CN114682303A - Preparation method for synthesizing noble metal @ MOF core-shell catalyst by in-situ one-step method - Google Patents
Preparation method for synthesizing noble metal @ MOF core-shell catalyst by in-situ one-step method Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000011258 core-shell material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 238000004729 solvothermal method Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 93
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 81
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 24
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 16
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 12
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001448 anilines Chemical class 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 6
- 229910019029 PtCl4 Inorganic materials 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- KYBBBPXPSOMZQU-UHFFFAOYSA-N 6-hydroxy-4-phenylcyclohexa-2,4-diene-1,1-dicarboxylic acid Chemical compound OC1C=C(C=CC1(C(=O)O)C(=O)O)C1=CC=CC=C1 KYBBBPXPSOMZQU-UHFFFAOYSA-N 0.000 claims description 5
- 229910020427 K2PtCl4 Inorganic materials 0.000 claims description 5
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 5
- NBSQSLMPSHYHHO-UHFFFAOYSA-N OC1(C=C(C=CC1(C(=O)O)C(=O)O)C1=CC=CC=C1)O Chemical compound OC1(C=C(C=CC1(C(=O)O)C(=O)O)C1=CC=CC=C1)O NBSQSLMPSHYHHO-UHFFFAOYSA-N 0.000 claims description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910003609 H2PtCl4 Inorganic materials 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 108010006654 Bleomycin Proteins 0.000 claims 1
- 229960001561 bleomycin Drugs 0.000 claims 1
- OYVAGSVQBOHSSS-UAPAGMARSA-O bleomycin A2 Chemical compound N([C@H](C(=O)N[C@H](C)[C@@H](O)[C@H](C)C(=O)N[C@@H]([C@H](O)C)C(=O)NCCC=1SC=C(N=1)C=1SC=C(N=1)C(=O)NCCC[S+](C)C)[C@@H](O[C@H]1[C@H]([C@@H](O)[C@H](O)[C@H](CO)O1)O[C@@H]1[C@H]([C@@H](OC(N)=O)[C@H](O)[C@@H](CO)O1)O)C=1N=CNC=1)C(=O)C1=NC([C@H](CC(N)=O)NC[C@H](N)C(N)=O)=NC(N)=C1C OYVAGSVQBOHSSS-UAPAGMARSA-O 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000003750 conditioning effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000002860 competitive effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 229910002836 PtFe Inorganic materials 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000013118 MOF-74-type framework Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
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- 229920001223 polyethylene glycol Polymers 0.000 description 5
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000012918 MOF catalyst Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
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- 239000001301 oxygen Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 description 1
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- SYZVQXIUVGKCBJ-UHFFFAOYSA-N 1-ethenyl-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(C=C)=C1 SYZVQXIUVGKCBJ-UHFFFAOYSA-N 0.000 description 1
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydroxy-4, 4-biphenyldicarboxylic acid Chemical compound 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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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
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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Abstract
The invention provides a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method, which comprises the following steps: preparing noble metal-Fe nanoparticles; and mixing the noble metal-Fe nano particles with trivalent metal salt, a ligand and a first solvent, and carrying out solvothermal reaction to obtain the noble metal @ MOF core-shell catalyst. The catalyst prepared by the preparation method can be used for the reaction of preparing the aniline derivative with high added value by the selective reduction of the nitroarene containing competitive reducing group, has the characteristics of high selectivity, high activity and high stability, and has the advantages of mild reaction conditions and common adaptability.
Description
Technical Field
The invention belongs to the field of catalyst synthesis, relates to a preparation method of a MOF core-shell catalyst, and particularly relates to a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method.
Background
The nitroaromatic is widely applied to industrial production, but the nitroaromatic has biotoxicity, can cause cancers or other diseases, and the selective hydrogenation of the nitro group and the conjugated reducible functional group in the nitroaromatic is an effective way for preparing the aniline derivative with high added value; however, it is a challenge to strike a balance between catalytic activity and selectivity of aniline derivatives under mild conditions.
The key for improving the activity and selectivity of the hydrogenation reaction is effective activation of hydrogen and selective adsorption of a substrate, and a Metal Organic Framework (MOFs) is a novel porous material which is a one-dimensional, two-dimensional and three-dimensional structure material formed by assembling Metal atoms and Organic ligands, and has the characteristics of large specific surface, highly ordered pore structure, pore size, structure adjustability and the like. The coordinated unsaturated metal sites inside the MOFs can easily regulate the interaction between the MOFs and the reactant, activate the target chemical bond in the reactant, and thereby lower the reaction energy barrier for the desired chemical conversion.
