CN106076419A - 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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- CN106076419A CN106076419A CN201610387905.8A CN201610387905A CN106076419A CN 106076419 A CN106076419 A CN 106076419A CN 201610387905 A CN201610387905 A CN 201610387905A CN 106076419 A CN106076419 A CN 106076419A
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- organic frame
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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 13
- 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 15
- 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 12
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 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
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 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
- 238000007654 immersion Methods 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
- 238000011946 reduction process Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 2
- 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
- 239000007788 liquid Substances 0.000 claims 1
- 238000010025 steaming 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
- 230000008859 change Effects 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000002829 reductive effect Effects 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
- 230000008901 benefit Effects 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 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
- 229960003742 phenol Drugs 0.000 description 2
- 229910052697 platinum Inorganic materials 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
- 238000010521 absorption reaction 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
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 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
- 230000009514 concussion Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination 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
- 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
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000004044 response Effects 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
- 238000005406 washing 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
-
- B01J35/393—
-
- B01J35/399—
-
- B01J35/643—
-
- B01J35/653—
-
- 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
Abstract
The invention belongs to a kind of load type metal organic frame composite, disclose a kind of composite catalyzing material based on porous crystalline state metal-organic framework material carried noble metal (Ag) and the application in catalysis paranitrophenol reduction thereof.The present invention uses two-step method synthetic technology, first with organic ligand 3,5 two (2,5 dicarboxyphenyi) benzoic acid and zinc nitrate be at N, N dimethyl acetylamide obtains porous metals organic framework materials with self assembly in the mixed solution of water, then ultraviolet light reduction technique is utilized, noble metal nano particles is loaded in matrix and the duct of metal-organic framework material, finally obtain and be evenly distributed and size is homogeneous, the Ag noble metal nano particles of diameter 3～10nm, noble-metal-supported amount is adjustable.This catalyst demonstrates stable and superior catalysis activity in catalysis paranitrophenol reduction.
Description
Technical field
The invention belongs to crystalline material and support type composite technology of preparing thereof and catalytic applications, be specifically related to
Five yuan of carboxylic acids are organic ligand and zinc nitrate constructs a kind of porous metal-organic framework material and the expensive gold of this material load
Belong to the application being catalyzed reduction paranitrophenol after forming 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, as bridging, is often formed and has
The crystalline material of the long-range order of regular pore canal.Compared with conventional porous materials, it has: 1, duct size is adjustable 2, specific surface
The plurality of advantages such as regulation can be modified in long-pending big 3, framework ingredient variation 4, duct.In view of above-mentioned advantage, metal-organic framework material
Optical, electrical, magnetic, sense, adsorb, the field such as catalysis has important application prospect.Catalytic applications therein has except metal
Machine frame material itself can be as the catalyst of some organic reaction system or specific reaction beyond, utilize its high-specific surface area
And the pore passage structure of regular uniform distribution carries out the weight that the load of noble metal nano particles is also catalyst material design preparation
Want one of direction.
Meanwhile, paranitrophenol (4-NP) is the most 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
Phase electrion, biological bacterium degraded etc., utilize efficient different-phase catalyst that paranitrophenol is reduced into para-aminophenol, be
A kind of good and the most attractive measure；Still further aspect be exactly one of the product of this degradation reaction 4-AP be important
Industrial chemicals.Para-aminophenol, also known as " para hydroxybenzene amine ", be a kind of widely used industrial chemicals, chemical industry,
The industrial circles such as medicine, fuel, rubber and oil dope all have critically important application.Therefore, will be bigger to environmental injury
Reactant be converted into utilizable chemical industry intermediate raw material, there is great economy, social meaning.
Known noble metal nano-particle is usually facing some problems in actual application, and they tend to occur
Reuniting and reduce catalytic effect, noble metal nano particles is supported on various solid phase carrier by one of them solution route exactly
To protect them from reuniting, reduce the consumption of noble metal simultaneously.In conjunction with the construction features of above-mentioned metal-organic framework material, its
Supported precious metal nano-particle is prepared composite catalyzing material and is had important prospect.
Summary of the invention
The invention provides a kind of method preparing porous metals organic framework materials and support type composite thereof, and will
Composite is applied to be catalyzed paranitrophenol reduction reaction, and its preparation method is rationally simple, and catalysed reductive can be stable, catalysis
Reduction efficiency is higher.
