CN106046032B - A kind of metal-organic framework material, synthetic method and its catalytic applications that is constructed based on 5-membered aromatic carboxylic acid - Google Patents
A kind of metal-organic framework material, synthetic method and its catalytic applications that is constructed based on 5-membered aromatic carboxylic acid Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 42
- 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 8
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 14
- 239000002178 crystalline material Substances 0.000 claims abstract description 13
- 239000013110 organic ligand Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 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
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 6
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 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
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- WXBLLCUINBKULX-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 WXBLLCUINBKULX-UHFFFAOYSA-N 0.000 claims 2
- 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
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 19
- 238000012360 testing method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000013384 organic framework Substances 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 239000005300 metallic glass Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000000376 reactant Substances 0.000 description 4
- 239000000758 substrate Substances 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
- 239000002243 precursor 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
- 230000008859 change Effects 0.000 description 2
- 229940126678 chinese medicines Drugs 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 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
- 238000003786 synthesis reaction Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-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
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 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
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 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
- 239000007788 liquid Substances 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil 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
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 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
- 239000003643 water by type Substances 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
A kind of metal-organic framework material synthetic method that is constructed based on 5-membered aromatic carboxylic acid and its catalytic applications, belong to crystalline material and catalytic applications technical field.The metal-organic framework material chemical molecular formula is：{[Ag2(ddcba)(4,4’‑bipy)2]}n, wherein n represents just infinite, and ddcba represents that 3,5 two (2,5 dicarboxyphenyi) benzoic acid, 4,4 ' bipy represent 4,4 ' bipyridyls.Under sealing condition, polybasic carboxylic acid organic ligand under hydrothermal conditions, by sodium hydroxide regulation system pH value, and is added surfactant as additive, obtains amorphous metal organic framework materials via hydro-thermal reaction with silver nitrate.Further test shows that the material shows higher catalysis activity in the reaction of reduction paranitrophenol and its isomerss.
Description
Technical field
The present invention relates to a kind of metal-organic framework material synthetic method that is constructed based on 5-membered aromatic carboxylic acid and its catalysis
Application, belongs to crystalline material and catalytic applications technical field.Specifically based on five yuan of carboxylic acid Organic substances, part, itrogenous organic substance are
Assistant ligand, transition metal silver show the crystalline substance for metal center through being self-assembly of metal-organic framework material (MOF), test
State material has higher catalytic activity in catalysis reduction paranitrophenol and its isomerism precursor reactant.
Background technology
Metal-organic framework material (Metal-Organic Frameworks, abbreviation MOFs) is that a kind of new micropore is brilliant
State material.Metal-organic framework material with metal ion or metal ion cluster as node, with organic ligand as bridging, with coordinate bond is
Active force is attached, and forms the crystal space structure of long-range order.So far, aromatics polybasic carboxylic acid part widely should
For constructing metal-organic framework materials, it is current most study, the most successful class part.Compared with conventional porous materials,
Which has：1st, many advantages, such as duct size is adjustable 2, specific surface area is big 3, framework ingredient variation 4, duct can modify regulation.Mirror
In above-mentioned advantage, metal-organic framework material has important application prospect in fields such as light, electricity, magnetic, sensing, absorption, catalysis.Its
In catalytic applications in carry out noble metal nano particles except the pore passage structure being distributed using its high-specific surface area and regular uniform
Load beyond, metal-organic framework material itself also can be used as some organic reaction systems or the catalyst of specific reaction.
At the same time, the phenol organic matter with paranitrophenol (4-NP) as representative is very intractable one in industrial wastewater
Organic pollution is planted, under low concentration, serious harm can be caused to human body and organism in water.The degraded of paranitrophenol is arranged
Apply and concentrate on phase autoclave electric discharge, biological bacterium degraded etc., it is right to be reduced into paranitrophenol using efficient different-phase catalyst
Amino-phenol, is a kind of good and very 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 ", are a kind of widely used chemical industry
Raw material, has critically important application in industrial circles such as chemical industry, medicine, fuel, rubber and oil dopes.Therefore, will be right
The larger reactant of environmental injury is converted into utilizable chemical industry intermediate raw material, with great economy, social meaning.