Noble metals have a dissociation activation capability for hydrogen gas superior to other metals, but unmodified noble metals do not achieve high selectivity when performing selective catalytic reactions. And the catalyst loaded with noble metal nano particles is unstable, and the metal particles are easy to agglomerate, so that the catalytic activity is reduced. The MOF shell layer in the core-shell MOF catalyst can protect metal particles from agglomeration, the stability is high, and high selectivity is realized due to the interaction between the MOF shell layer and a substrate.
The transitional low-valence metal can preferentially adsorb the nitro group, but the transitional low-valence metal is Fe2+The synthesis of MOF-74 which is a node requires a very harsh environment for removing water and oxygen, the mass transfer capacity of the synthesized MOF-74(Fe) is greatly reduced for a catalytic reaction because most of the synthesized MOF-74(Fe) is 3-5 mu m, and few reports are reported for synthesizing a catalyst with a core-shell structure by taking the MOF-74 as a carrier at present.
Disclosure of Invention
In order to solve the technical problems, the application provides a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method, the catalyst prepared by the preparation method can be used for the reaction of preparing high value-added aniline derivatives by selective reduction of nitroarenes containing competitive reducing groups, and the catalyst has the characteristics of high selectivity, high activity and high stability, is mild in reaction conditions and has the advantage of common adaptability.
In order to achieve the technical effect, the invention adopts the following technical scheme:
one purpose of the invention is to provide a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by a one-step method, which is characterized by comprising the following steps:
preparing noble metal-Fe nanoparticles;
and mixing the noble metal-Fe nano particles with trivalent metal salt, a ligand and a first solvent, and carrying out solvothermal reaction to obtain the noble metal @ MOF core-shell catalyst.
In the invention, ferrous iron salt is adopted in the previous synthetic scheme, and the ferrous iron is very easy to oxidize, so that Fe is easily oxidized when water and oxygen are not isolated2+To Fe3+Fe (II) -MOF-74 could not be obtained. In the synthesis method of the invention, Fe in ferric salt3+With Fe in PtFe nanoparticles0A neutralization reaction takes place, the neutralization reaction is thermodynamically favorable, and Fe is generated2+Then coordinated with ligand to generate Pt @ MOF-74(Fe) in situ on Pt particles, the reaction is rapid, so Fe (II) -MOF-74 can be obtained without isolating water and oxygen, and the ligand and Fe are used as cores because PtFe nanoparticles are used as cores2+Coordinate to the PtFe nanoparticles and thus allow synthesis of MOF catalysts of smaller size.
As a preferred embodiment of the present invention, the method for preparing noble metal-Fe nanoparticles comprises: mixing a noble metal source, an iron source and a second solvent, adding a stabilizer, a regulator and a reducing agent, and reacting under the conditions of heating and/or refluxing to obtain the noble metal-Fe nano-particles.
As a preferred embodiment of the present invention, the noble metal source comprises H2PtCl4、H2PtCl6、K2PtCl4、K2PtCl6、Na2PtCl4、Na2PtCl6Or Pt (acac)2Any one or at least two combinations of the following, typical but non-limiting examples being: h2PtCl4And H2PtCl6Combination of (1), H2PtCl6And K2PtCl4Combination of (1), K2PtCl4And K2PtCl6Combination of (1), K2PtCl6And Na2PtCl4Combination of (A) and (B), Na2PtCl4And Na2PtCl6Combination of (A) and (B), Na2PtCl6And Pt (acac)2Or Pt (acac)2And H2PtCl4Combinations of (a), (b), and the like.
Preferably, the iron source comprises FeCl3、FeCl2、Fe(acac)3Or Fe (acac)2Any one or at least two combinations of the following, typical but non-limiting examples being: FeCl3And FeCl2Combination of (1), FeCl2And Fe (acac)3Combination of (1), Fe (acac)3And Fe (acac)2Combination of (1), Fe (acac)2And FeCl3Combinations of (5) or FeCl3、FeCl2And Fe (acac)3Combinations of (a), (b), and the like.
Preferably, the molar ratio of the noble metal source to the iron source is 1:1 to 10, such as 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, or 1:9, but is not limited to the recited values, and other unrecited values within this range are equally applicable.
