CN115400798A - Preparation method and application of bimetallic modified porphyrin-based MOF catalyst - Google Patents
Preparation method and application of bimetallic modified porphyrin-based MOF catalyst Download PDFInfo
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- CN115400798A CN115400798A CN202211052683.6A CN202211052683A CN115400798A CN 115400798 A CN115400798 A CN 115400798A CN 202211052683 A CN202211052683 A CN 202211052683A CN 115400798 A CN115400798 A CN 115400798A
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- copper
- mof
- porphyrin
- modified porphyrin
- acid
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- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000012918 MOF catalyst Substances 0.000 title claims abstract description 14
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 230000002093 peripheral effect Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 51
- 239000011259 mixed solution Substances 0.000 claims description 39
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- -1 gallium ions Chemical class 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 239000011941 photocatalyst Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000007605 air drying Methods 0.000 claims description 12
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012917 MOF crystal Substances 0.000 claims description 11
- 239000013110 organic ligand Substances 0.000 claims description 11
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 150000005181 nitrobenzenes Chemical group 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910001449 indium ion Inorganic materials 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229940044658 gallium nitrate Drugs 0.000 claims description 3
- 239000000852 hydrogen donor Substances 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PXWYZLWEKCMTEZ-UHFFFAOYSA-N 1-ethyl-2-nitrobenzene Chemical group CCC1=CC=CC=C1[N+]([O-])=O PXWYZLWEKCMTEZ-UHFFFAOYSA-N 0.000 claims description 2
- CFBYEGUGFPZCNF-UHFFFAOYSA-N 2-nitroanisole Chemical group COC1=CC=CC=C1[N+]([O-])=O CFBYEGUGFPZCNF-UHFFFAOYSA-N 0.000 claims description 2
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical group CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 claims description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 239000000460 chlorine Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Chemical group 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 150000002828 nitro derivatives Chemical class 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 description 5
- 150000001448 anilines Chemical class 0.000 description 4
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical group CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 4
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 3
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical class O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 2
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical compound C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 102000018832 Cytochromes Human genes 0.000 description 1
- 108010052832 Cytochromes Proteins 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000386 donor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B01J35/39—
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- 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
- C07C209/325—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 reduction by other means than indicated in C07C209/34 or C07C209/36
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/32—Gallium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/33—Indium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/54—Bismuth
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Abstract
The invention discloses a preparation method and application of a bimetal modified porphyrin-based MOF catalyst, wherein coordination of metal is directionally induced by using active sites of a central ring and peripheral carboxyl of meso-tetra (4-carboxyphenyl) porphyrin. The bimetallic-modified porphyrin MOF prepared by the method expands the photoresponse interval of porphyrin, greatly improves the light absorption capacity of the porphyrin, effectively promotes the migration of carriers, and successfully solves the defect of high recombination rate of photo-generated electron hole pairs of monometallic porphyrin MOF. In addition, the nitro derivative is selectively reduced to generate corresponding aniline under mild conditions, a feasible method is provided for developing a green catalytic system, and the method is expected to be widely applied to actual production.
Description
Technical Field
The invention belongs to the technical field of material synthesis and photocatalysis, and particularly relates to a preparation method and application of a bimetal modified porphyrin-based MOF catalyst.
Background
Porphyrins are highly conjugated pi-electron heterocyclic macromolecules, widely found in natural animals and plants, such as cytochrome and chlorophyll. Because porphyrin molecules have the advantages of large specific surface area, rich pore channels, wide visible light absorption, flexible structure and the like, porphyrins have been applied to various fields including biomimetic chemistry, catalysis and biological detection. Porphyrins are commonly used as functional molecules in homogeneous systems, which are very unfavorable for recovery and recycling, and thus, in the last decades, efforts have been made to develop and design porphyrin-based complexes for heterogeneous systems. Among them, porphyrin-based metal organic frameworks have attracted much attention. As a very important branching material of MOFs, porphyrin-based MOFs are novel periodic network-like framework materials constructed by porphyrin as a structural unit and metal ions or metal clusters. Because a large number of active sites exist between the metal cluster and the organic ligand, a plurality of novel multifunctional porphyrin compounds can be synthesized by adjusting the metal center, the organic ligand and the reaction conditions.
