CN104324762B - A kind of trielement composite material preparation method and application - Google Patents
A kind of trielement composite material preparation method and application Download PDFInfo
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Abstract
The preparation method that the present invention relates to a kind of trielement composite material, belongs to the technical fields such as material science, nano material, catalysis.The present invention is with melamine chloro hexabasic carboxylic acid part and copper nitrate for raw material, prepare the porous metals organic framework Cu-MOF of hydrothermally stable, with Cu-MOF for carrier, at its surface anchoring nanometer silver, and coated porous titanium dioxide shell, prepare trielement composite material Cu-MOFAgTiO2.This composite has the performance of the catalysis reduction unsaturated organic compound of excellence, has a good application prospect in heterogeneous catalysis reduction reaction.
Description
Technical field
The present invention relates to a kind of trielement composite material preparation method and application, be specifically related to a kind of Cu-MOFAgTiO2The preparation method of catalyst and the catalysis organic application of reduction thereof, belong to the technical fields such as material science, nano material, metal organic complex, chemical industry, catalysis.
Background technology
Metal-organic framework thing (MOFs) material, being based on different metal ions and all kinds of rigidity or flexible organic ligand, the class aperture formed by ligand complex effect is adjustable, hole wall can design and the supermolecule porous structure material that can modify after synthesizing.Compared with other porous material, this material specific surface area is big, porosity is high, structure is close with potential characteristic relation, in many-sides such as catalysis, absorption, separation, thin film, sensing, identification, proton conduction, medicament slow releases, show the multi-functional porous structure material that other conventional porous materials can not be compared, but, one general deficiency of MOFs material is that hydrothermal stability is poor, this property limits MOFs material and applies on a large scale in the industry.
Nano metal is the class particle diameter metal material less than 100nm, for bulk metal material, due to unique construction featuress such as its particle size are little, specific surface area is big, show and update and more excellent characteristic, have become as indispensable catalyst in catalysis technical field.For improving the catalysis activity of nanometer silver, its preparation is for the purpose of the particle obtaining single dispersing, controlled shape, but because its specific surface energy is big, very easily reunites, thus causing that its catalysis activity reduces in synthesis and catalytic process.One of method solving nano metal reunion problem is to adopt porous carrier load, porous carrier is conducive to improving the dispersion of silver on the one hand, especially the consumption of silver can be reduced, reduce catalyst cost, on the other hand, its synergism can being played, carry high catalytic activity, improve stability and extend the service life of catalyst, if having the porous structure material loaded nano silver composite material catalyst of the features such as preparation is simple, energy consumption of reaction is low concurrently, must have broad application prospects.
Summary of the invention
One of technical assignment of the present invention is to make up the deficiencies in the prior art, it is provided that a kind of trielement composite material preparation method and application, is specifically related to the composite of a kind of MOF loading nano silvery cladding titanium dioxide shell, i.e. Cu-MOFAgTiO2Preparation method, the raw materials used cost of the method is low, and preparation technology is simple, and energy consumption of reaction is low, has prospects for commercial application.
The two of the technical assignment of the present invention are to provide the purposes of this composite, and this composite has MOF, nanometer silver and titanium dioxide synergism, and the hydro-reduction for catalysis unsaturated compounds reacts, and consumption is few, and catalysis activity is high.
Technical scheme is as follows:
1. a preparation method for trielement composite material, preparation process is as follows:
(1) Cu-MOF is prepared
By 1.7-1.8gCu (NO3)23H2O, 0.30-0.50g melamine chloro hexahydric acid part H6L、10-20mLDMA、5-10mLDMSO、1-1.5mLH2O and 9-10mLHBF4It is added in the vial of 50mL and mixes, 60 DEG C, the ultrasonic 6-10min of 120W, cooling, will wash with EtOH after solid centrifugation, dry at 75 DEG C, obtain blue Porous Cu-organic polymer crystal Cu-MOF, productivity is 87-90%；
Described part H6L, preparation process is as follows:
Take the 5-amino p-phthalic acid of 23.0-25.0g, 12.0-15.0g sodium hydroxide and water 200mL, stirring 30min, add cyanuric trichloride 8.0-8.5g, 1,4-dioxane 40-50mL, it is heated to reflux 8-10h, pH=2 is adjusted with hydrochloric acid, sucking filtration with distilled water wash solid 3 times, solid drying is obtained part H6L；Chemical formula is C3N3(NH)3(C6H3)3(COOH)6, molecular formula is C27H18N6O12；Preparation H6L reaction equation is as follows:
Described Cu-MOF, chemical formula is [Cu3L(H2O)3]·10H2O 5DMA, is the porous metals organic coordination compound with 3D structure；Structure is uniform-distribution with the cage that internal diameter is 1.2nm, 0.91nm and 1.72nm；Occupied by object hydrone and DMA molecule in cage；220 DEG C of heating, it is possible to elimination guest molecule；
(2) Cu-MOFAg is prepared
Cu-MOF is heated to 220 DEG C, and insulation 10-12h removes object solvent, is cooled to room temperature, adds 0.35mmol/LAgNO3Alcoholic solution 20-30mL, lucifuge dipping 10-12h；The solid being centrifugally separating to obtain, washes 3 times with water；Use UV illumination 10-15h, centrifugal and water washing solid, dry, prepare the surface anchoring Cu-MOF of nanometer Ag, i.e. Cu-MOFAg；
Described nanometer Ag, particle diameter 5-8nm；
(3) Cu-MOFAgTiO is prepared2
Cu-MOFAg is dispersed in the ethanol of 30-50mL, add the alcoholic solution 30-50mL of the butyl titanate that volume fraction is 30%, drip the water of 0.8-1mL with the time of 30min after, be heated to reflux 1h, it is centrifuged and with the solid that washing with alcohol obtains, is trielement composite material Cu-MOFAgTiO2。
2. the trielement composite material that prepared by preparation method as above, for catalysis reduction 4-nitrophenol, methyl orange, rhodamine B, naphthol green B, bromophenol blue, bromine cresol chlorine or C.I. 13020..