As a preferred embodiment of the present invention, the second solvent includes benzyl alcohol.
Preferably, the modifier comprises aniline.
Preferably, the reducing agent comprises benzyl alcohol.
Preferably, the stabiliser comprises any one of PVP, PVA or PEG, or a combination of at least two of these, typical but non-limiting examples being: combinations of PVP and PVA, PVA and PEG, PEG and PVA, PVP, PVA and PEG, and the like.
Preferably, the molar ratio of the total amount of the noble metal source and the iron source to the stabilizer is 1:4 to 100, such as 1:5, 1:8, 1:10, 1:15, 1:20, 1:25, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, or 1:90, but not limited to the recited values, and other values not recited within this range of values are equally applicable.
Preferably, the molar ratio of the total amount of the noble metal source and the iron source to the modifier is 1:5 to 50, such as 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, or 1:45, but is not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the molar volume ratio of the total amount of the noble metal source and the iron source to the second solvent is 1:200 to 500, such as 1:250, 1:300, 1:350, 1:400, or 1:450, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the reaction temperature is 150 to 200 ℃, for example, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ or 195 ℃, but the reaction temperature is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction time is 12-24 h, such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, after the metal particles are synthesized, solid-liquid separation and washing are carried out; the solid-liquid separation method comprises centrifugation; the washing solvent comprises acetone, ethanol or/and N, N-dimethylformamide.
As a preferred embodiment of the present invention, the trivalent metal salt comprises FeCl3、Fe(acac)3、Fe(NO3)3Or Fe (OH) (CH)3COO)2Any one or a combination of at least two of the following, typical but non-limiting examples being: FeCl3And Fe (acac)3Combination of (1), Fe (acac)3And Fe (NO)3)3Combination of (5) Fe (NO)3)3And Fe (OH) (CH)3COO)2Combination of (1), Fe (OH) (CH)3COO)2And FeCl3Combinations of (5) or FeCl3、Fe(acac)3And Fe (NO)3)3Combinations of (A), (B), and the like。
Preferably, the ligand comprises any one of 2-hydroxyterephthalic acid, 2, 5-dihydroxyterephthalic acid, 3-hydroxy-4, 4-biphenyldicarboxylic acid or 3, 3-dihydroxy-4, 4-biphenyldicarboxylic acid or a combination of at least two of these, typical but non-limiting examples being: a combination of 2-hydroxyterephthalic acid and 2, 5-dihydroxyterephthalic acid, a combination of 2, 5-dihydroxyterephthalic acid and 3-hydroxy-4, 4-biphenyldicarboxylic acid, a combination of hydroxy-4, 4-biphenyldicarboxylic acid and 3, 3-dihydroxy-4, 4-biphenyldicarboxylic acid, a combination of 3, 3-dihydroxy-4, 4-biphenyldicarboxylic acid and 2-hydroxyterephthalic acid, a combination of 2-hydroxyterephthalic acid, 2, 5-dihydroxyterephthalic acid and 3-hydroxy-4, 4-biphenyldicarboxylic acid, and the like.
In a preferred embodiment of the present invention, the molar ratio of the noble metal-Fe nanoparticles to the trivalent metal salt is 1:2 to 10, such as 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, or 1:9, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the bosch ratio of the trivalent metal salt to the ligand is 5 to 9:9, such as 5.5:9, 6:9, 6.5:9, 7:9, 7.5:9, 8:9, or 8.5:9, but is not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the first solvent includes a mixed solvent of N, N-dimethylformamide and methanol.
Preferably, the volume ratio of N, N-dimethylformamide to methanol in the mixed solvent is 25:2 to 4, such as 25:2.2, 25:2.5, 25:2.8, 25:3, 25:3.2, 25:3.5 or 25:3.8, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the molar volume ratio of the noble metal-Fe nanoparticles to the first solvent is 1:350 to 500, such as 1:360, 1:380, 1:400, 1:420, 1:450, or 1:480, but not limited to the recited values, and other values not recited within this range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the solvothermal reaction is 80 to 160 ℃, for example, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but the temperature is not limited to the recited values, and other values not recited in the above range are also applicable.
Preferably, the solvothermal reaction time is 16-48 h, such as 20h, 24h, 28h, 32h, 36h, 40h or 44h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, after the solvothermal reaction, the method also comprises the steps of carrying out solid-liquid separation and washing on the product, wherein the solid-liquid separation method comprises centrifugation, and the washed solvent comprises methanol or/and N, N-dimethylformamide.