The present invention uses solvent-thermal method, and utilizing polybasic carboxylic acid organic ligand and zinc salt self assembly preparation to form porous metals has
Machine frame material, then utilizes ultraviolet light reduction technique in the solution of precious metal salt configuration, grows in conjunction with porous material confinement
Nanoparticle principle, loads to noble metal nano particles duct and the surface of porous metals organic framework materials, finally obtains
Good dispersion, the load type metal organic frame composite that catalysis activity is high.
For achieving the above object, the technical solution used in the present invention is:
A kind of load type metal organic frame composite, this composite is that precious metals ag is carried on crystalline material；Institute
The crystalline material stated is loose structure, and pore size is 1nm-2nm, and specific surface area is 639m2/g-929m2/g；Described Ag is
Nano-particle, homoepitaxial is in the surface and duct of amorphous metal organic framework materials, and the nanoparticle size of Ag is 3nm-
10nm.The load capacity of Ag can be the load capacity in 0.5wt%～50wt%, this example by Ag be that its catalysis effect is described as a example by 50%
Fruit and electromicroscopic photograph effect.
Described metal-organic framework material material can also provide load matrix for other noble metal nano particles, such as Pt
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 there is the new of high-efficiency catalytic activity
The preparation method of type complex function nanocatalyst includes the most several step:
(1) take a certain amount of organic ligand 3,5-bis-(2,5-dicarboxyphenyi) benzoic acid and zinc nitrate is 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, it is incubated 60-80 hour, 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 immersion 48 hours, within every 24 hours, changes once
Ethanol solution.It is dried 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) obtains is joined in deionized water, add 0.5ml
～the concentration of 2ml is the silver nitrate solution of 10mg/L, shakes 24 hours under room temperature, utilize the mercury lamp that power is 300W to utilize ultraviolet
The mixed system that photo-reduction obtains, the mixed liquor product obtained after filtering, uses distilled water and dehydrated alcohol to wash respectively successively
Washing three times, the metal that the product obtained i.e. can get loaded Ag nanoparticle for 4-6 hour 30 DEG C～100 DEG C vacuum drying is organic
Frame composite material.
The present invention also provides for being applied by above-mentioned load type metal organic frame composite on degraded paranitrophenol
Example.Concretely comprising the following steps composite and being added to concentration in the ratio of 0.15g/L～0.5g/L is the right of 14mg/L～25mg/L
In the solution of nitrophenol, and be proportionally added into certain mass potassium borohydride, reaction in room nature light or the condition of dark
Under carry out, reaction temperature is room temperature, and the response time is 3min～20min, can complete the reduction of whole paranitrophenols
Journey.
In the reaction of catalysis reduction paranitrophenol, it is carried on the Ag nanoparticle on metal-organic framework material and rises
Arrive the effect of transmission electronics.Under conditions of borane reducing agent hydrofining exists, BH4 -Electronics is passed to by Ag nanoparticle
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 dyestuff, medicine and the raw material of pesticide, as acid-base indicator and analytical reagent.Right
Nitrophenol 4-NP, is that one is present in industrial wastewater and the most intractable containing one of phenolic comp ' ds pollution, produces at a lot of pesticide
Also can produce this material in the middle of the preparation process of product such as Insecticides (tech) & Herbicides (tech) etc., environment can be caused the biggest pollution by it,
The health of the mankind and other biological is threatened simultaneously.Paranitrophenol is reduced into para-aminophenol be a kind of well and
The most attractive measure；It is the most aobvious that still further aspect is exactly the importance of the product para-aminophenol 4-AP of this reaction
Write.Along with the demand of Antipyretics thing is continuously increased, rubber and the fast development of dye industry, 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 this reaction.
Accompanying drawing explanation
Fig. 1 is the minimum asymmetrical junction composition of the amorphous metal organic framework materials prepared by embodiment 1；
Fig. 2 is the three-dimensional accumulation graph of crystal prepared by embodiment 1；
Fig. 3: the high-resolution-ration transmission electric-lens figure of the advanced composite material (ACM) of the carried noble metal silver prepared for embodiment 2；
Fig. 4: the transmission electron microscope picture of the advanced composite material (ACM) of the carried noble metal silver prepared for embodiment 2；
Fig. 5: the advanced composite material (ACM) catalysis reduction paranitrophenol ultraviolet of the carried noble metal silver prepared for embodiment 2-
Visible absorption spectra phenogram；
Fig. 6: for the advanced composite material (ACM) catalysis reduction paranitrophenol color change of the carried noble metal silver that embodiment 2 prepares
Change pictorial diagram；
Detailed description of the invention:
Below in conjunction with being embodied as case row, 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 having read the present invention, those skilled in the art are various etc. to the present invention's
The amendment of valency form all falls within the application claims limited range.