Nitroaromatic compounds, which are widely used as raw materials for dyes, explosives, pesticides and medicines, are notoriously odorous pollutants in water, which pose high risks to ecology and human health, and thus, detoxification thereof is essential. Generally, nitrobenzene derivatives can be reductively converted to nitrosobenzenes, azobenzenes, and azobenzenes and anilines and their derivatives. Among them, aniline derivatives are widely used as one of key intermediates for synthesizing dyes, medical drugs and pesticides. Generally, the industrial selective conversion of nitro compounds to aniline derivatives is achieved by hydrogenation of nitroarenes under pressurized hydrogenation conditions using noble metal-based catalysts, which are costly and potentially hazardous. Therefore, the development of green sustainable catalysts for the selective reduction of nitrobenzene and its derivatives under economical, mild and environmentally friendly conditions is a great challenge.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a bimetal modified porphyrin-based MOF catalyst. The method for synthesizing the bimetallic MOF has the advantages of low cost, less energy consumption, short time and simple preparation process, and has a large-scale preparation prospect in industry.
The bimetallic modified porphyrin-based MOF photocatalyst prepared by the invention overcomes the defect of high recombination rate of photon-generated carriers of monometallic porphyrin MOF, and improves the photoresponse range. The catalyst prepared by the invention can selectively reduce nitro compounds to generate aniline under mild conditions, and avoids the use of noble metal catalysts, strong lamp source irradiation and pressurized hydrogen. The method is simple and convenient to operate, has lasting and stable photocatalytic reduction performance, and provides a potential application value for developing a green catalytic system.
The preparation method of the bimetal modified porphyrin-based MOF catalyst utilizes the active sites of the central ring and the peripheral carboxyl of the meso-tetra (4-carboxyphenyl) porphyrin to directionally induce the coordination of metals, and specifically comprises the following steps:
s1: preparation of copper-modified porphyrin central ring MOF
Dissolving a proper amount of meso-tetra (4-carboxyphenyl) porphyrin and copper nitrate in an N, N-dimethylformamide solution by taking the meso-tetra (4-carboxyphenyl) porphyrin as an organic ligand and the copper nitrate as a copper source, performing ultrasonic treatment to obtain a uniform mixed solution, then placing the mixed solution in a test tube to perform condensation reflux reaction at a proper temperature, performing mechanical stirring reaction for 3 hours, cooling to room temperature, and performing centrifugation, washing and vacuum drying treatment to obtain a copper-modified porphyrin MOF crystal; the reaction scheme is shown in FIG. 1.
S2: preparation of copper-gallium bimetal modified porphyrin MOF
Taking copper-modified porphyrin MOF prepared in S1 as an organic ligand, taking trivalent gallium ions as a metal source, dissolving a proper amount of copper-modified porphyrin MOF, the metal source and polyvinylpyrrolidone in a mixed solution of N, N-dimethylformamide and acid, performing ultrasound to obtain a uniform mixed solution, then placing the mixed solution in a forced air drying oven to react for 12 hours at a proper temperature, cooling to room temperature, and performing centrifugation, washing and vacuum drying to obtain purple copper-gallium double-metal modified porphyrin MOF crystals;
s3: preparation of copper-bismuth bimetal modified porphyrin MOF
Taking copper-modified porphyrin MOF prepared in S1 as an organic ligand, taking trivalent bismuth ions as a metal source, dissolving a proper amount of copper-modified porphyrin MOF, the metal source and polyvinylpyrrolidone in a mixed solution of N, N-dimethylformamide and acid, performing ultrasound to obtain a uniform mixed solution, then placing the mixed solution in a forced air drying oven to react for 12 hours at a proper temperature, cooling to room temperature, and performing centrifugation, washing and vacuum drying to obtain purple copper-bismuth bimetal modified porphyrin MOF crystals;
s4: preparation of copper-indium bimetal modified porphyrin MOF
Taking copper-modified porphyrin MOF prepared in S1 as an organic ligand, taking trivalent indium ions as a metal source, dissolving a proper amount of copper-modified porphyrin MOF, the metal source and polyvinylpyrrolidone in a mixed solution of N, N-dimethylformamide and acid, performing ultrasound to obtain a uniform mixed solution, then placing the mixed solution in a forced air drying oven to react for 12h at a proper temperature, cooling to room temperature, and performing centrifugation, washing and vacuum drying to obtain a purple copper-indium bimetal modified porphyrin MOF crystal. The reaction scheme is shown in FIG. 2.