The second purpose of the invention is to provide a noble metal @ MOF core-shell catalyst, which is prepared by the preparation method of the first purpose.
The third purpose of the invention is to provide an application of the noble metal @ MOF core-shell catalyst, which is used for the reaction of preparing aniline derivatives by selective reduction of nitroarenes containing competitive reducing groups.
In the present invention, the nitroarene includes nitrobenzene derivatives having substituents and/or nitrobenzene containing no substituents.
Preferably, the substituents are selected from-C ═ C, -CHO, -C ═ O, -CH3-X (halogen), -OCH3、-COCH3、-COOCH3or-COOCH2CH3At least one of (1).
Preferably, the position of the substituent in the nitroarene includes at least one of ortho, meta and para positions.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention provides a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method, which is simple to operate and can realize the synthesis of small-size MOF-74(Fe) without strictly removing water and oxygen;
(2) the invention provides a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method, wherein the core-shell MOF catalyst prepared by the preparation method is used for preparing aniline derivatives by selectively reducing nitroarenes containing competitive reducing groups under mild conditions, wherein the nitroarenes have high conversion rate and the aniline derivatives have high selectivity of more than 95%;
(3) the invention provides a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method, wherein the core-shell MOF catalyst prepared by the preparation method has high stability when used for preparing aniline derivatives by selectively reducing nitroarenes containing competitive reducing groups under mild conditions, and the conversion rate and the selectivity are not obviously reduced after repeated reactions;
(4) the invention provides a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method, and the method for preparing aniline derivatives by catalyzing nitroarenes by using the catalyst prepared by the preparation method is suitable for preparing the aniline derivatives by selectively reducing various substituent-containing nitroarenes.
Drawings
FIG. 1 is a TEM image of PtFe nanoparticles prepared in example 1 of the present invention;
FIG. 2 is a TEM image of core-shell structured catalyst Pt @ MOF-74(Fe) prepared in example 1 of the present invention;
FIG. 3 is a HAADF-TEM image of core-shell structured catalyst Pt @ MOF-74(Fe) prepared in example 1 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method, and the preparation method comprises the following steps:
preparing noble metal-Fe nanoparticles:
(1) dissolving platinum acetylacetonate (0.1mmol), ferric acetylacetonate (1mmol), polyvinylpyrrolidone (7mmol) and aniline (0.5mL) in benzyl alcohol (25mL), and ultrasonically stirring to prepare a precursor solution;
(2) and (2) transferring the precursor solution in the step (1) into a reaction kettle, and reacting for 12h at 180 ℃.
(3) Centrifugally separating the prepared PtFe nanoparticles, washing the PtFe nanoparticles for a plurality of times by using acetone and N, N-dimethylformamide, and re-dispersing the PtFe nanoparticles into the N, N-dimethylformamide for later use;
mixing the noble metal-Fe nanoparticles with a trivalent metal salt, a ligand and a first solvent, and obtaining the noble metal @ MOF core-shell catalyst through solvothermal reaction:
(a) dissolving ferric acetylacetonate (0.1mmol) and 2, 5-dihydroxyterephthalic acid (0.18mmol) in a mixed solvent of 10mL of N, N-dimethylformamide and 1.8mL of methanol;
(b) dispersing PtFe (containing 1mg of Pt) in 5mL of N, N-dimethylformamide, and performing ultrasonic dispersion;
(c) and (c) uniformly mixing the solutions in the step (a) and the step (b), transferring the mixture into a reaction kettle, and reacting for 20 hours at 120 ℃.
(d) The prepared Pt @ MOF-74 was centrifuged, washed with N, N-dimethylformamide, and dispersed in N, N-dimethylformamide.
Example 2
The embodiment provides a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method, and the preparation method comprises the following steps:
preparing noble metal-Fe nanoparticles:
(1) will K2PtCl6(0.1mmol)，FeCl3(0.1mmol), polyvinyl alcohol (10mmol) and aniline (0.5mL) are dissolved in benzyl alcohol (25mL), and precursor solution is prepared by ultrasonic stirring;
(2) and (2) transferring the precursor solution in the step (1) into a reaction kettle, and reacting for 24 hours at 150 ℃.
