CN114682303B - 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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- CN114682303B CN114682303B CN202210368807.5A CN202210368807A CN114682303B CN 114682303 B CN114682303 B CN 114682303B CN 202210368807 A CN202210368807 A CN 202210368807A CN 114682303 B CN114682303 B CN 114682303B
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- 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 27
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000004729 solvothermal method Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 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 70
- 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
- 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
- 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 11
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 6
- 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 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 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 1
- 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 1
- 230000002860 competitive effect Effects 0.000 abstract description 5
- 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 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 8
- 239000002253 acid Substances 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 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
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 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
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 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
- 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
- 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 1
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 description 1
- 102100024452 DNA-directed RNA polymerase III subunit RPC1 Human genes 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 101000689002 Homo sapiens DNA-directed RNA polymerase III subunit RPC1 Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 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
- 238000009776 industrial production Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- 239000011877 solvent mixture Substances 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
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- 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
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
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 nano particles; and mixing the noble metal-Fe nano particles with trivalent metal salt, a ligand and a first solvent, and performing 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 with the competitive reduction group, and has the characteristics of high selectivity, high activity and high stability, and the reaction condition is mild and has the advantage of universality.
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 of a noble metal@MOF core-shell catalyst synthesized by an in-situ one-step method.
Background
Nitroarenes are widely applied to industrial production, but the nitroarenes have biotoxicity and can cause cancer or other diseases, and selective hydrogenation of nitro and conjugated reducible functional groups in the nitroarenes is an effective way for preparing aniline derivatives with high added value; however, it is a challenge to break the balance between catalytic activity and selectivity of aniline derivatives under mild conditions.
The key to improving hydrogenation reaction activity and selectivity is effective activation of hydrogen and selective adsorption of substrate, and the metal organic framework material (Metal Organic Frameworks, MOFs) is used as a novel porous material, is a one-dimensional, two-dimensional and three-dimensional structural material formed by assembling metal atoms and organic ligands, and has the characteristics of large specific surface area, highly ordered pore structure, pore channel size, structural adjustability and the like. The coordination unsaturated metal sites within the MOFs can readily modulate the interaction between the MOFs and the reactant, activating target chemical bonds in the reactant, thereby lowering the reaction energy barrier for the desired chemical conversion.
Noble metals have better dissociative activation capacity for hydrogen than other metals, but unmodified noble metals do not achieve high selectivity when subjected to selective catalytic reactions. And the catalyst is unstable after the noble metal nano particles are loaded, the metal particles are easy to agglomerate, and the catalytic activity is reduced. The MOF shell layer in the MOF catalyst with the core-shell structure can protect metal particles from agglomeration, has high stability, and realizes high selectivity due to the interaction between the shell MOF and a substrate.
Transition low-valence metal can preferentially adsorb nitro groups, but uses Fe 2+ The synthesis of MOF-74 as a node requires a very strict environment for removing water and oxygen, the synthesized MOF-74 (Fe) is mostly 3-5 mu m, the mass transfer capacity is greatly reduced for the catalytic reaction, and few catalysts which take MOF-74 as a carrier to synthesize a core-shell structure are reported 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, wherein the catalyst prepared by the preparation method can be used for the reaction of preparing aniline derivatives with high added value by selectively reducing nitroaromatics with competitive reducing groups, and the catalyst has the characteristics of high selectivity, high activity and high stability, and has the advantages of mild reaction conditions and universality.
In order to achieve the technical effects, the invention adopts the following technical scheme:
the invention aims at providing a preparation method of a one-step synthesis noble metal@MOF core-shell catalyst, which is characterized by comprising the following steps of:
preparing noble metal-Fe nano particles;
and mixing the noble metal-Fe nano particles with trivalent metal salt, a ligand and a first solvent, and performing solvothermal reaction to obtain the noble metal@MOF core-shell catalyst.