Embodiment 1
Accurately weigh 0.05mmol 3,5-bis-(2,5-dicarboxyphenyi) benzoic acid, 0.05mmol zinc nitrate, 5ml DMA,
5ml H2O, is equipped with in the stainless steel cauldron of Teflon liner, and isothermal reaction 72h at 140 DEG C, then with 2-3 DEG C/h
At the uniform velocity it is cooled to room temperature, obtains water white transparency bulk porous crystalline state metal-organic framework material.I.e. Zn-MOF.(chemical general formula is:
{[Zn5(ddcba)2]}n, n is the most infinite, and n only to represent crystalline material be that the structure being repeated to build by minimum unit is special
Point, for formula literary style).
Embodiment 2
1) the porous crystalline state metal-organic framework material obtained in embodiment 1 is made after solvent displaces guest molecule
For carrier, (guest molecule refers mainly to hydrone and the DMA molecule introduced in crystalline material synthesis, owing to this material possesses duct knot
Structure, both have certain residual in duct).Substitute mode is: crystalline material sample is placed in ethanol solution immersion 48
Hour, within every 24 hours, change an ethanol solution, then be vacuum dried 6 hours at 80 DEG C.Take crystalline state material transposed for 100mg subsequently
Material joins in 15ml deionized water, is subsequently adding the silver nitrate solution of the 10mg/L of 0.5ml, by above-mentioned mixed system concussion
24 hours.
2) above-mentioned mixed system is transferred in the quartz test tube of photochemical reactor, under conditions of stirring, utilize
Power is that the mercury lamp of 300W utilizes ultraviolet light to irradiate 3h, and reduction obtains new mixed system.
3), after the product obtained is separated by filtration, uses distilled water and dehydrated alcohol to wash respectively successively three times, obtain
Product 80 DEG C vacuum drying i.e. can get Ag Zn-MOF advanced composite material (ACM).
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 it is shown on figure 3, know that Ag nano particles is grown in surface and the duct of Zn-MOF uniformly from electromicroscopic photograph analysis.
The advanced composite material (ACM) of above-mentioned preparation is carried out the catalysis reduction of paranitrophenol, 1mgAg@Zn-MOF is combined
It is in the solution that concentration is the paranitrophenol of 14mg/L that material is added to concentration, and add 3mg potassium borohydride, reaction exist
Carrying out under conditions of room nature light or dark, reaction temperature is room temperature.Take out solution testing at regular intervals, utilize the ultraviolet can
See light spectrophotometer, judge catalysis process situation, warp by measuring solution at the absorbance of maximum absorption wavelength (400nm)
The time of mistake is 8min, can complete the catalysis reduction of paranitrophenol 100%.
Accompanying drawing illustrates:
The minimum asymmetric cell that accompanying drawing 1: reflecting metal has frame material, i.e. carrier material (Zn-MOF) are internal
Basic composition and coordination situation.Specifically indicate that how organic ligand and metal occur when constructing metal-organic framework material
Coordination.
Accompanying drawing 2: reflect the microstructure in metal-organic framework material interior three-dimensional duct, specifically present organic ligand
How three-dimensional open-framework is built with after metal-complexing.
Accompanying drawing 3: reflect Ag nanometer particle load to metal-organic framework material after Nanoparticle Size situation.
Accompanying drawing 4: reflect Ag nanometer particle load to metal-organic framework material after Nanoparticle Size and
It disperses situation.
Accompanying drawing 5: reflect material catalysis reduction time used by paranitrophenol and catalytic process.Each absorbs song
Line represents catalytic reaction and proceeds to the residual concentration of catalytic substrate during this time.
Accompanying drawing 6: reflect the material catalysis reduction macroscopic superficial appearance of paranitrophenol.
Claims (8)
1. a load type metal organic frame composite, it is characterised in that this composite is for possessing regular porous structure
Ag load type metal organic frame crystalline material, chemical general formula is { [Zn5(ddcba)2]}n, ddcba represents 3,5-bis-(2,5-
Dicarboxyphenyi) benzoic acid, n is the most infinite.