(3) Centrifugally separating the prepared PtFe nanoparticles, washing the PtFe nanoparticles for a plurality of times by using acetone and N, N-dimethylformamide, and re-dispersing the PtFe nanoparticles into the N, N-dimethylformamide for later use;
mixing the noble metal-Fe nanoparticles with a trivalent metal salt, a ligand and a first solvent, and obtaining the noble metal @ MOF core-shell catalyst through solvothermal reaction:
(a) FeCl is added3(0.1mmol) and 3-hydroxy-4, 4-biphenyldicarboxylic acid (0.18mmol) were dissolved in a mixed solvent of 10mL of N, N-dimethylformamide and 1.8mL of methanol;
(b) dispersing PtFe (containing 1mg of Pt) in 5mL of N, N-dimethylformamide, and performing ultrasonic dispersion;
(c) and (c) uniformly mixing the solutions in the step (a) and the step (b), transferring the mixture into a reaction kettle, and reacting for 48 hours at 80 ℃.
(d) The prepared Pt @ MOF-74 was centrifuged, washed with N, N-dimethylformamide, and dispersed in N, N-dimethylformamide.
Example 3
The embodiment provides a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method, and the preparation method comprises the following steps:
preparing noble metal-Fe nanoparticles:
(1) will K2PtCl4(0.1mmol)，FeCl2(0.1mmol), polyethylene glycol (0.4mmol) and aniline (0.5mL) are dissolved in benzyl alcohol (25mL), and precursor solution is prepared by ultrasonic stirring;
(2) and (2) transferring the precursor solution in the step (1) into a reaction kettle, and reacting for 12h at 200 ℃.
(3) Centrifugally separating the prepared PtFe nanoparticles, washing the PtFe nanoparticles for a plurality of times by using acetone and N, N-dimethylformamide, and re-dispersing the PtFe nanoparticles into the N, N-dimethylformamide for later use;
mixing the noble metal-Fe nanoparticles with a trivalent metal salt, a ligand and a first solvent, and obtaining the noble metal @ MOF core-shell catalyst through solvothermal reaction:
(a) mixing Fe (NO)3)3(0.1mmol) and 2-hydroxyterephthalic acid (0.18mmol) were dissolved in a mixed solvent of 10mL of N, N-dimethylformamide and 1.8mL of methanol;
(b) dispersing PtFe (containing 1mg of Pt) in 5mL of N, N-dimethylformamide, and performing ultrasonic dispersion;
(c) and (c) uniformly mixing the solutions in the step (a) and the step (b), transferring the mixture into a reaction kettle, and reacting for 16 hours at 160 ℃.
(d) The prepared Pt @ MOF-74 was centrifuged, washed with N, N-dimethylformamide, and dispersed in N, N-dimethylformamide.
Example 4
The embodiment provides a preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method, and the preparation method comprises the following steps:
preparing noble metal-Fe nanoparticles:
(1) mixing Na2PtCl4(0.1mmol)，Fe(acac)2(0.1mmol), polyvinylpyrrolidone (7mmol) and aniline (0.5mL) are dissolved in benzyl alcohol (25mL), and precursor solution is prepared by ultrasonic stirring;
(2) and (2) transferring the precursor solution in the step (1) into a reaction kettle, and reacting for 12h at 180 ℃.
(3) Centrifugally separating the prepared PtFe nanoparticles, washing the PtFe nanoparticles for a plurality of times by using acetone and N, N-dimethylformamide, and re-dispersing the PtFe nanoparticles into the N, N-dimethylformamide for later use;
mixing the noble metal-Fe nanoparticles with a trivalent metal salt, a ligand and a first solvent, and obtaining the noble metal @ MOF core-shell catalyst through solvothermal reaction:
(a) reacting Fe (OH) (CH)3COO)2(0.1mmol) and 3, 3-dihydroxy-4, 4-biphenyldicarboxylic acid (0.18mmol) were dissolved in a mixed solvent of 10mL of N, N-dimethylformamide and 1.8mL of methanol;
(b) dispersing PtFe (containing 1mg of Pt) in 5mL of N, N-dimethylformamide, and performing ultrasonic dispersion;
(c) and (c) uniformly mixing the solutions in the step (a) and the step (b), transferring the mixture into a reaction kettle, and reacting for 20 hours at 120 ℃.
(d) The prepared Pt @ MOF-74 was centrifuged, washed with N, N-dimethylformamide, and dispersed in N, N-dimethylformamide.
Comparative example
This comparative example was synthesized with Fe in a water-and oxygen-removing environment2+MOF-74(Fe) (3-5 μm) as a node was used for comparison.
