of the aniline compound in the solvent is 0.25-1mol/L, preferably 0.5mol/L;
the molar ratio of the 4-hydroxy-2-butanone to the aniline compound is 1:2-2:1, and the preferable molar ratio is 1:1;
the solvent is acetone and/or butanone;
the dosage of the biochar-supported iron single-atom catalyst in 2mL of solvent is 10-30mg, preferably 15-20mg;
the reaction time is 4 to 12 hours, preferably 6 to 8 hours.
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