In the invention, ferrous salt is adopted in the prior synthesis scheme, and ferrous iron is extremely easy to oxidize, so Fe is not isolated from water and oxygen 2+ Change to Fe 3+ Fe (II) -MOF-74 could not be obtained. In the synthesis method of the invention, fe in ferric salt 3+ And Fe in PtFe nano particles 0 The reaction is favorable in thermodynamics and generates Fe 2+ Then the Pt@MOF-74 (Fe) is generated in situ by coordination with the ligand, the reaction is very rapid, so that the Fe (II) -MOF-74 can be obtained without isolating water and oxygen, and the ligand and Fe are also because PtFe nano particles are taken as cores 2+ Coordination is attached to PtFe nanoparticles, so that smaller-sized MOF catalysts can be synthesized.
As a preferred technical scheme of the invention, the method for preparing the noble metal-Fe nano particles comprises the following steps: and mixing a noble metal source with an iron source and a second solvent, adding a stabilizer, a regulator and a reducing agent, and reacting under heating and/or reflux conditions to obtain the noble metal-Fe nano particles.
As a preferred embodiment of the present invention, the noble metal source comprises H 2 PtCl 4 、H 2 PtCl 6 、K 2 PtCl 4 、K 2 PtCl 6 、Na 2 PtCl 4 、Na 2 PtCl 6 Or Pt (acac) 2 Any one or at least two combinations of these, typical but non-limiting examples of which are: h 2 PtCl 4 And H 2 PtCl 6 Is combined with H 2 PtCl 6 And K 2 PtCl 4 Combinations of (K) 2 PtCl 4 And K 2 PtCl 6 Combinations of (K) 2 PtCl 6 And Na (Na) 2 PtCl 4 Is a combination of (a) and (b) 2 PtCl 4 And Na (Na) 2 PtCl 6 Is a combination of (a) and (b) 2 PtCl 6 And Pt (acac) 2 Or Pt (acac) 2 And H 2 PtCl 4 Combinations of (a) and the like.
Preferably, the iron source comprises FeCl 3 、FeCl 2 、Fe(acac) 3 Or Fe (acac) 2 Any one or at least two combinations of these, typical but non-limiting examples of which are: feCl 3 And FeCl 2 Is a combination of FeCl 2 And Fe (acac) 3 Is Fe (acac) 3 And Fe (acac) 2 Is Fe (acac) 2 And FeCl 3 Or FeCl 3 、FeCl 2 And Fe (acac) 3 Combinations of (a) and the like.
Preferably, the molar ratio of the noble metal source to the iron source is 1:1-10, 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 non-recited values within the range are equally applicable.
As a preferred embodiment of the present invention, the second solvent includes benzyl alcohol.
Preferably, the modulator 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, typical but non-limiting examples of which are: a combination of PVP and PVA, a combination of PVA and PEG, a combination of PEG and PVA, or a combination of PVP, PVA and PEG, etc.
Preferably, the molar ratio of the total amount of noble metal source to iron source to the stabilizer is 1:4-100, 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, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the molar ratio of the total amount of noble metal source to iron source to the regulator 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 non-recited values within the range of values 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 1:200-500, such as 1:250, 1:300, 1:350, 1:400 or 1:450, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
In a preferred embodiment of the present invention, the temperature of the reaction is 150 to 200℃such as 155℃160℃165℃170℃175℃180℃185℃190℃195℃or the like, but the reaction is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the reaction time is 12 to 24 hours, such as 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours or 23 hours, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the synthesis of the metal particles comprises solid-liquid separation and washing; 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 FeCl 3 、Fe(acac) 3 、Fe(NO 3 ) 3 Or Fe (OH) (CH 3 COO) 2 Any one or a combination of at least two, typical but non-limiting examples of which are: feCl 3 And Fe (acac) 3 Is Fe (acac) 3 And Fe (NO) 3 ) 3 Is a combination of Fe (NO) 3 ) 3 And Fe (OH) (CH 3 COO) 2 Combinations of (2), fe (OH) (CH 3 COO) 2 And FeCl 3 Or FeCl 3 、Fe(acac) 3 And Fe (NO) 3 ) 3 Combinations of (a) and the like.