The performance of the catalysts provided in examples 1 to 4 and comparative examples in catalyzing the reaction for preparing aniline derivatives by selective reduction of nitroarenes containing competitive reducing groups was tested by the following specific method: weighing 0.5mmol of 3-nitrostyrene and 0.5 mu mol of Pt @ MOF-74 (or equimolar MOF-74(Fe)) in a magnetically-driven high-pressure reaction kettle, adding 10mL of N, N-dimethylformamide, reacting at a pressure of 0.1MPa and a reaction temperature of 60 ℃, stirring at a speed of 600rpm for 4h, and after the reaction is finished, analyzing each component in the catalytic system by using Shimadzu gas chromatograph, wherein the results are shown in Table 1.
TABLE 1
| Selectivity to 3-aminostyrene | |
| Example 1 | 96.3％ |
| Example 2 | 94.6％ |
| Example 3 | 93.2％ |
| Example 4 | 94.8％ |
| Comparative example | 0 |
According to the test results, the invention provides the noble metal @ MOF core-shell catalyst synthesized by the in-situ one-step method for preparing the aniline derivative by catalyzing the selective reduction of the nitroaromatic under the mild condition, and compared with the traditional preparation method of the supported catalyst, the core-shell structure Pt @ MOF-74 nano catalyst prepared by the invention has high selectivity, activity and stability on the selective hydrogenation of the nitroaromatic under the mild condition.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method for synthesizing a noble metal @ MOF core-shell catalyst by an in-situ one-step method is characterized by comprising the following steps:
preparing noble metal-Fe nanoparticles;
and mixing the noble metal-Fe nano particles with trivalent metal salt, a ligand and a first solvent, and carrying out solvothermal reaction to obtain the noble metal @ MOF core-shell catalyst.
2. The method of preparing according to claim 1, wherein the method of preparing noble metal-Fe nanoparticles comprises: mixing a noble metal source, an iron source and a second solvent, adding a stabilizer, a regulator and a reducing agent, and reacting under the conditions of heating and/or refluxing to obtain the noble metal-Fe nano-particles.
3. The method of claim 2, wherein said noble metal source comprises H2PtCl4、H2PtCl6、K2PtCl4、K2PtCl6、Na2PtCl4、Na2PtCl6Or Pt (acac)2Any one or a combination of at least two of;
preferably, the iron source comprises FeCl3、FeCl2、Fe(acac)3Or Fe (acac)2Any one or a combination of at least two of;
preferably, the molar ratio of the noble metal source to the iron source is 1: 1-10.
4. The production method according to claim 2 or 3, wherein the second solvent comprises benzyl alcohol;
preferably, the conditioning agent comprises aniline;
preferably, the reducing agent comprises benzyl alcohol;
preferably, the stabilizer comprises any one or a combination of at least two of PVP, PVA or PEG;
preferably, the molar ratio of the total amount of the noble metal source and the iron source to the stabilizer is 1: 4-100;
preferably, the molar ratio of the total amount of the noble metal source and the iron source to the regulator is 1: 5-50;
preferably, the molar volume ratio of the total amount of the noble metal source and the iron source to the second solvent is 1:200 to 500.
5. The method according to any one of claims 2 to 4, wherein the reaction temperature is 150 to 200 ℃;
preferably, the reaction time is 12-24 h.
6. The method according to any one of claims 1 to 5, wherein the trivalent metal salt comprises FeCl3、Fe(acac)3、Fe(NO3)3Or Fe (OH) (CH)3COO)2Any one or a combination of at least two of;
preferably, the ligand comprises any one of 2-hydroxyterephthalic acid, 2, 5-dihydroxyterephthalic acid, 3-hydroxy-4, 4-biphenyldicarboxylic acid or 3, 3-dihydroxy-4, 4-biphenyldicarboxylic acid or a combination of at least two thereof.
7. The method according to any one of claims 1 to 6, wherein the molar ratio of the noble metal-Fe nanoparticles to the trivalent metal salt is 1:2 to 10;
preferably, the bleomycin ratio of the trivalent metal salt to the ligand is 5-9: 9;
preferably, the first solvent includes a mixed solvent of N, N-dimethylformamide and methanol;
preferably, the volume ratio of the N, N-dimethylformamide to the methanol in the mixed solvent is 25: 2-4;
preferably, the molar volume ratio of the noble metal-Fe nanoparticles to the first solvent is 1: 350-500.