Content of the invention
The invention provides a kind of metal-organic framework material synthetic method that is constructed based on 5-membered aromatic carboxylic acid, and should
Crystalline material is applied in catalysis reduction paranitrophenol and its isomerism precursor reactant.
A kind of metal-organic framework material (Ag-MOF) that is constructed based on five yuan of carboxylic acids, second bipyridine and silver nitrate, the gold
Category organic framework materials are Ag and five yuan of carboxylic acid organic ligand, nitrogenous auxiliary with 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 just infinite, and ddcba represents 3,5- bis-
(2,5- dicarboxyphenyi) benzoic acid, 4,4 '-bipy represent 4,4'-Bipyridine.
The 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 in table
Face activating agent is used as the metal-organic framework material obtained under conditions of additive with crystal structure, i.e. Ag-MOF materials.
Wherein five yuan carboxylic acid organic ligands, nitrogenous auxiliary with being 1 with the ratio of the mole of silver nitrate:1-2:1-4, per
The deionized water of the corresponding 4ml-6ml of five yuan of carboxylic acid organic ligands of 0.02mmol, corresponding 5-20mg surfactants, corresponding NaOH
0.01-0.04mmol.The condition of hydro-thermal reaction is 100-160 DEG C, and the response time is 60-80 hours.
More preferably five yuan carboxylic acid organic ligands, nitrogenous auxiliary with being 1 with the mol ratio of silver nitrate:1:1, per
The deionized water of the corresponding 5ml of the organic ligand polybasic carboxylic acid 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 one kind by Ag-MOF materials applications in catalysis reduction paranitrophenol and its isomerism precursor reactant
Method, take a certain amount of metal organic frame crystalline material for preparing, be added to paranitrophenol and its isomerss are water-soluble
In liquid, a certain amount of potassium borohydride is simultaneously introduced, system can react under room temperature condition, quickly complete catalytic reduction process.
Room temperature wherein 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 expression.
The present invention relates to the test and research of metal-organic framework material Thermogravimetric Data.
The present invention relates to metal-organic framework material crystal structural data collected by application X ray single crystal diffractometer.
The present invention develops one kind based on 3,5- bis- (2,5- dicarboxyphenyi) benzoic metal-organic framework material, real
Checking is bright, and the 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 small molecule type Advances in crystal X-ray diffraction instrument of Rigaku companies of application Japan carries out structure determination to crystal, utilizes
Graphite monochromator, the Mo K alpha rays of wavelength X=0.071073nm measure diffracted intensity and the data such as cell parameter under 297.8K,
And scanning technique is used, and collected data are carried out with empirical absorption correction, acquired results adopt Shelxtl-97 programs with direct
Method is parsed, and uses complete matrix least square method correction.Obtain actual crystal data as shown in the table：
1 Ag-MOF crystallographic parameters of table
Ag-MOF materials disclosed by the invention prepare the advantage of synthesis and are：
(1) synthetic method is simple, favorable reproducibility, and yield is high and relatively low to temperature requirement, it is easy to control the temperature of reaction system
Degree；
(2) purposefully synthesis possesses the feature crystalline material of good catalytic, and structure is, it is known that structure activity relationship is bright
Clear.
(3) material serves transmission electronics in the course of reaction of catalysis reduction paranitrophenol and its isomerss
Effect, thus reducing agent potassium borohydride exist under conditions of, electronics passes to nitro substrate via the material, reduces
Reaction.
The method of infrared spectrum measurement of the present invention is as follows：Metal-organic framework material is surveyed with KBr mixed grindings laminated flake
Determine infrared spectrum.
It is as follows that the present invention carries out gravitational thermal analysis method to crystalline material sample：Sample is scanned with 10 DEG C/min heating rates
TG curves, 25～800 DEG C of sweep limitss temperature range.
