CN106076419B - A kind of load type metal organic frame composite, preparation method and applications - Google Patents
A kind of load type metal organic frame composite, preparation method and applications Download PDFInfo
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- CN106076419B CN106076419B CN201610387905.8A CN201610387905A CN106076419B CN 106076419 B CN106076419 B CN 106076419B CN 201610387905 A CN201610387905 A CN 201610387905A CN 106076419 B CN106076419 B CN 106076419B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000463 material Substances 0.000 claims abstract description 40
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000009467 reduction Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 6
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- 229910001868 water Inorganic materials 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 239000002178 crystalline material Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 16
- 229910000510 noble metal Inorganic materials 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 8
- 239000002082 metal nanoparticle Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000013384 organic framework Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 13
- 239000011157 advanced composite material Substances 0.000 description 12
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 10
- 229910007566 Zn-MOF Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229960003742 phenol Drugs 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 241000894006 Bacteria Species 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
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002696 acid base indicator Substances 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 229940125716 antipyretic agent Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- -1 hydroxybenzene amine Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
-
- 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
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to a kind of load type metal organic frame composite, discloses a kind of composite catalyzing material based on porous crystalline state metal-organic framework material carried noble metal (Ag) and its application in catalysis paranitrophenol reduction.The present invention adopts two-step method synthetic technology, first with organic ligand 3,5 two (2,5 dicarboxyphenyis) benzoic acid and zinc nitrate be in N, N dimethyl acetylamide obtains porous metals organic framework materials with self assembly in the mixed solution of water, then using ultraviolet light reduction technique, noble metal nano particles are loaded in the matrix and duct of metal-organic framework material, finally obtain and be evenly distributed and size is homogeneous, the Ag noble metal nano particles of 3～10nm of diameter, noble-metal-supported amount is adjustable.The catalyst shows stable and superior catalysis activity in catalysis paranitrophenol reduction.
Description
Technical field
The invention belongs to crystalline material and its support type composite technology of preparing and catalytic applications, and in particular to
Five yuan of carboxylic acids are that organic ligand and zinc nitrate construct a kind of porous metal-organic framework material and the expensive gold of the material load
Category forms the application of catalysis reduction paranitrophenol after composite.
Background technology
Metal-organic framework material (MOFs) is that a class is new by be self-assembly of based on organic ligand and metal ion
Type microporous crystalline material.Metal ion or metal cluster serve as node wherein, and organic ligand is often formed and had as bridging
The crystalline material of the long-range order of regular pore canal.Compared with conventional porous materials, which has：1st, duct size is adjustable 2, specific surface
Long-pending big 3, many advantages, such as framework ingredient variation 4, duct can modify regulation.In view of above-mentioned advantage, metal-organic framework material
There is important application prospect in fields such as light, electricity, magnetic, sensing, absorption, catalysis.Except metal has in catalytic applications therein
Beyond machine frame frame material itself can be as the catalyst of some organic reaction systems or specific reaction, using its high-specific surface area
And the pore passage structure of regular uniform distribution carries out weight prepared by the load and catalyst material design of noble metal nano particles
Want one of direction.
At the same time, paranitrophenol (4-NP) is very intractable a kind of organic contamination containing phenols in industrial wastewater
Thing, under low concentration, can cause serious harm to human body and organism in water.The degraded measure of paranitrophenol concentrates on liquid
Paranitrophenol is reduced into para-aminophenol using efficient different-phase catalyst, is by phase electrion, biological bacterium degraded etc.
A kind of good and very attractive measure；It is important that still further aspect is exactly one of the product of this degradation reaction 4-AP
Industrial chemicals.Para-aminophenol, also known as " para hydroxybenzene amine ", are a kind of widely used industrial chemicals, chemical industry,
The industrial circles such as medicine, fuel, rubber and oil dope have critically important application.Therefore, will be larger to environmental injury
Reactant be converted into utilizable chemical industry intermediate raw material, with great economy, social meaning.
Known noble metal nano-particle is usually facing some problems in actual application, and they tend to occurs
Reunite and reduce catalytic effect, one of solution route is exactly supported on noble metal nano particles on various solid phase carriers
To protect them from reuniting, while reducing the consumption of noble metal.In conjunction with the construction featuress of above-mentioned metal-organic framework material, its
Supported precious metal nano-particle prepares composite catalyzing material and there is important prospect.
Content of the invention
The invention provides a kind of method for preparing porous metals organic framework materials and its support type composite, and will
Composite is applied to be catalyzed paranitrophenol reduction reaction, and its preparation method is rationally simple, and catalytic reduction performance is stable, catalysis
Reduction efficiency is higher.