Preferably, the ligand comprises any one or a combination of at least two of 2-hydroxyterephthalic acid, 2, 5-dihydroxyterephthalic acid, 3-hydroxy-4, 4-biphthalic acid, or 3, 3-dihydroxy-4, 4-biphthalic acid, typical but non-limiting examples of such combinations being: a combination of 2-hydroxyterephthalic acid and 2, 5-dihydroxyterephthalic acid, a combination of 2, 5-dihydroxyterephthalic acid and 3-hydroxy-4, 4-diphthalic acid, -a combination of hydroxy-4, 4-diphthalic acid and 3, 3-dihydroxy-4, 4-diphthalic acid, a combination of 3, 3-dihydroxy-4, 4-diphthalic acid and 2-hydroxyterephthalic acid, or a combination of 2-hydroxyterephthalic acid, 2, 5-dihydroxyterephthalic acid and 3-hydroxy-4, 4-diphthalic acid, and the like.
As a preferred technical solution of the present invention, the molar ratio of the noble metal-Fe nanoparticle 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 not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the Bovin ratio of the trivalent metal salt to the ligand is from 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, etc., but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the first solvent comprises 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, such as 25:2.2, 25:2.5, 25:2.8, 25:3, 25:3.2, 25:3.5 or 25:3.8, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the molar volume ratio of the noble metal-Fe nanoparticle to the first solvent is 1:350-500, such as 1:360, 1:380, 1:400, 1:420, 1:450, or 1:480, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a preferred embodiment of the present invention, the solvothermal reaction temperature is 80 to 160 ℃, such as 90 ℃, 100 ℃, 110 ℃,120 ℃, 130 ℃, 140 ℃,150 ℃, or the like, but the solvothermal reaction temperature is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the solvothermal reaction time is 16-48 h, such as 20h, 24h, 28h, 32h, 36h, 40h or 44h, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In the invention, the solvent thermal reaction is followed by solid-liquid separation and washing of the product, wherein the solid-liquid separation method comprises centrifugation, and the washing 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 one of the purposes.
The invention also aims to provide the application of the noble metal @ MOF core-shell catalyst for preparing aniline derivatives by selectively reducing nitroaromatics containing competitive reducing groups.
In the present invention, the nitroaromatic hydrocarbon includes a nitrobenzene derivative having a substituent and/or nitrobenzene not including a substituent.
Preferably, the substituents are selected from-c=c, -CHO, -c=o, -CH 3 -X (halogen), -OCH 3 、-COCH 3 、-COOCH 3 or-COOCH 2 CH 3 At least one of them.
Preferably, the position of the substituent in the nitroarene includes at least one of ortho, meta and para.
Compared with the prior art, the invention has at least 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 of a noble metal@MOF core-shell catalyst synthesized by an in-situ one-step method, wherein the core-shell MOF catalyst prepared by the preparation method is used in the process of preparing aniline derivatives by selectively reducing nitroaromatics containing competitive reducing groups under mild conditions, the nitroaromatics have high conversion rate and high selectivity of more than 95% for the aniline derivatives;
(3) The invention provides a preparation method of a noble metal@MOF core-shell catalyst synthesized by an in-situ one-step method, wherein the core-shell MOF catalyst prepared by the preparation method has high stability in the process of preparing aniline derivatives by selectively reducing nitroaromatics containing competitive reducing groups under mild conditions, and the conversion rate and selectivity are not obviously reduced after repeated cyclic reactions;
(4) The invention provides a preparation method of a noble metal@MOF core-shell catalyst synthesized by an in-situ one-step method, and the method for preparing aniline derivatives by catalyzing nitroaromatics by the catalyst prepared by the preparation method is suitable for preparing aniline derivatives by selectively reducing various nitroaromatics containing substituents.