Description of the drawings
Fig. 1 is the minimum asymmetrical junction composition of the material prepared by embodiment 1.
Three-dimensional accumulation graphs of the Fig. 2 for material prepared by embodiment 1.
Thermogravimetric analysis figures of the Fig. 3 for material prepared by embodiment 1.
Infrared analysiss collection of illustrative plates of the Fig. 4 for material prepared by embodiment 1.
Uv absorption spectras of the Fig. 5 for material catalysis reduction paranitrophenol obtained in embodiment 1.
Fig. 6 is material catalysis reduction paranitrophenol color change pictorial diagram prepared by embodiment 1.
Uv absorption spectras of the Fig. 7 for material catalysis reduction onitrophenol obtained in embodiment 1.
Specific embodiment
Following embodiments is illustrative, is not determinate, it is impossible to limit the guarantor of the present invention with following embodiments
Shield scope.The raw material of the present invention is commercially available.
Raw materials used in embodiment can be obtained from market.Silver nitrate, analyzes pure, Alpha；, 3,5- bis- (2,5- dicarboxyls
Base phenyl) benzoic acid, analyze pure, Jinan perseveranceization；4,4 '-bipy, analyze pure, Jinan perseveranceization.NaOH, analyzes pure, Chinese medicines group；
Caprylic acid sodium, analyzes pure, Chinese medicines group.
Embodiment 1
(1) five yuan of Carboxylic acid ligand 0.02mmol (0.009g), 0.02mmol silver nitrate are accurately weighed with electronic balance
(0.0034g), 0.02mmol 4,4 '-bipy (0.0031g) measure 5ml deionized waters, Deca 0.1M NaOH solution 0.4ml,
Caprylic acid sodium 10mg is weighed, above-mentioned substance is added in the stainless steel cauldron equipped with Teflon liner in the lump, is put 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 with 2-3 DEG C/h speed, passes through
Solvent deionized water is filtered to remove, water white transparency bulk crystals are finally given, is i.e. (chemical general formula is Ag-MOF：{[Ag2
(ddcba)(4,4’-bipy)2]}n, during n=1, specific molecular formula is：C43H28N4O10Ag2).
(2) the p-nitrophenyl phenol solution 3ml that concentration is 14mg/L is taken, is moved in cuvette, add 1mgAg-MOF catalysis
Agent, is simultaneously introduced 3mg KBH4, its absorption curve is tested with ultraviolet spectrophotometer, tracking wavelengths are the absorption value at 400nm.
The change of absorption value reflects the residual concentration of substrate.
(3) the ortho-nitrophenyl phenol solution 3ml that concentration is 60mg/L is taken, is moved in cuvette, add 1mgAg-MOF catalysis
Agent, is simultaneously introduced 3mg KBH4, its absorption curve is tested with ultraviolet spectrophotometer.Absorption value at tracking 414nm.
(4) the m-nitro phenol solution 3ml that concentration is 60mg/L is taken, is moved in cuvette, add 1mgAg-MOF catalysis
Agent, is simultaneously introduced 3mg KBH4, its absorption curve is tested with ultraviolet spectrophotometer.Absorption value at tracking 390nm.
(5) meaning of absorption curve in accompanying drawing is described by taking the catalysis reduction of paranitrophenol as an example.Paranitrophenol and also
When former agent potassium borohydride coexists, testing which through ultraviolet spectrophotometer has obvious absorption peaks value at 400nm, can be considered as the body
The characteristic absorption peak of system.After adding catalyst material, detect that the absorption value at the wavelength can be used to table at set intervals
Levy the concentration of remaining substrate.(as substrate paranitrophenol is reduced by constantly catalysis, under its absorption peak at 400 is continuous
Drop).
Remaining description of the drawings：
Accompanying drawing 1：Reflect minimum asymmetric cell composition situation, i.e. material internal organic ligand and the gold of the crystalline material
The situation of category coordination.