Preferably, in S1, the dosage of the meso-tetra (4-carboxyphenyl) porphyrin, the dosage of the copper nitrate and the N, N-dimethylformamide are respectively 80-100mg, 60-70mg, 30-100mL, the reaction temperature of condensation reflux is 80-120 ℃, and the temperature of vacuum drying is 60-80 ℃.
Preferably, in S2, the dosage of the copper-modified porphyrin MOF is 40-60mg, the trivalent gallium ion is one of gallium chloride and gallium nitrate and is 30-50mg, and the dosage of the polyvinylpyrrolidone is 10-30mg; the acid is any one of nitric acid, hydrochloric acid, sulfuric acid, acetic acid and trifluoroacetic acid, the concentration of the acid is 1-3mol/L, the total volume of the mixed solution is 30-90mL, and the proportion is V (N, N-dimethylformamide) V (acid) = 5; the reaction temperature in the forced air drying oven is 80-120 ℃, and the vacuum drying temperature is 60-80 ℃.
Preferably, in S3, the dosage of the copper-modified porphyrin MOF is 40-60mg, the trivalent bismuth ion is one of bismuth chloride and bismuth nitrate and is 40-60mg, and the dosage of the polyvinylpyrrolidone is 10-30mg; the acid is any one of nitric acid, hydrochloric acid, sulfuric acid, acetic acid and trifluoroacetic acid, the concentration of the acid is 1-3mol/L, the total volume of the mixed solution is 30-90mL, and the proportion is V (N, N-dimethylformamide) V (acid) = 4; the reaction temperature in the forced air drying oven is 90-100 deg.C, and the vacuum drying temperature is 60-80 deg.C.
Preferably, in S4, the dosage of the copper-modified porphyrin MOF is 40-60mg, the trivalent indium ion is one of indium chloride and indium nitrate and is 50-70mg, and the dosage of the polyvinylpyrrolidone is 10-30mg; the acid is any one of nitric acid, hydrochloric acid, sulfuric acid, acetic acid and trifluoroacetic acid, the concentration of the acid is 1-3mol/L, the total volume of the mixed solution is 30-90mL, and the proportion is V (N, N-dimethylformamide) V (acid) = 4; the reaction temperature in the forced air drying oven is 80-120 deg.C, and the vacuum drying temperature is 60-80 deg.C.
The bimetallic modified porphyrin-based MOF catalyst prepared by the invention is used as a photocatalyst for selectively catalyzing and reducing a nitrobenzene compound to generate corresponding aniline.
When the photocatalyst is irradiated by visible light, a large number of photo-generated electron-hole pairs can be excited to be generated. These holes generated from VB of the photocatalyst are rapidly quenched by the sacrificial electron donor of methanol, and at the same time, photoinduced electrons on the photocatalyst CB can be easily retained at the interface to efficiently participate in the reduction reaction. E in porphyrin MOF production - H provided with hydrazine hydrate + With the coordination of (a), nitrobenzene is firstly converted into nitrosobenzene, phenylhydroxylamine, azoxybenzene, azobenzene and reduced azobenzene, and finally is completely converted into aniline with the passage of time, and the specific reaction path is shown in figure 5.
The nitrobenzene compound comprises methyl nitrobenzene, methoxy nitrobenzene, ethyl nitrobenzene, chlorine substituted nitrobenzene, fluorine substituted nitrobenzene, cyano substituted nitrobenzene, bromine substituted nitrobenzene, amino substituted nitrobenzene and the like, and all substituent nitrobenzene comprises ortho-position, meta-position or para-position.
The bimetal modified porphyrin-based MOF catalyst is copper-gallium bimetal modified porphyrin MOF, copper-bismuth bimetal modified porphyrin MOF or copper-indium bimetal modified porphyrin MOF.
