CN106046032A - MOF (metal-organic framework) material constructed on basis of pentabasic aromatic carboxylic acid as well as synthesis method and catalytic application of MOF material - Google Patents
MOF (metal-organic framework) material constructed on basis of pentabasic aromatic carboxylic acid as well as synthesis method and catalytic application of MOF material Download PDFInfo
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- CN106046032A CN106046032A CN201610394830.6A CN201610394830A CN106046032A CN 106046032 A CN106046032 A CN 106046032A CN 201610394830 A CN201610394830 A CN 201610394830A CN 106046032 A CN106046032 A CN 106046032A
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- carboxylic acid
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- organic framework
- aromatic carboxylic
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 47
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 title abstract description 9
- 238000001308 synthesis method Methods 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013110 organic ligand Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims abstract 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- 239000002178 crystalline material Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- HGCHUZIWRLBTGP-UHFFFAOYSA-N octanoic acid;sodium Chemical group [Na].CCCCCCCC(O)=O HGCHUZIWRLBTGP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- XRRQZKOZJFDXON-UHFFFAOYSA-N nitric acid;silver Chemical compound [Ag].O[N+]([O-])=O XRRQZKOZJFDXON-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- ZXKXJHAOUFHNAS-FVGYRXGTSA-N (S)-fenfluramine hydrochloride Chemical compound [Cl-].CC[NH2+][C@@H](C)CC1=CC=CC(C(F)(F)F)=C1 ZXKXJHAOUFHNAS-FVGYRXGTSA-N 0.000 abstract 1
- RWSISFYNEVCJME-UHFFFAOYSA-N 2-[3-carboxy-5-(2,5-dicarboxyphenyl)phenyl]terephthalic acid Chemical compound C(=O)(O)C1=C(C=C(C=C1)C(=O)O)C=1C=C(C(=O)O)C=C(C=1)C1=C(C=CC(=C1)C(=O)O)C(=O)O RWSISFYNEVCJME-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229960003742 phenol Drugs 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940126680 traditional chinese medicines Drugs 0.000 description 2
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- -1 hydroxybenzene amine Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/17—Silver
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an MOF (metal-organic framework) material constructed on basis of pentabasic aromatic carboxylic acid as well as a synthesis method and a catalytic application of the MOF material and belongs to the technical field of crystalline-state materials and catalytic applications. The MOF material has a chemical molecular formula as follows: {[Ag2(ddcba)(4,4'-bipy)2]}n, wherein n denotes positive infinity, ddcba denotes 3,5-bis(2,5-dicarboxyl phenyl) benzoic acid, and 4,4'-bipy denotes 4,4'-dipyridyl. Under the closed condition, the pH values of a system of polycarboxylic acid organic ligands and silver nitrate are adjusted through sodium hydroxide under the hydrothermal condition, a surfactant is added to serve as an additive, and the crystalline-state MOF material is obtained through a hydrothermal reaction. A further test proves that the material has relatively high catalytic activity in a reduction reaction of p-nitrophenol and an isomeride of p-nitrophenol.
Description
Technical field
The present invention relates to a kind of metal-organic framework material synthetic method constructed based on 5-membered aromatic carboxylic acid and catalysis thereof
Application, belongs to crystalline material and catalytic applications technical field.It is specifically that main part, itrogenous organic substance are with five yuan of carboxylic acid Organic substances
Assistant ligand, transition metal silver is that metal center process is self-assembly of metal-organic framework material (MOF), and test shows this crystalline substance
State material has higher catalytic activity in catalysis reduction paranitrophenol and isomerism precursor reactant thereof.