Drawings
FIG. 1 is a TEM image of PtFe nanoparticles prepared according to example 1 of the present invention;
FIG. 2 is a TEM image of the core-shell catalyst Pt@MOF-74 (Fe) prepared in example 1 of the invention;
FIG. 3 is a HAADF-TEM image of the core-shell catalyst Pt@MOF-74 (Fe) prepared in example 1 of the present invention.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present 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, which comprises the following steps:
preparation of noble metal-Fe nanoparticles:
(1) Platinum acetylacetonate (0.1 mmol), iron acetylacetonate (1 mmol), polyvinylpyrrolidone (7 mmol), aniline (0.5 mL) were dissolved in benzyl alcohol (25 mL), and the precursor solution was prepared by ultrasonic stirring;
(2) And (3) transferring the precursor solution in the step (1) into a reaction kettle, and reacting for 12 hours at 180 ℃.
(3) Centrifugally separating the prepared PtFe nano particles, washing the PtFe nano particles with acetone and N, N-dimethylformamide for a plurality of times, and redispersing the PtFe nano particles into the N, N-dimethylformamide for later use;
mixing the noble metal-Fe nano particles with trivalent metal salt, ligand and a first solvent, and performing solvothermal reaction to obtain the noble metal@MOF core-shell catalyst:
(a) Ferric acetylacetonate (0.1 mmol) and 2, 5-dihydroxyterephthalic acid (0.18 mmol) were dissolved in 10mL of a mixed solvent of N, N-dimethylformamide and 1.8mL of methanol;
(b) PtFe (containing 1mg Pt) was dispersed in 5mL of N, N-dimethylformamide, and the dispersion was performed by sonication;
(c) And (3) uniformly mixing the solutions in the step (a) and the step (b), and transferring the solutions into a reaction kettle for reaction for 20 hours at 120 ℃.
(d) The prepared Pt@MOF-74 was centrifuged and 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, which comprises the following steps:
preparation of noble metal-Fe nanoparticles:
(1) Will K 2 PtCl 6 (0.1mmol)，FeCl 3 (0.1 mmol), polyvinyl alcohol (10 mmol), aniline (0.5 mL) were dissolved in benzyl alcohol (25 mL), and the precursor solution was prepared by ultrasonic stirring;
(2) And (3) 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 nano particles, washing the PtFe nano particles with acetone and N, N-dimethylformamide for a plurality of times, and redispersing the PtFe nano particles into the N, N-dimethylformamide for later use;
mixing the noble metal-Fe nano particles with trivalent metal salt, ligand and a first solvent, and performing solvothermal reaction to obtain the noble metal@MOF core-shell catalyst:
(a) FeCl is added 3 (0.1 mmol) and3-hydroxy-4, 4-biphenyldicarboxylic acid (0.18 mmol) was dissolved in 10mL of N, N-dimethylformamide and 1.8mL of methanol in a solvent mixture;
(b) PtFe (containing 1mg Pt) was dispersed in 5mL of N, N-dimethylformamide, and the dispersion was performed by sonication;
(c) And (3) uniformly mixing the solutions in the step (a) and the step (b), and transferring the solutions into a reaction kettle for reaction at 80 ℃ for 48 hours.
(d) The prepared Pt@MOF-74 was centrifuged and 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, which comprises the following steps:
preparation of noble metal-Fe nanoparticles:
(1) Will K 2 PtCl 4 (0.1mmol)，FeCl 2 (0.1 mmol), polyethylene glycol (0.4 mmol), aniline (0.5 mL) were dissolved in benzyl alcohol (25 mL), and the precursor solution was prepared by ultrasonic agitation;
(2) And (3) transferring the precursor solution in the step (1) into a reaction kettle, and reacting for 12 hours at 200 ℃.
(3) Centrifugally separating the prepared PtFe nano particles, washing the PtFe nano particles with acetone and N, N-dimethylformamide for a plurality of times, and redispersing the PtFe nano particles into the N, N-dimethylformamide for later use;
mixing the noble metal-Fe nano particles with trivalent metal salt, ligand and a first solvent, and performing solvothermal reaction to obtain the noble metal@MOF core-shell catalyst:
(a) Fe (NO) 3 ) 3 (0.1 mmol) and 2-hydroxyterephthalic acid (0.18 mmol) were dissolved in 10mL of a mixed solvent of N, N-dimethylformamide and 1.8mL of methanol;
(b) PtFe (containing 1mg Pt) was dispersed in 5mL of N, N-dimethylformamide, and the dispersion was performed by sonication;
(c) And (3) uniformly mixing the solutions in the step (a) and the step (b), and transferring the solutions into a reaction kettle for reaction at 160 ℃ for 16 hours.