Accompanying drawing 2：Reflect the accumulation situation of the crystalline material interior three-dimensional.
Accompanying drawing 3：Reflect material degree of stability in a heated condition.
Accompanying drawing 4：The situation of material internal hydroxy-acid group and metal-complexing effect is reflected, is that auxiliary is characterized.
Accompanying drawing 5：Reflect the time used by material catalysis reduction 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 onitrophenol used by time, 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. a kind of metal-organic framework material that is constructed based on 5-membered aromatic carboxylic acid, it is characterised in that the metal organic frame material
Expect for 3-dimensional metal organic backbone crystalline material, its chemical molecular formula is { [Ag2(ddcba)(4,4’-bipy)2]}n, ddcba is
3,5- bis-（2,5- dicarboxyphenyis）Benzoic acid, 4,4 '-bipy are 4,4'-Bipyridine, and n is just infinite, as the material is brilliant
State material, the characteristics of possess long-range order, thus chemical formula represents the basic composition situation of each minimum asymmetric cell, n
It is to be repeated the construction featuress of structure by minimum unit only to represent crystalline material, is formula literary style.
2. the metal-organic framework material that is constructed based on 5-membered aromatic carboxylic acid described in claim 1, it is characterised in that：
The crystalline material belongs to monoclinic system, and space group isPc, cell parameter is：A=10.954, b=9.664, c=
17.4127, α=γ=90 °, β=97.711 °.
3. the preparation method of the metal-organic framework material that is 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- dicarboxyphenyis）Benzoic acid, 4,4 '-bipyridyl and nitric acid
Silver in deionized water, through sodium hydroxide regulation system acid-base value, then via hydro-thermal reaction, and in surfactant as interpolation
Under conditions of agent, surfactant is added to reaction system together with raw material and participates in hydro-thermal reaction jointly, obtains tying with crystal
The metal-organic framework material that is constructed based on 5-membered aromatic carboxylic acid of structure, abbreviation Ag-MOF materials.
4. the preparation method of the metal-organic framework material that is constructed based on 5-membered aromatic carboxylic acid described in claim 3, its feature
It is, wherein the ratio of the mole of five yuan of carboxylic acid organic ligands, 4,4'-Bipyridine and silver nitrate is 1：1-2：1-4；And, per
Five yuan of carboxylic acid organic ligands of 0.02 mmol add the deionized water of 4ml-6ml, 5-20mg surfactants, NaOH 0.01-
0.04mmol；The temperature of hydro-thermal reaction is 100-160 DEG C, and the response time is 60-80 hours.
5. the preparation method of the metal-organic framework material that is constructed based on 5-membered aromatic carboxylic acid described in claim 4, its feature
It is, wherein the mol ratio of five yuan of carboxylic acid organic ligands, 4,4'-Bipyridine and silver nitrate is 1：1：1；And, every 0.02 mmol's
Organic ligand polybasic carboxylic acid adds the deionized water of 5ml, surfactant 10mg, NaOH 0.04mmol；The temperature of hydro-thermal reaction
For 110 DEG C, the response time is 72 hours.
6. the preparation side of the metal-organic framework material that is 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 that is constructed based on 5-membered aromatic carboxylic acid described in any one of claim 1-6 is in p-nitrophenyl
Application on the catalytic reduction reaction of phenol and its isomerss.
8. the application described in claim 7, it is characterised in that concrete steps include as follows：To be constructed based on 5-membered aromatic carboxylic acid
Metal-organic framework material to be added to concentration in the ratio of 0.15 g/L ~ 0.5 g/L be 14 mg/L ~ 25 mg/L to nitro
In the solution of phenol and its isomerss, potassium borohydride, reaction is added to carry out under conditions of natural light or dark, reaction temperature
Spend for room temperature, the response time is 3 min ~ 20 min, you can complete the reduction of paranitrophenol and its isomerss.
9. the application described in claim 8, it is characterised in that potassium borohydride concentration is 0.3 g/L ~ 1 g/L.
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