2. the load type metal organic frame composite described in claim 1, it is characterised in that it is oblique that this crystalline material belongs to three
Crystallographic system, space group is P-1, and cell parameter is: 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) taking 3,5-bis-(2,5-dicarboxyphenyi) 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 hour,
Until separating out colourless amorphous material, clear crystal being collected by filtration, at 80 DEG C, being vacuum dried 12h, obtain crystallite sample；
(2) the crystallite sample obtained in (1) is placed in ethanol solution immersion 48 hours, within every 24 hours, changes an ethanol molten
Liquid, then be vacuum dried 6 hours at 80 DEG C；
(3) take (2) obtain treat that load sample immerses in silver nitrate aqueous solution, after shaking 24 hours under room temperature, use power
Mercury lamp for 300W utilizes UV Light reduction to obtain mixed liquor, and the mixed liquor product obtained after filtering, uses steaming successively
Distilled water and dehydrated alcohol wash three times respectively, the product obtained, and product are vacuum dried at 30 DEG C～100 DEG C 4-6 hour i.e.
The metal organic frame composite of available loaded Ag nanoparticle.
The preparation method of load type metal organic frame composite the most according to claim 2, it is characterised in that wherein
3,5-bis-(2,5-dicarboxyphenyi) benzoic acid and the usage ratio of zinc nitrate are that (1:2/2:1 is available to 1:1 (mol ratio)
Mol ratio), N,N-dimethylacetamide is that (1:2/1:3/2:1/3:1 is for being available for for 1:1 (mol ratio) with the ratio of deionized water
The mol ratio selected)；Every 0.04mmol organic ligand correspondence 2ml deionized water and 2ml N,N-dimethylacetamide.
5. the preparation method of the load type metal organic frame composite described in claim 1, it is characterised in that step (3)
In, the load capacity of Ag is 0.5wt%～50wt%, and every 20mg treats that load sample correspondence 5mg-20mg silver nitrate and 3ml-10ml go
Ionized water (treats load sample: silver nitrate: deionized water quality compares: 4:1～4:1～2).
6. load type metal organic frame composite described in any one of claim 1-5 catalytic degradation paranitrophenol and/
Or the application on isomers.
7. the application described in claim 6, it is characterised in that concrete steps include the following: load type metal organic frame multiple
Condensation material in the ratio of 0.15g/L～0.5g/L be added to paranitrophenol that concentration is 14mg/L～25mg/L and/or with point
In the solution of isomer, adding potassium borohydride, react and carry out under conditions of natural light or dark, reaction temperature is room temperature, instead
It is 3min～20min between Ying Shi, the reduction process of whole paranitrophenols and/or isomers can be completed.
8. the application described in claim 7, it is characterised in that potassium borohydride concentration is 0.3g/L～1g/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656104A (en) * | 2002-05-30 | 2005-08-17 | 巴斯福股份公司 | Shaped bodies containing metal-organic frameworks |
| CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
| CN102336774A (en) * | 2011-07-20 | 2012-02-01 | 中国科学院化学研究所 | Method for synthesizing BTC (1,3,5-benzenetricarboxylic acid)-based nanoscale organometallic framework material |
| CN103347885A (en) * | 2010-07-20 | 2013-10-09 | 加利福尼亚大学董事会 | Functionalization of organic molecules using metal-organic frameworks (mofs) as catalysts |
-
2016
- 2016-06-02 CN CN201610387905.8A patent/CN106076419B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656104A (en) * | 2002-05-30 | 2005-08-17 | 巴斯福股份公司 | Shaped bodies containing metal-organic frameworks |
| CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
| CN103347885A (en) * | 2010-07-20 | 2013-10-09 | 加利福尼亚大学董事会 | Functionalization of organic molecules using metal-organic frameworks (mofs) as catalysts |
| CN102336774A (en) * | 2011-07-20 | 2012-02-01 | 中国科学院化学研究所 | Method for synthesizing BTC (1,3,5-benzenetricarboxylic acid)-based nanoscale organometallic framework material |
Non-Patent Citations (1)
| Title |
|---|
| JIANG LI等: "Two Microporous Metal−Organic Frameworks with Suitable Pore", 《CRYSTAL GROWTH & DESIGN》 * |
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