The present invention adopts solvent-thermal method, prepares to form porous metals and have using polybasic carboxylic acid organic ligand and zinc salt self assembly
Machine frame frame material, is then grown in conjunction with porous material confinement using ultraviolet light reduction technique in the solution of precious metal salt configuration
Nanoparticle principle, the duct and surface that noble metal nano particles are loaded to porous metals organic framework materials, finally obtains
Good dispersion, catalysis activity high load type metal organic frame composite.
For achieving the above object, the technical solution used in the present invention is：
A kind of load type metal organic frame composite, the composite are carried on crystalline material for precious metals ag；Institute
The crystalline material that states is loose structure, and pore size is 1nm-2nm, and specific surface area is 639m2/g-929m2/g；Described Ag is
Nano-particle, in the surface and duct of amorphous metal organic framework materials, the nanoparticle size of Ag is 3nm- to homoepitaxial
10nm.The load capacity of Ag can be 0.5wt%～50wt%, illustrate which is catalyzed effect in this example so that the load capacity of Ag is for 50% as an example
Fruit and electromicroscopic photograph effect.
Described metal-organic framework material material can also provide load matrix, such as Pt for other noble metal nano particles
Or Au or Pd；Described Pt or Au or Pd is nano-particle, and homoepitaxial is in the surface and duct of metal-organic framework material.
Porous metal organic framework materials of the present invention and carried noble metal with the new of high-efficiency catalytic activity
The preparation method of type complex function nanocatalyst includes several steps：
(1) take bis- (2,5- dicarboxyphenyis) benzoic acid of a certain amount of organic ligand 3,5- and zinc nitrate be dissolved in a certain amount of
Deionized water and N,N-dimethylacetamide in, stirring 30min after, be transferred in hydrothermal reaction kettle, be heated to 110 DEG C -180
DEG C, 60-80 hours are incubated, until separating out colourless amorphous material.Clear crystal is collected by filtration, is vacuum dried at 80 DEG C
12h, obtains crystallite sample.
(2) the crystallite sample obtained in step (1) is placed in ethanol solution and is soaked 48 hours, changed once per 24 hours
Ethanol solution.Dry 6 hours under 80 DEG C of vacuum environments after guest molecule in solvent displaces duct.
(3) the porous metal organic framework materials that step (2) is obtained are added in deionized water, add 0.5ml
Silver nitrate solution of the concentration of～2ml for 10mg/L, shakes 24 hours under room temperature, using the mercury lamp that power is 300W using ultraviolet
The mixed system that photo-reduction is obtained, the mixed liquor product for obtaining after filtering, are washed using distilled water and dehydrated alcohol successively respectively
Wash three times, the product for obtaining is organic in the metal that 30 DEG C～100 DEG C vacuum drying 4-6 hours are obtained loaded Ag nanoparticle
Frame composite material.
The present invention is also provided and applies above-mentioned load type metal organic frame composite on degraded paranitrophenol
Example.Concretely comprise the following steps composite concentration is added to for the right of 14mg/L～25mg/L in the ratio of 0.15g/L～0.5g/L
In the solution of nitrophenol, and the potassium borohydride of certain mass is proportionally added into, is reacted in room natural light or the condition of dark
Under carry out, reaction temperature is room temperature, and the response time is 3min～20min, you can complete the reduction of whole paranitrophenols
Journey.
In the reaction of catalysis reduction paranitrophenol, it is carried on the Ag nanoparticles on metal-organic framework material and rises
The effect of transmission electronics is arrived.Under conditions of reducing agent potassium borohydride is present, BH4 -Electronics is passed to by Ag nanoparticles
Catalytic substrate paranitrophenol completes reduction process.
Catalytic reduction method described in above-mentioned steps, the potassium borohydride concentration being proportionally added in reactant liquor is
0.3g/L～1g/L.
Described paranitrophenol is used as the raw material of dyestuff, medicine and pesticide, as acid-base indicator and analytical reagent.Right
Nitrophenol 4-NP, is that one kind is present in industrial wastewater and very intractable containing one of phenolic comp ' ds pollution, produces in a lot of pesticide
This material can also be produced in the middle of the preparation process of product such as Insecticides (tech) ＆ Herbicides (tech) etc., it can cause very big pollution to environment,
Simultaneously the health of the mankind and other biological is threatened.By paranitrophenol be reduced into para-aminophenol be a kind of well and
Very attractive measure；Still further aspect is exactly that the importance of the product para-aminophenol 4-AP of this reaction especially shows
Write.As the demand of Antipyretics thing is continuously increased, the fast development of rubber and dye industry is industrial to amino
The demand of phenol (4-AP) is continuously increased.Therefore, the preparation technology innovation of para-aminophenol is particularly important, and wherein utilizes
It is exactly one of solution route that new catalyst is catalyzed the reaction.