Background technology
Metal-organic framework material (Metal-Organic Frameworks is called for short MOFs) is a kind of novel micropore
Crystalline material.Metal-organic framework material is with metal ion or metal ion bunch as node, with organic ligand as bridging, with coordination
Key is that active force is attached, and forms the crystal space structure of long-range order.Up to now, aromatics polybasic carboxylic acid part is by extensively
General being applied to constructs metal-organic framework materials, is current most study, the most successful class part.Same conventional porous
Material is compared, and it has: 1, duct size is adjustable 2, specific surface area is big 3, regulation etc. can be modified in framework ingredient variation 4, duct
Plurality of advantages.In view of above-mentioned advantage, metal-organic framework material optical, electrical, magnetic, sense, adsorb, the field such as catalysis has important
Application prospect.Except utilizing the pore passage structure of its high-specific surface area and regular uniform distribution to carry out in catalytic applications therein
Beyond the load of noble metal nano particles, metal-organic framework material itself also can be as some organic reaction system or specific
The catalyst of reaction.
Meanwhile, it is in industrial wastewater the most intractable one with the paranitrophenol (4-NP) phenol organic matter as representative
Plant organic pollution, under low concentration, human body and organism in water can be caused serious harm.The degraded of paranitrophenol is arranged
Execute and concentrate on phase autoclave electric discharge, biological bacterium degraded etc., utilize efficient different-phase catalyst to be reduced into by paranitrophenol right
Amino-phenol, is a kind of good and the most attractive measure；Still further aspect be exactly this degradation reaction product it
One 4-AP is important industrial chemicals.Para-aminophenol, also known as " para hydroxybenzene amine ", is a kind of widely used chemical industry
Raw material, all has critically important application at industrial circles such as chemical industry, medicine, fuel, rubber and oil dopes.Therefore, by right
The reactant that environmental injury is bigger is converted into utilizable chemical industry intermediate raw material, has great economy, social meaning.
Summary of the invention
The invention provides a kind of metal-organic framework material synthetic method constructed based on 5-membered aromatic carboxylic acid, and should
Crystalline material is applied in catalysis reduction paranitrophenol and isomerism precursor reactant thereof.
A kind of metal-organic framework material (Ag-MOF) constructed based on five yuan of carboxylic acids, second bipyridine and silver nitrate, this gold
Belong to organic framework materials to be Ag and five yuan of carboxylic acid organic ligands, nitrogenous auxiliary join the 3-dimensional metal organic backbone crystal being self-assembly of
Material, its chemical general formula is: { [Ag2(ddcba)(4,4’-bipy)2]}n, wherein n represents the most infinite, and ddcba represents 3,5-bis-
(2,5-dicarboxyphenyi) benzoic acid, 4,4 '-bipy represent 4,4'-Bipyridine.
This crystalline material belongs to monoclinic system, and space group is Pc, and cell parameter is: α=γ=90 °, β=97.711 °.
The preparation method of described metal-organic framework material, comprises the following steps: under sealing condition, organic ligand 3,
5-bis-(2,5-dicarboxyphenyi) benzoic acid, 4,4'-Bipyridine and silver nitrate in aqueous, via hydro-thermal reaction, and at table
Face activating agent as obtaining the metal-organic framework material with crystal structure under conditions of additive, i.e. Ag-MOF material.
Wherein five yuan of carboxylic acid organic ligands, ratios of the nitrogenous auxiliary mole joined with silver nitrate are 1:1-2:1-4, often
The deionized water of five yuan of carboxylic acid organic ligand correspondences 4ml-6ml of 0.02mmol, corresponding 5-20mg surfactant, corresponding NaOH
0.01-0.04mmol.The condition of hydro-thermal reaction is 100-160 DEG C, and the response time is 60-80 hour.
More preferably five yuan of carboxylic acid organic ligands, nitrogenous auxiliary mol ratios joined with silver nitrate are 1:1:1, often
The deionized water of organic ligand polybasic carboxylic acid correspondence 5ml of 0.02mmol, corresponding surfactant 10mg, corresponding NaOH
0.04mmol.The condition of hydro-thermal reaction is 110 DEG C, and the response time is 72 hours.
The present invention also provides for a kind of that Ag-MOF materials application is anti-in catalysis reduction paranitrophenol and isomers thereof
The method answered, takes a certain amount of metal organic frame crystalline material prepared, joins paranitrophenol and isomerism thereof
In body aqueous solution, being simultaneously introduced a certain amount of potassium borohydride, system can react under room temperature condition, is quickly completed catalysis
Reduction process.