8. The method according to any one of claims 1 to 7, wherein the temperature of the solvothermal reaction is 80 to 160 ℃;
preferably, the solvothermal reaction time is 16-48 h.
9. A noble metal @ MOF core-shell catalyst, characterized in that it is prepared by the preparation method of any one of claims 1 to 8.
10. Use of a noble metal @ MOF core-shell catalyst according to claim 9 for the selective reduction of nitroarenes containing competing reducing groups to aniline derivatives.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115837286A (en) * | 2022-11-14 | 2023-03-24 | 北京师范大学 | Limited-domain nano reactor for peroxide activation and preparation method thereof |
| CN115888831A (en) * | 2022-09-30 | 2023-04-04 | 云南大学 | Preparation method and application of platinum-loaded tin-iron bimetallic organic framework material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949286A (en) * | 2014-04-16 | 2014-07-30 | 国家纳米科学中心 | MOFs (Metal-Organic Frameworks)@noble metal@MOFs catalyst applicable to selective hydrogenation reaction, as well as preparation method and application thereof |
| CN109638304A (en) * | 2018-12-29 | 2019-04-16 | 江苏大学 | A kind of preparation method and purposes of M-MOF-74/ graphene composite cathode material |
| CN110756225A (en) * | 2019-08-30 | 2020-02-07 | 北京化工大学 | Metal/MOFs nano catalyst and preparation method and application thereof |
| US20200102337A1 (en) * | 2017-02-02 | 2020-04-02 | Centre National De La Recherche Scientifique | Low temperature process for the synthesis of mof carboxylate nanoparticles |
| CN113694966A (en) * | 2020-05-21 | 2021-11-26 | 国家纳米科学中心 | Bimetallic MOF catalyst for synthesizing cyclic lactone by serially catalyzing cyclic alcohol and preparation method and application thereof |
-
2022
- 2022-04-08 CN CN202210368807.5A patent/CN114682303B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949286A (en) * | 2014-04-16 | 2014-07-30 | 国家纳米科学中心 | MOFs (Metal-Organic Frameworks)@noble metal@MOFs catalyst applicable to selective hydrogenation reaction, as well as preparation method and application thereof |
| US20200102337A1 (en) * | 2017-02-02 | 2020-04-02 | Centre National De La Recherche Scientifique | Low temperature process for the synthesis of mof carboxylate nanoparticles |
| CN109638304A (en) * | 2018-12-29 | 2019-04-16 | 江苏大学 | A kind of preparation method and purposes of M-MOF-74/ graphene composite cathode material |
| CN110756225A (en) * | 2019-08-30 | 2020-02-07 | 北京化工大学 | Metal/MOFs nano catalyst and preparation method and application thereof |
| CN113694966A (en) * | 2020-05-21 | 2021-11-26 | 国家纳米科学中心 | Bimetallic MOF catalyst for synthesizing cyclic lactone by serially catalyzing cyclic alcohol and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| KAI CHEN等: "Iron-incorporated nitrogen-doped carbon materials as oxygen reduction electrocatalysts for zinc-air batteries", 《CHINESE JOURNAL OF CATALYSIS》, vol. 41, no. 5, pages 858, XP086010058, DOI: 10.1016/S1872-2067(19)63507-2 * |
| XIAOPING ZHAO等: "Gold Nanorods/Metal−Organic Framework Hybrids: Photo-Enhanced Peroxidase-Like Activity and SERS Performance for Organic Dyestuff Degradation and Detection", 《ANALYTICAL CHEMISTRY》, vol. 94, pages 4484 * |
| 任雨峰 等: "基于金属有机框架材料的氧还原催化剂研究进展", 《材料导报》, vol. 36, no. 9 * |
| 徐光利 等: "金属有机框架物催化有机反应综述", 《有机化学》, vol. 36, pages 1513 - 1527 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115888831A (en) * | 2022-09-30 | 2023-04-04 | 云南大学 | Preparation method and application of platinum-loaded tin-iron bimetallic organic framework material |
| CN115888831B (en) * | 2022-09-30 | 2024-02-20 | 云南大学 | Preparation method and application of platinum-loaded tin-iron bimetallic organic frame material |
| CN115837286A (en) * | 2022-11-14 | 2023-03-24 | 北京师范大学 | Limited-domain nano reactor for peroxide activation and preparation method thereof |
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