Description of the drawings
Fig. 1 is the minimum asymmetrical junction composition of the amorphous metal organic framework materials prepared by embodiment 1；
Three-dimensional accumulation graphs of the Fig. 2 for crystal prepared by embodiment 1；
Fig. 3：The high-resolution-ration transmission electric-lens figure of the advanced composite material (ACM) of carried noble metal silver obtained in embodiment 2；
Fig. 4：The transmission electron microscope picture of the advanced composite material (ACM) of carried noble metal silver obtained in embodiment 2；
Fig. 5：Obtained in embodiment 2 carried noble metal silver advanced composite material (ACM) catalysis reduction paranitrophenol ultraviolet-
Visible absorption spectra phenogram；
Fig. 6：The advanced composite material (ACM) catalysis reduction paranitrophenol color of carried noble metal silver obtained in embodiment 2 becomes
Change pictorial diagram；
Specific embodiment：
With reference to case row are embodied as, the present invention is expanded on further, it should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention, after the present invention has been read, those skilled in the art are to of the invention various etc.
The modification of valency form falls within the application claims limited range.
Embodiment 1
0.05mmol 3 accurately weighed, 5- bis- (2,5- dicarboxyphenyi) benzoic acid, 0.05mmol zinc nitrates, 5ml DMA,
5ml H2O, adds in the stainless steel cauldron equipped with Teflon liner, and isothermal reaction 72h at 140 DEG C, then with 2-3 DEG C/h
Room temperature is cooled at the uniform velocity, water white transparency bulk porous crystalline state metal-organic framework material is obtained.That is Zn-MOF.(chemical general formula is：
{[Zn5(ddcba)2]}n, n for just infinite, and n only to represent crystalline material be that the structure repeated to build by minimum unit is special
Point, is formula literary style).
Embodiment 2
1) the porous crystalline state metal-organic framework material obtained in embodiment 1 is displaced through solvent and make after guest molecule
For carrier, (guest molecule refers mainly to hydrone and the DMA molecules introduced in crystalline material synthesis, as the material possesses duct knot
Structure, both have certain residual in duct).Substitute mode is：Crystalline material sample is placed in ethanol solution and soaks 48
Hour, an ethanol solution was changed per 24 hours, then was vacuum dried 6 hours at 80 DEG C.100mg transposed crystalline state material is subsequently taken
Material is added in 15ml deionized waters, is subsequently adding the silver nitrate solution of the 10mg/L of 0.5ml, and above-mentioned mixed system is shaken
24 hours.
2) above-mentioned mixed system is transferred in the quartz test tube of photochemical reactor, under conditions of stirring, is utilized
Power utilizes ultraviolet light 3h, reduction to obtain new mixed system for the mercury lamp of 300W.
3), after the product for obtaining is separated by filtration, is washed respectively three times using distilled water and dehydrated alcohol successively, obtained
80 DEG C of vacuum drying of product are obtained Ag Zn-MOF advanced composite material (ACM)s.
The transmission electron microscope picture of the metal organic frame composite (Ag Zn-MOF) of the precious metals ag load of above-mentioned preparation
As shown in figure 3, knowing that Ag nano particles are uniformly grown in the surface and duct of Zn-MOF from electromicroscopic photograph analysis.
The catalysis reduction that the advanced composite material (ACM) of above-mentioned preparation is carried out paranitrophenol, 1mgAg@Zn-MOF are combined
Material is added in solution of the concentration for the paranitrophenol that concentration is 14mg/L, and adds the potassium borohydride of 3mg, is reacted and is existed
Carry out under conditions of room natural light or dark, reaction temperature is room temperature.At regular intervals take out solution testing, using ultraviolet can
See light spectrophotometer, by absorbance of the solution in maximum absorption wavelength (400nm) being determined judging catalysis process situation, pass through
The time is spent for 8min, you can complete the catalysis reduction of paranitrophenol 100%.
Description of the drawings：
Accompanying drawing 1：Reflect the minimum asymmetric cell that metal has frame material, i.e. carrier material (Zn-MOF) internal
Basic composition and coordination situation.Specifically indicate that how organic ligand and metal occur when metal-organic framework material is constructed
Coordination.
Accompanying drawing 2：The microstructure in metal-organic framework material interior three-dimensional duct is reflected, organic ligand is specifically presented
How three-dimensional open-framework is built with after metal-complexing.
Accompanying drawing 3：Nanoparticle Size situation after Ag nanometer particle loads are reflected to metal-organic framework material.
Accompanying drawing 4：Nanoparticle Size after Ag nanometer particle loads are reflected to metal-organic framework material and
Which disperses situation.