Room temperature the most involved in the present invention refers both to the ambient temperature under normal pressure.
The present invention relates to the Opacity in lens method of metal organic frame, method of testing and structured data express.
The present invention relates to test and the research of metal-organic framework material Thermogravimetric Data.
The present invention relates to apply X-ray single crystal diffractometer to collect metal-organic framework material crystal structural data.
The present invention develops a kind of based on 3, and 5-bis-(2,5-dicarboxyphenyi) benzoic metal-organic framework material is real
Verifying bright, this material has good heat stability, can be applicable to catalysis material field.
The present invention further discloses the preparation method of this kind of metal-organic framework material: obtained by hydro-thermal method self assembly
Crystalline material.The little molecule-type Advances in crystal X-ray diffraction instrument of Rigaku company of application Japan carries out structure determination to crystal, utilizes
Graphite monochromator, the Mo K alpha ray of wavelength X=0.071073nm, record the data such as diffracted intensity and cell parameter under 297.8K,
And by scanning technique, collected data being carried out empirical absorption correction, acquired results uses Shelxtl-97 program with directly
Method resolves, and uses complete matrix least square refinement.Obtain actual crystal data as shown in the table:
Table 1 Ag-MOF crystallographic parameter
The advantage of Ag-MOF material disclosed by the invention preparation synthesis is:
(1) synthetic method is simple, favorable reproducibility, and productivity is high and relatively low to temperature requirement, it is easy to control the temperature of reaction system
Degree；
(2) purposively synthesis possesses the functional crystalline material of good catalytic, and structure is it is known that structure activity relationship is bright
Clear.
(3) this material serves transmission electronics in the course of reaction of catalysis reduction paranitrophenol and isomers thereof
Effect, thus borane reducing agent hydrofining exist under conditions of, electronics passes to nitro substrate via this material, reduces
Reaction.
The method of infrared spectrum measurement of the present invention is as follows: metal-organic framework material surveyed with KBr mixed grinding laminated flake
Determine infrared spectrum.
It is as follows that the present invention carries out gravitational thermal analysis method to crystalline material sample: with 10 DEG C/min heating rate scanning sample
TG curve, sweep limits temperature range 25～800 DEG C.
Accompanying drawing explanation
Fig. 1 is the minimum asymmetrical junction composition of the material prepared by embodiment 1.
Fig. 2 is the three-dimensional accumulation graph of material prepared by embodiment 1.
Fig. 3 is the thermogravimetric analysis figure of material prepared by embodiment 1.
Fig. 4 is the infrared analysis collection of illustrative plates of material prepared by embodiment 1.
Fig. 5 is the uv absorption spectra of the material catalysis reduction paranitrophenol that embodiment 1 prepares.
Fig. 6 is the material catalysis reduction paranitrophenol color change pictorial diagram of embodiment 1 preparation.
Fig. 7 is the uv absorption spectra of the material catalysis reduction onitrophenol that embodiment 1 prepares.
Detailed description of the invention
Following embodiment is illustrative, is not determinate, it is impossible to limit the guarantor of the present invention with following embodiment
Protect scope.The described raw material of the present invention is commercially available.
Raw materials used in embodiment all can obtain from market.Silver nitrate, analytical pure, Alpha；, 3,5-bis-(2,5-dicarboxyls
Base phenyl) benzoic acid, analytical pure, Jinan perseverance；4,4 '-bipy, analytical pure, Jinan perseverance.NaOH, analytical pure, traditional Chinese medicines group；
Caprylic acid sodium, analytical pure, traditional Chinese medicines group.