Specifically, the method comprises the following steps: A10W white light lamp is used as an irradiation source, hydrazine hydrate is used as a hydrogen donor, methanol is used as a solvent at room temperature, and a bimetallic modified porphyrin-based MOF catalyst is used for catalyzing and reducing a nitrobenzene compound.
Preferably, the dosage of hydrazine hydrate is 0.5-1.5mmol, the dosage of nitrobenzene compound is 0.2-1mmol, the dosage of methanol is 4-10mL, the dosage of catalyst is 2-5mg, and the illumination time is 3-10h.
The invention has the following beneficial effects:
the selective reduction of nitroarenes to the corresponding amines typically requires complex conditions including pressurized hydrogen, noble metal-based catalysts and higher temperatures. In the invention, hydrazine hydrate is used as a hydrogen donor, methanol is used as a solvent and a cavity sacrificial agent, and a series of porphyrin-based MOF photocatalysts (copper gallium porphyrin MOF, copper bismuth porphyrin MOF or copper indium porphyrin MOF) are successfully prepared by a simple solvothermal method so as to effectively and selectively reduce nitroarenes into corresponding anilines. As the MOF with a novel structure, due to rich pore channels, strong light absorption capacity, well-matched band gap and the synergistic effect of bimetallic ions, the prepared photocatalyst has excellent photoinduced electron and hole migration efficiency, and more importantly, the defect of high recombination rate of photoinduced electron hole pairs of monometallic porphyrin MOF is successfully solved. In addition, the photocatalyst showed excellent conversion (100%) and selectivity (99%) to the screened nitro compound under mild conditions. The invention provides a feasible method for preparing a novel and high-activity bimetallic modified porphyrin-based photocatalyst and developing a green catalytic system, and is expected to be widely applied to actual production.
Drawings
FIG. 1 shows the synthesis path of copper-modified porphyrin center ring MOF of the present invention, in which copper ions are coordinated with the nitrogen element of the porphyrin center ring.
FIG. 2 is a synthetic route of a bimetallic modified porphyrin MOF of the present invention, wherein on the basis of a copper modified porphyrin central ring, single gallium, bismuth and indium ions form coordination with carboxyl oxygen elements from four porphyrin organic ligands.
FIG. 3 is an XPS N1s spectrum of meso-tetra (4-carboxyphenyl) porphyrin and copper porphyrin MOFs prepared according to the invention: in the spectrum of pure porphyrin N1s, C = N-C and C-NH-C groups of the porphyrin ring were observed, corresponding binding energies were at 397.5 and 399.7eV, respectively, and after copper modification of the porphyrin, there was a significant change in the binding energy of N, the binding energy at 398eV corresponding to the Cu-N group, indicating that the central ring of the meso-tetra (4-carboxyphenyl) porphyrin was copper metallized.
FIG. 4 is a microscopic picture of the copper-bismuth bimetal modified porphyrin MOF prepared by the invention, the morphology structure of the copper-bismuth bimetal modified porphyrin MOF is similar to a long cubic block, and the crystallization is regular and uniform.
FIG. 5 is a reaction scheme for reducing nitrobenzene according to the present invention, with nitrobenzene first converted to nitrosobenzene and then to phenylhydroxylamine or azoxybenzene, with intermediate products again producing azobenzene and reduced azobenzene, all of which are converted to aniline over time.
FIG. 6 is a nuclear magnetic hydrogen spectrum of a substrate obtained by reducing nitrobenzene in example 1 of the present invention, and the result shows that the substrate produced is aniline, which indicates that copper gallium modified porphyrin MOF photocatalyst successfully reduces nitrobenzene to aniline, and the conversion rate and selectivity are as high as 100% and 99%, respectively.
FIG. 7 is a nuclear magnetic hydrogen spectrum of a substrate obtained by reducing p-methylnitrobenzene in example 2 of the present invention, and the result shows that the substrate is p-methylaniline, which indicates that the copper bismuth modified porphyrin MOF photocatalyst successfully reduces p-methylnitrobenzene to p-methylaniline, and the conversion rate and selectivity are as high as 100% and 99%, respectively.