(d) The prepared Pt@MOF-74 was centrifuged and 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, which comprises the following steps:
preparation of noble metal-Fe nanoparticles:
(1) Na is mixed with 2 PtCl 4 (0.1mmol)，Fe(acac) 2 (0.1 mmol), polyvinylpyrrolidone (7 mmol), aniline (0.5 mL) in benzyl alcohol (25 mL), and ultrasonic stirring to prepare a precursor solution;
(2) And (3) transferring the precursor solution in the step (1) into a reaction kettle, and reacting for 12 hours at 180 ℃.
(3) Centrifugally separating the prepared PtFe nano particles, washing the PtFe nano particles with acetone and N, N-dimethylformamide for a plurality of times, and redispersing the PtFe nano particles into the N, N-dimethylformamide for later use;
mixing the noble metal-Fe nano particles with trivalent metal salt, ligand and a first solvent, and performing solvothermal reaction to obtain the noble metal@MOF core-shell catalyst:
(a) By reacting Fe (OH) (CH 3 COO) 2 (0.1 mmol) and 3, 3-dihydroxy-4, 4-biphthalic acid (0.18 mmol) were dissolved in a mixed solvent of 10mL of N, N-dimethylformamide and 1.8mL of methanol;
(b) PtFe (containing 1mg Pt) was dispersed in 5mL of N, N-dimethylformamide, and the dispersion was performed by sonication;
(c) And (3) uniformly mixing the solutions in the step (a) and the step (b), and transferring the solutions into a reaction kettle for reaction for 20 hours at 120 ℃.
(d) The prepared Pt@MOF-74 was centrifuged and washed with N, N-dimethylformamide and dispersed in N, N-dimethylformamide.
Comparative example
Fe synthesized in the environment of removing water and deoxidizing in the comparative example 2+ MOF-74 (Fe) (3-5 μm) as a node was used as a comparison.
The performance of the catalysts provided in examples 1-4 and comparative examples in catalyzing the reaction of selective reduction of nitroaromatics containing competing reducing groups to aniline derivatives was tested by: 0.5mmol of 3-nitrostyrene and 0.5 mu mol of Pt@MOF74 (or equimolar MOF-74 (Fe)) containing Pt are weighed and placed in a magnetically driven high-pressure reaction kettle, 10mL of N, N-dimethylformamide is added, the reaction pressure is 0.1MPa, the reaction temperature is 60 ℃, the stirring speed is 600rpm, the reaction time is 4 hours, after the reaction is finished, each component in the catalytic system is analyzed by an Shimadzu gas chromatograph, and the results are shown in Table 1.
TABLE 1
| Selectivity of 3-aminostyrene | |
| Example 1 | 96.3％ |
| Example 2 | 94.6％ |
| Example 3 | 93.2％ |
| Example 4 | 94.8％ |
| Comparative example | 0 |
As can be seen from the test results, the noble metal@MOF core-shell catalyst synthesized by an in-situ one-step method for preparing the aniline derivative by catalyzing the selective reduction of the nitroaromatic hydrocarbon under the mild condition is provided, 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 for the selective hydrogenation of the nitroaromatic hydrocarbon under the mild condition.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (24)
1. The preparation method of the noble metal@MOF core-shell catalyst synthesized by an in-situ one-step method is characterized by comprising the following steps of:
preparing noble metal-Fe nano particles;
mixing the noble metal-Fe nano particles with trivalent metal salt, ligand and a first solvent, and obtaining the noble metal@MOF core-shell catalyst through solvothermal reaction;
wherein the ligand comprises any one or a combination of at least two of 2-hydroxy terephthalic acid, 2, 5-dihydroxy terephthalic acid, 3-hydroxy-4, 4-biphenyl dicarboxylic acid or 3, 3-dihydroxy-4, 4-biphenyl dicarboxylic acid.