Embodiment 1
(1) five yuan of Carboxylic acid ligand 0.02mmol (0.009g), 0.02mmol silver nitrate is accurately weighed with electronic balance
(0.0034g), 0.02mmol 4,4 '-bipy (0.0031g), measure 5ml deionized water, drip 0.1M NaOH solution 0.4ml,
Weighing caprylic acid sodium 10mg, above-mentioned substance is equipped with in the lump in the stainless steel cauldron of Teflon liner, puts into freeze-day with constant temperature
In case, isothermal reaction 72h at 110 DEG C.Reaction takes out reactor after terminating, and is at the uniform velocity cooled to room temperature, warp with 2-3 DEG C/h speed
Be filtered to remove solvent deionized water, finally give water white transparency bulk crystals, i.e. (chemical general formula is Ag-MOF: { [Ag2
(ddcba)(4,4’-bipy)2]}n, during n=1, concrete molecular formula is: C43H28N4O10Ag2)。
(2) take the p-nitrophenyl phenol solution 3ml that concentration is 14mg/L, move in cuvette, add 1mgAg-MOF catalysis
Agent, is simultaneously introduced 3mg KBH4, test its absorption curve with ultraviolet spectrophotometer, tracking wavelengths is the absorption value at 400nm.
The change of absorption value reflects the residual concentration of substrate.
(3) take the ortho-nitrophenyl phenol solution 3ml that concentration is 60mg/L, move in cuvette, add 1mgAg-MOF catalysis
Agent, is simultaneously introduced 3mg KBH4, test its absorption curve with ultraviolet spectrophotometer.Follow the tracks of the absorption value at 414nm.
(4) take the m-nitro phenol solution 3ml that concentration is 60mg/L, move in cuvette, add 1mgAg-MOF catalysis
Agent, is simultaneously introduced 3mg KBH4, test its absorption curve with ultraviolet spectrophotometer.Follow the tracks of the absorption value at 390nm.
(5) meaning of absorption curve in accompanying drawing is described as a example by the catalysis reduction of paranitrophenol.Paranitrophenol and also
When former dose of potassium borohydride coexists, testing it through ultraviolet spectrophotometer has obvious absorption peaks value at 400nm, can be considered as this body
The characteristic absorption peak of system.After adding catalyst material, detect the absorption value at this wavelength at set intervals and i.e. can be used to table
Levy the concentration of residue substrate.(along with substrate paranitrophenol is constantly catalyzed reduction, under its absorption peak at 400 is continuous
Fall).
Remaining accompanying drawing illustrates:
Accompanying drawing 1: reflect minimum asymmetric cell the composition situation, i.e. material internal organic ligand and gold of this crystalline material
Belong to the situation of coordination.
Accompanying drawing 2: reflect the accumulation situation of this crystalline material interior three-dimensional.
Accompanying drawing 3: reflect material degree of stability in a heated condition.
Accompanying drawing 4: reflect material internal hydroxy-acid group and the situation of metal-complexing effect, characterizes for auxiliary.
Accompanying drawing 5: reflect the material catalysis reduction time used by paranitrophenol.Curve be followed successively by from top to bottom 0min,
1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, wherein, the curve co-insides of 0min, 1min, 2min.
Accompanying drawing 6: reflect the macroscopic superficial appearance of material catalysis reduction nitropheneol reaction.
Accompanying drawing 7: reflect material catalysis reduction time used by onitrophenol, curve be followed successively by from top to bottom 0min,
1min、2min、3min、4min、5min、6min、7min、8min、9min、10min、11min、12min。
Claims (9)
1. the metal-organic framework material constructed based on 5-membered aromatic carboxylic acid, it is characterised in that this metal organic frame material
Material is 3-dimensional metal organic backbone crystalline material, and its chemical molecular formula is { [Ag2(ddcba)(4,4’-bipy)2]}n, ddcba is
3,5-bis-(2,5-dicarboxyphenyi) benzoic acid, 4,4 '-bipy are 4,4'-Bipyridine, and n is the most infinite.Owing to this material is brilliant
State material, possesses the feature of long-range order, thus chemical formula represents the basic composition situation of each minimum asymmetric cell, n
Only representing crystalline material is to be repeated the construction features of structure by minimum unit, for formula literary style.