FIG. 8 is a nuclear magnetic hydrogen spectrum of a substrate obtained by reducing p-fluoronitrobenzene in example 3 of the present invention, and the result shows that the substrate produced is p-fluoroaniline, which indicates that the copper indium modified porphyrin MOF photocatalyst successfully reduces p-fluoronitrobenzene to p-fluoroaniline, and the conversion rate and selectivity are as high as 100% and 99%, respectively.
Fig. 9 is PL spectrum data of copper porphyrin MOF and copper indium bimetallic porphyrin MOF in the present invention, and the results show that, compared with monometallic copper porphyrin MOF, copper indium bimetallic porphyrin MOF has very low PL intensity, indicating that the synergistic effect of bimetallic ions effectively promotes the migration of photo-generated carriers, thereby enhancing the photocatalytic activity.
Detailed Description
The technical solution of the present invention is described in more detail with reference to the following embodiments.
Example 1:
preparation of copper-modified porphyrin central ring MOF: dissolving 90mg of meso-tetra (4-carboxyphenyl) porphyrin and 65mg of copper nitrate in a beaker containing 50mLN, N-dimethylformamide solution, magnetically stirring to obtain a uniform mixed solution, then placing the mixed solution in a reaction tube to perform condensation reflux reaction at 120 ℃, mechanically stirring for reaction for 3 hours, cooling to room temperature, centrifuging, washing and performing vacuum drying treatment at 60 ℃ to obtain the Cu modified porphyrin MOF.
Preparation of copper gallium double metal modified porphyrin MOF: 50mg of the prepared Cu porphyrin MOF,40mg of gallium nitrate, 20mg of polyvinylpyrrolidone, 50mL of N, N-dimethylformamide and 10mL of sulfuric acid solution with the concentration of 2mol/L are placed in a 200mL beaker, and are magnetically stirred to obtain a uniform mixed solution, and then the mixed solution is placed in a forced air drying oven to react for 12 hours at 100 ℃, and after the mixed solution is cooled to room temperature, the mixed solution is centrifuged, washed and vacuum-dried at 60 ℃ to obtain purple copper-gallium bimetal modified porphyrin MOF crystals.
Reduction of nitro compounds: using a 10W white light lamp as an irradiation source, taking 1mmol of hydrazine hydrate, 0.2mmol of nitrobenzene, 2mg of copper-gallium modified porphyrin MOF and 4mL of methanol in a 10mL reactor at room temperature, magnetically stirring for 30min under a dark condition to form a uniform suspension, then placing the reactor under the 10W white light lamp for irradiation for 5h, separating a catalyst and a product through filtration and rotary evaporation treatment after the reaction is finished, and carrying out a cycle test on the catalyst and carrying out nuclear magnetic hydrogen spectrum detection on the product.
Example 2:
preparation of copper-modified porphyrin central ring MOF: dissolving 100mg of meso-tetra (4-carboxyphenyl) porphyrin and 70mg of copper nitrate in a beaker containing a 60mLN, N-dimethylformamide solution, magnetically stirring to obtain a uniform mixed solution, then placing the mixed solution in a reaction tube to perform condensation reflux reaction at 100 ℃, mechanically stirring for reaction for 3 hours, cooling to room temperature, centrifuging, washing and performing vacuum drying treatment at 70 ℃ to obtain the Cu modified porphyrin MOF.
Preparation of copper-bismuth bimetal modified porphyrin MOF: putting 45mg of prepared copper porphyrin MOF,50mg of bismuth nitrate, 25mg of polyvinylpyrrolidone (PVP), 40mL of N, N-dimethylformamide and 10mL of sulfuric acid solution with the concentration of 1mol/L into a 200mL beaker, magnetically stirring to obtain a uniform mixed solution, then putting the mixed solution into a forced air drying oven to react for 12 hours at 90 ℃, cooling to room temperature, centrifuging, washing and carrying out vacuum drying treatment at 65 ℃ to obtain purple copper-bismuth bimetal modified porphyrin MOF crystals.