Compared with prior art, the preparation method of the trielement composite material of the present invention, its prominent feature is:
(1) ultrasonic method is used efficiently to prepare Cu-MOF
Due to the immense pressure that ultrasonic cavitation bubble produces, namely powerful shock wave, can accelerating and control the complexation reaction between raw material greatly, the present invention is by melamine chloro hexahydric acid part H6L and copper nitrate heating are ultrasonic: 1) growth of its crystal is only accomplished within a few minutes, and adopt identical proportioning, 85 DEG C of three talent of heating can prepare crystal, namely ultrasonic method can substantially speed up nucleation and the growth of this crystal, significantly improving of preparation efficiency, greatly reduces production cost；2) due to the immense pressure that cavitation bubble produces, the crystal that the Cu-MOF crystalline size of generation prepares than heating is made evenly；3) adopt identical proportioning, heating 85 DEG C three talent to prepare the productivity of crystal lower than 80%, and the application productivity is 87-90%.
(2) catalysis activity is high
The present invention have selected porous metals organic frame complex Cu-MOF loading nano silvery, owing to this MOF porous framework exists a large amount of unsaturated site, so, very easily adsorb Ag+, when using ultraviolet lighting, by Ag+It is reduced into nano silver particles, due to the restriction effect of this metal organic complex framework, the reunion of nanometer silver can be prevented effectively from；The shell titanium dioxide at its Surface coating, this composite is heated to reflux one day in boiling water, or room temperature is placed one month, characterizes through XRD, and its loose structure is not destroyed；Additionally, trielement composite material synergism makes this composite, has higher catalysis activity, and not only efficient catalytic Reduction of Aromatic Nitro Compounds becomes aromatic amine, moreover, it is also possible to efficient catalytic reduction methyl orange, rhodamine B, naphthol green B, bromophenol blue, bromine cresol chlorine or C.I. 13020..
(3) prospects for commercial application is good
Aromatic nitro compound is the important intermediate of synthetic dyestuffs, pigment, explosive and other fine chemicals, being widely present in the industrial wastewaters such as dyestuff, medicine, pesticide, explosive, belong to difficult for biological degradation organic compound, directly discharge is big to bio-toxicity, polluted water region, destroys ecology.Additionally, azo-compound waste water is not treated is directly discharged into water body, the growth of aquatic animals and plants can be affected, promote BOD, COD index in water body, the most seriously azo-compound and some derivants of producing in natural water thereof, there is carcinogenic, teratogenesis, mutagenic three-induced effect, aquatic ecological environment is had tremendous influence.Therefore, before azo material waste water enters water body, it is carried out effective process very necessary.Aromatic nitro compound high efficiency catalysis can be reduced to aromatic amine compounds by the application catalyst, by unsaturated high chroma material efficient catalytic reduction such as azo materials, aromatic nitro compound and high chroma material poisoning environmental microorganism can be reduced, create condition for further bioprocessing industry waste water；Compared with precious metals platinum catalyst, the cost of this catalyst significantly reduces；Compared with Raney's nickel catalyst, simply, easily operate, cost of material is relatively low for this catalyst preparation process；This catalyst has good prospects for commercial application.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not only limited to embodiment, the change that technical solution of the present invention is made by this field professional, all should belong in protection scope of the present invention.
Embodiment 1
A kind of melamine chloro hexabasic carboxylic acid part H6The preparation method of L: take the 5-amino p-phthalic acid of 23.0g, 12.0g sodium hydroxide and water 200mL, stirs 30min, add cyanuric trichloride 8.0g, 1,4-dioxane 40mL, is heated to reflux 8h, adjusts pH=2 with hydrochloric acid, sucking filtration with distilled water wash solid 3 times, obtains part H by solid drying6L；Productivity is 95%；Chemical formula is C3N3(NH)3(C6H3)3(COOH)6, molecular formula is C27H18N6O12。
Embodiment 2
A kind of melamine chloro hexabasic carboxylic acid part H6The preparation method of L: take the 5-amino p-phthalic acid of 25.0g, 15.0g sodium hydroxide and water 200mL, stirs 30min, add cyanuric trichloride 8.5g, 1,4-dioxane 50mL, is heated to reflux 10h, adjusts pH=2 with hydrochloric acid, sucking filtration with distilled water wash solid 3 times, obtains part H by solid drying6L；Productivity is 95%；Chemical formula is with embodiment 1, and molecular formula is with embodiment 1.