2. The method of preparing the noble metal-Fe nanoparticle according to claim 1, comprising: and mixing a noble metal source with an iron source and a second solvent, adding a stabilizer, a regulator and a reducing agent, and reacting under heating and/or reflux conditions to obtain the noble metal-Fe nano particles.
3. The method of claim 2, wherein the noble metal source comprises H 2 PtCl 4 、H 2 PtCl 6 、K 2 PtCl 4 、K 2 PtCl 6 、Na 2 PtCl 4 、Na 2 PtCl 6 Or Pt (acac) 2 Any one or a combination of at least two of the above.
4. The method of claim 2, wherein the iron source comprises feci 3 、FeCl 2 、Fe(acac) 3 Or Fe (acac) 2 Any one or a combination of at least two of the above.
5. The method of claim 2, wherein the molar ratio of the noble metal source to the iron source is 1:1-10.
6. The method of claim 2, wherein the second solvent comprises benzyl alcohol.
7. The method of claim 2, wherein the modulator comprises aniline.
8. The method of claim 2, wherein the reducing agent comprises benzyl alcohol.
9. The method of claim 2, wherein the stabilizer comprises any one or a combination of at least two of PVP, PVA, or PEG.
10. The method according to claim 2, wherein the molar ratio of the total amount of the noble metal source and the iron source to the stabilizer is 1:4 to 100.
11. The method according to claim 2, wherein the molar ratio of the total amount of the noble metal source and the iron source to the regulator is 1:5 to 50.
12. The method according to claim 2, wherein 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.
13. The process according to claim 2, wherein the temperature of the reaction is 150 to 200 ℃.
14. The method according to claim 2, wherein the reaction time is 12 to 24 hours.
15. The method of claim 1, wherein the trivalent metal salt comprises feci 3 、Fe(acac) 3 、Fe(NO 3 ) 3 Or Fe (OH) (CH 3 COO) 2 Any one or a combination of at least two of these.
16. The method of claim 1, wherein the molar ratio of the noble metal-Fe nanoparticle to the trivalent metal salt is 1:2-10.
17. The method of claim 1, wherein the molar ratio of the trivalent metal salt to the ligand is from 5 to 9:9.
18. The method according to claim 1, wherein the first solvent comprises a mixed solvent of N, N-dimethylformamide and methanol.
19. The method according to claim 18, wherein the volume ratio of N, N-dimethylformamide to methanol in the mixed solvent is 25:2-4.
20. The method of claim 1, wherein the molar volume ratio of the noble metal-Fe nanoparticle to the first solvent is 1:350-500.
21. The process of claim 1, wherein the solvothermal reaction is at a temperature of 80 to 160 ℃.
22. The method of claim 1, wherein the solvothermal reaction time is 16-48 hours.
23. A noble metal @ MOF core-shell catalyst prepared by the method of any one of claims 1-22.
24. Use of the noble metal @ MOF core-shell catalyst of claim 23 for the selective reduction of nitroaromatic hydrocarbons containing competing reducing groups to prepare aniline derivatives.
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Citations (4)
| 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 |
| 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 |
Family Cites Families (1)
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-
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Patent Citations (4)
| 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 |
| 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 (5)
| Title |
|---|
| Gold Nanorods/Metal−Organic Framework Hybrids: Photo-Enhanced Peroxidase-Like Activity and SERS Performance for Organic Dyestuff Degradation and Detection;Xiaoping Zhao等;《Analytical Chemistry》;第94卷;第4484−4494页 * |
| Iron-incorporated nitrogen-doped carbon materials as oxygen reduction electrocatalysts for zinc-air batteries;Kai Chen等;《Chinese Journal of Catalysis》;第41卷(第5期);第858–867页 * |
| 基于金属有机框架材料的氧还原催化剂研究进展;任雨峰 等;《材料导报》;第36卷(第9期);全文 * |
| 李宏 等.《新型特种玻璃》.武汉理工大学出版社,2020,第225页. * |
| 金属有机框架物催化有机反应综述;徐光利 等;《有机化学》;第36卷;第1513-1527页 * |
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