Accompanying drawing 5：Reflect the time used by material catalysis reduction paranitrophenol and catalytic process.Each absorbs song
Line represents the residual concentration of catalytic substrate when catalytic reaction proceeds to the time.
Accompanying drawing 6：Reflect the macroscopic superficial appearance of material catalysis reduction paranitrophenol.
Claims (8)
1. a kind of load type metal organic frame composite, it is characterised in that the composite is for possessing regular porous structure
Ag load type metal organic frame crystalline materials, chemical general formula be { [Zn5(ddcba)2]}n, ddcba represents 3,5- bis-（2,5-
Dicarboxyphenyi）Benzoic acid, n are just infinite.
2. the load type metal organic frame composite described in claim 1, it is characterised in that it is oblique that the crystalline material belongs to three
Crystallographic system, space group is P-1, and cell parameter is：A=12.194, b=12.647, c=12.699, α=83.837 °, β=
83.660 °, γ=77.272 °.
3. the preparation method of the load type metal organic frame composite described in claim 1 or 2, it is characterised in that include
Following steps：
(1) 3,5- bis- is taken（2,5- dicarboxyphenyis）Benzoic acid and zinc nitrate are dissolved in deionized water and N,N-dimethylacetamide
Mixed solution in, stirring 30min after, be transferred in hydrothermal reaction kettle, be heated to 110 DEG C -180 DEG C, be incubated 60-80 hours,
Until separating out colourless amorphous material, clear crystal is collected by filtration, 12 h are vacuum dried at 80 DEG C, obtain crystallite sample；
(2) will（1）In the crystallite sample that obtains be placed in ethanol solution and soak 48 hours, changed an ethanol per 24 hours molten
Liquid, then be vacuum dried 6 hours at 80 DEG C；
(3) take（2）In obtain treat load sample immersion silver nitrate aqueous solution in, under room temperature shake 24 hours after, using power
Mercury lamp for 300 W obtains mixed liquor using UV Light reduction, and the mixed liquor product for obtaining is adopted after filtering, successively and steamed
Distilled water and dehydrated alcohol are washed three times respectively, the product for obtaining, and product is vacuum dried at 30 DEG C ~ 100 DEG C 4-6 hours
The metal organic frame composite of loaded Ag nanoparticle is obtained.
4. the preparation method of load type metal organic frame composite according to claim 2, it is characterised in that wherein
3,5- bis-（2,5- dicarboxyphenyis）Benzoic acid is 1 with the mol ratio of zinc nitrate:1, N,N-dimethylacetamide and deionized water
Mol ratio be 1:1；Corresponding 2ml deionized waters and 2ml N,N-dimethylacetamide per 0.04mmol organic ligands.
5. the preparation method of the load type metal organic frame composite described in claim 2, it is characterised in that step（3）
In, the load capacity of Ag is 0.5 wt% ~ 50 wt %, treats that per 20mg the corresponding 5mg-20mg silver nitrate of load sample and 3ml-10ml go
Ionized water, treats load sample：Silver nitrate：Deionized water quality ratio：4:1~4:1~2.
6. load type metal organic frame composite described in claim 1 is in catalytic degradation paranitrophenol and/or different with dividing
Application on structure body.
7. the application described in claim 6, it is characterised in that concrete steps include as follows：Load type metal organic frame is multiple
Condensation material in the ratio of 0.15 g/L ~ 0.5 g/L be added to concentration be 14 mg/L ~ 25 mg/L paranitrophenol and/or with
In the solution of enantiomers, potassium borohydride, reaction is added to carry out under conditions of natural light or dark, reaction temperature is room temperature,
Response time is 3 min ~ 20 min, you can complete the reduction process of whole paranitrophenols and/or isomerss.
8. the application described in claim 7, it is characterised in that potassium borohydride concentration is 0.3 g/L ~ 1 g/L.
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| CN111296480B (en) * | 2020-02-21 | 2022-03-01 | 衢州学院 | Iron-based metal-organic framework material loaded with silver nanoparticles and preparation method and application thereof |
| CN112473737A (en) * | 2020-09-25 | 2021-03-12 | 盐城工学院 | Ag @ MOF material, and preparation method and application thereof |
| CN113368900B (en) * | 2021-05-26 | 2022-11-25 | 长春工业大学 | Preparation method and application of zirconium-based microporous coordination polymer composite material loaded by heteropoly acid or heteropoly acid salt |
| CN113603894B (en) * | 2021-07-23 | 2022-08-16 | 上海应用技术大学 | Ag-MOF/AuNRs nano composite material and preparation and application thereof |
| CN114190373B (en) * | 2021-11-10 | 2022-11-22 | 浙江大学 | Metal organic framework composite material, preparation method and application |
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