Reduction of nitro compounds: using a 10W white light lamp as an irradiation source, taking 1.2mmol of hydrazine hydrate, 0.4mmol of p-methylnitrobenzene, 3mg of copper-bismuth modified porphyrin MOF and 5mL of methanol in a 10mL reactor at room temperature, magnetically stirring for 30min under a dark condition to form a uniform suspension, then placing the reactor under the 10W white light lamp for irradiation for 6h, separating out a catalyst and a product through filtration and rotary evaporation treatment after the reaction is finished, and carrying out a cycle test on the catalyst and carrying out nuclear magnetic hydrogen spectrum detection on the product.
Example 3:
preparation of copper-modified porphyrin central ring MOF: dissolving 80mg of meso-tetra (4-carboxyphenyl) porphyrin and 60mg of copper nitrate in a beaker containing 75mLN, N-dimethylformamide solution, magnetically stirring to obtain uniform mixed solution, then placing the mixed solution in a reaction tube for condensation reflux reaction at 80 ℃, mechanically stirring for reaction for 3 hours, cooling to room temperature, centrifuging, washing and vacuum drying at 80 ℃ to obtain the Cu modified porphyrin MOF.
Preparation of copper indium bimetal modified porphyrin MOF: putting 55mg of prepared copper porphyrin MOF,65mg of indium chloride, 30mg of polyvinylpyrrolidone, 60mL of N, N-dimethylformamide and 10mL of sulfuric acid solution with the concentration of 2.5mol/L into a 200mL beaker, magnetically stirring to obtain a uniform mixed solution, then putting the mixed solution into a forced air drying oven to react for 12 hours at 80 ℃, cooling to room temperature, centrifuging, washing and carrying out vacuum drying treatment at 80 ℃ to obtain purple copper indium bimetal modified porphyrin MOF crystals.
Reduction of nitro compounds: using a 10W white light lamp as an irradiation source, taking 0.8mmol of hydrazine hydrate, 0.3mmol of p-fluoronitrobenzene, 4mg of copper-indium modified porphyrin MOF and 3mL of methanol in a 10mL reactor at room temperature, magnetically stirring for 30min under a dark condition to form a uniform suspension, then placing the reactor under the 10W white light lamp for irradiation for 4h, separating out a catalyst and a product through filtration and rotary evaporation treatment after the reaction is finished, and performing a cycle test on the catalyst and performing nuclear magnetic hydrogen spectrum detection on the product.
Claims (10)
1. A preparation method of a bimetallic modified porphyrin-based MOF catalyst is characterized by comprising the following steps:
the method utilizes the active sites of the central ring and the peripheral carboxyl of the meso-tetra (4-carboxyphenyl) porphyrin to directionally induce the coordination of metals, and specifically comprises the following steps:
s1: preparation of copper-modified porphyrin central ring MOF
Dissolving a proper amount of meso-tetra (4-carboxyphenyl) porphyrin and copper nitrate in an N, N-dimethylformamide solution by taking the meso-tetra (4-carboxyphenyl) porphyrin as an organic ligand and the copper nitrate as a copper source, performing ultrasonic treatment to obtain a uniform mixed solution, then placing the mixed solution in a test tube for condensation reflux reaction at a proper temperature, performing mechanical stirring reaction for 3 hours, cooling to room temperature, and performing centrifugation, washing and vacuum drying treatment to obtain a copper-modified porphyrin MOF crystal;
s2: preparation of copper-gallium bimetal modified porphyrin MOF
Taking copper-modified porphyrin MOF prepared in S1 as an organic ligand, taking trivalent gallium ions as a metal source, dissolving a proper amount of copper-modified porphyrin MOF, the metal source and polyvinylpyrrolidone in a mixed solution of N, N-dimethylformamide and acid, performing ultrasound to obtain a uniform mixed solution, then placing the mixed solution in a forced air drying oven to react for 12 hours at a proper temperature, cooling to room temperature, and performing centrifugation, washing and vacuum drying to obtain purple copper-gallium double-metal modified porphyrin MOF crystals;
s3: preparation of copper-bismuth bimetal modified porphyrin MOF
Taking the copper-modified porphyrin MOF prepared in the S1 as an organic ligand, taking trivalent bismuth ions as a metal source, dissolving a proper amount of copper-modified porphyrin MOF, the metal source and polyvinylpyrrolidone in a mixed solution of N, N-dimethylformamide and acid, performing ultrasound to obtain a uniform mixed solution, then placing the mixed solution in a forced air drying oven to react at a proper temperature for 12 hours, cooling to room temperature, and performing centrifugation, washing and vacuum drying to obtain a purple copper-bismuth bimetal-modified porphyrin MOF crystal;
s4: preparation of copper indium bimetal modified porphyrin MOF
Taking copper-modified porphyrin MOF prepared in S1 as an organic ligand, taking trivalent indium ions as a metal source, dissolving a proper amount of copper-modified porphyrin MOF, the metal source and polyvinylpyrrolidone in a mixed solution of N, N-dimethylformamide and acid, performing ultrasound to obtain a uniform mixed solution, then placing the mixed solution in a forced air drying oven to react for 12h at a proper temperature, cooling to room temperature, and performing centrifugation, washing and vacuum drying to obtain a purple copper-indium bimetal modified porphyrin MOF crystal.