2. the metal-organic framework material constructed based on 5-membered aromatic carboxylic acid described in claim 1, it is characterised in that: this crystalline state
Material belongs to monoclinic system, and space group is Pc, and cell parameter is: α=γ
=90 °, β=97.711 °.
3. the preparation method of the metal-organic framework material constructed based on 5-membered aromatic carboxylic acid described in claim 1, its feature
It is, comprises the following steps: under air-proof condition, 3,5-bis-(2,5-dicarboxyphenyi) benzoic acid, 4,4'-Bipyridine and nitric acid
Silver in deionized water, through sodium hydroxide regulation system acid-base value, then via hydro-thermal reaction, and at surfactant as interpolation
Under conditions of agent, (surfactant joins reaction system together and jointly participates in hydro-thermal reaction with raw material) obtains having crystal knot
The metal-organic framework material constructed based on 5-membered aromatic carboxylic acid of structure, is called for short Ag-MOF material.
4. the preparation method of the metal-organic framework material constructed based on 5-membered aromatic carboxylic acid described in claim 3, its feature
Being, wherein five yuan of carboxylic acid organic ligands, 4,4'-Bipyridines are 1:1-2:1-4 with the ratio of the mole of silver nitrate；And, often
Five yuan of carboxylic acid organic ligands of 0.02mmol add the deionized water of 4ml-6ml, 5-20mg surfactant, NaOH 0.01-
0.04mmol；The temperature of hydro-thermal reaction is 100-160 DEG C, and the response time is 60-80 hour.
5. the preparation method of the metal-organic framework material constructed based on 5-membered aromatic carboxylic acid described in claim 4, its feature
Being, wherein five yuan of carboxylic acid organic ligands, 4,4'-Bipyridines are 1:1:1 with the mol ratio of silver nitrate；And, every 0.02mmol's
Organic ligand polybasic carboxylic acid adds the deionized water of 5ml, surfactant 10mg, NaOH 0.04mmol；The temperature of hydro-thermal reaction
Being 110 DEG C, the response time is 72 hours.
6. the preparation side of the metal-organic framework material constructed based on 5-membered aromatic carboxylic acid described in any one of claim 3-5
Method, it is characterised in that described surfactant is caprylic acid sodium.
7. the metal-organic framework material constructed based on 5-membered aromatic carboxylic acid described in any one of claim 1-6 is at p-nitrophenyl
Application on the catalytic reduction reaction of phenol and isomers thereof.
8. the application described in claim 7, it is characterised in that concrete steps include the following: will construct based on 5-membered aromatic carboxylic acid
Metal-organic framework material be added to, in the ratio of 0.15g/L～0.5g/L, the p-nitrophenyl that concentration is 14mg/L～25mg/L
In the solution of phenol and isomers thereof, add potassium borohydride, react and carry out under conditions of natural light or dark, reaction temperature
For room temperature, the response time is 3min～20min, can complete the reduction of paranitrophenol and isomers thereof.
9. the application described in claim 8, it is characterised in that potassium borohydride concentration is 0.3g/L～1g/L.
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| CN108421531B (en) * | 2018-02-10 | 2020-08-28 | 广东医科大学 | Preparation method and application of copper metal organic framework compound |
| CN109810258A (en) * | 2019-02-25 | 2019-05-28 | 重庆师范大学 | Using rigid aromatic polycarboxylic acids as the MOFs analogue enztme material and synthetic method of ligand |
| CN109810258B (en) * | 2019-02-25 | 2022-01-04 | 重庆师范大学 | MOFs mimic enzyme material using rigid aromatic polycarboxylic acid as ligand and synthetic method |
| CN112126073A (en) * | 2020-09-17 | 2020-12-25 | 华南农业大学 | Multifunctional fluorescence recognition Ag coordination polymer and preparation method and application thereof |
| CN112126073B (en) * | 2020-09-17 | 2021-06-08 | 华南农业大学 | Multifunctional fluorescence recognition Ag coordination polymer and preparation method and application thereof |
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