2. The method of claim 1, wherein:
in S1, the dosage of the meso-tetra (4-carboxyphenyl) porphyrin, the dosage of the copper nitrate and the N, N-dimethylformamide is 80-100mg, 60-70mg and 30-100mL respectively.
3. The production method according to claim 1, characterized in that:
in S2, the dosage of copper-modified porphyrin MOF is 40-60mg, trivalent gallium ions are one of gallium chloride and gallium nitrate and are 30-50mg, and the dosage of polyvinylpyrrolidone is 10-30mg; the acid is any one of nitric acid, hydrochloric acid, sulfuric acid, acetic acid and trifluoroacetic acid.
4. The method of claim 1, wherein:
in S3, the dosage of copper-modified porphyrin MOF is 40-60mg, the dosage of trivalent bismuth ions is 40-60mg of one of bismuth chloride and bismuth nitrate, and the dosage of polyvinylpyrrolidone is 10-30mg; the acid is any one of nitric acid, hydrochloric acid, sulfuric acid, acetic acid and trifluoroacetic acid.
5. The production method according to claim 1, characterized in that:
in S4, the dosage of copper-modified porphyrin MOF is 40-60mg, the dosage of trivalent indium ions is 50-70mg of indium chloride or indium nitrate, and the dosage of polyvinylpyrrolidone is 10-30mg; the acid is any one of nitric acid, hydrochloric acid, sulfuric acid, acetic acid and trifluoroacetic acid.
6. Use of a bimetallic modified porphyrin-based MOF catalyst prepared by the preparation method according to any one of claims 1 to 5, characterized in that: and selectively catalyzing and reducing a nitrobenzene compound by taking the bimetallic modified porphyrin-based MOF catalyst as a photocatalyst to generate corresponding aniline.
7. Use according to claim 6, characterized in that:
the nitrobenzene compound comprises methyl nitrobenzene, methoxy nitrobenzene, ethyl nitrobenzene, chlorine substituted nitrobenzene, fluorine substituted nitrobenzene, cyano substituted nitrobenzene, bromine substituted nitrobenzene or amino substituted nitrobenzene; all substituents nitrobenzene include ortho, meta or para.
8. Use according to claim 6, characterized in that:
the bimetal modified porphyrin-based MOF catalyst is copper-gallium bimetal modified porphyrin MOF, copper-bismuth bimetal modified porphyrin MOF or copper-indium bimetal modified porphyrin MOF.
9. Use according to claim 6, characterized in that:
A10W white light lamp is used as an irradiation source, hydrazine hydrate is used as a hydrogen donor, methanol is used as a solvent, and a bimetallic modified porphyrin-based MOF catalyst is used for catalyzing and reducing a nitrobenzene compound at room temperature.
10. Use according to claim 9, characterized in that:
the dosage of hydrazine hydrate is 0.5-1.5mmol, the dosage of nitrobenzene compound is 0.2-1mmol, the dosage of methanol is 4-10mL, the dosage of catalyst is 2-5mg, and the illumination time is 3-10h.
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