Embodiment 3
A kind of melamine chloro hexabasic carboxylic acid part H6The preparation method of L: take the 5-amino p-phthalic acid of 24g, 13.5g sodium hydroxide and water 200mL, stirs 30min, add cyanuric trichloride 8.25g, 1,4-dioxane 45mL, is heated to reflux 9h, adjusts pH=2 with hydrochloric acid, sucking filtration with distilled water wash solid 3 times, obtains part H by solid drying6L；Productivity is 95%；Chemical formula is same embodiment 1, and molecular formula is with embodiment 1.
Embodiment 4
The preparation method of a kind of Cu-MOF: by 1.7gCu (NO3)23H2The melamine chloro hexahydric acid part H that O, 0.30g embodiment 1, embodiment 2 or embodiment 3 prepare6L、10mLDMA、5mLDMSO、1mLH2O and 9mLHBF4It is added in the vial of 50mL and mixes, 60 DEG C, the ultrasonic 6min of 120W, cooling, will wash with EtOH after solid centrifugation, dry at 75 DEG C, obtain blue Porous Cu-organic polymer octahedral crystal Cu-MOF；Its chemical formula is [Cu3L(H2O)3]·10H2O 5DMA, is the porous metals organic coordination compound with 3D structure；Structure is uniform-distribution with the cage that internal diameter is 1.2nm, 0.91nm and 1.72nm；Occupied by object hydrone and DMA molecule in cage；220 DEG C of heating, it is possible to elimination guest molecule；
Cu-MOF is heated to reflux one day in boiling water, or room temperature is placed one month, characterizes through XRD, and its loose structure is not destroyed
Embodiment 5
The preparation method of a kind of Cu-MOF: by 1.8gCu (NO3)23H2The melamine chloro hexahydric acid part H that O, 0.50g embodiment 1, embodiment 2 or embodiment 3 prepare6L、20mLDMA、10mLDMSO、1.5mLH2O and 9-10mLHBF4It is added in the vial of 50mL and mixes, 60 DEG C, the ultrasonic 10min of 120W, cooling, will wash with EtOH after solid centrifugation, dry at 75 DEG C, obtain blue Porous Cu-organic polymer octahedral crystal Cu-MOF；Its structure, chemical formula and character are all with embodiment 4.
Embodiment 6
The preparation method of a kind of Cu-MOF: by 1.6gCu (NO3)23H2The melamine chloro hexahydric acid part H that O, 0.4g embodiment 1, embodiment 2 or embodiment 3 prepare6L、15mLDMA、7.5mLDMSO、1.25mLH2O and 9.5mLHBF4It is added in the vial of 50mL and mixes, 60 DEG C, the ultrasonic 8min of 120W, cooling, will wash with EtOH after solid centrifugation, dry at 75 DEG C, obtain blue Porous Cu-organic polymer octahedral crystal Cu-MOF；Its structure, chemical formula and character are all with embodiment 4.
Embodiment 7
A kind of method of Cu-MOFAg of preparation: the Cu-MOF that embodiment 4, embodiment 5 or embodiment 6 prepare is heated to 220 DEG C, and insulation 10h removes object solvent, is cooled to room temperature, adds 0.35mmol/LAgNO3Alcoholic solution 20mL, lucifuge dipping 10h；The solid being centrifugally separating to obtain, washes 3 times with water；Use UV illumination 10h, centrifugal and water washing solid, dry, prepare the surface anchoring Cu-MOF of nanometer Ag, i.e. Cu-MOFAg；The particle diameter of nanometer Ag is about 5nm.
Embodiment 8
A kind of method of Cu-MOFAg of preparation: the Cu-MOF that embodiment 4, embodiment 5 or embodiment 6 prepare is heated to 220 DEG C, and insulation 12h removes object solvent, is cooled to room temperature, adds 0.35mmol/LAgNO3Alcoholic solution 30mL, lucifuge dipping 12h；The solid being centrifugally separating to obtain, washes 3 times with water；Use UV illumination 15h, centrifugal and water washing solid, dry, prepare the surface anchoring Cu-MOF of nanometer Ag, i.e. Cu-MOFAg；The particle diameter of nanometer Ag is about 8nm.
Embodiment 9
A kind of method of Cu-MOFAg of preparation: the Cu-MOF that embodiment 4, embodiment 5 or embodiment 6 prepare is heated to 220 DEG C, and insulation 11h removes object solvent, is cooled to room temperature, adds 0.35mmol/LAgNO3Alcoholic solution 25mL, lucifuge dipping 11h；The solid being centrifugally separating to obtain, washes 3 times with water；Use UV illumination 13h, centrifugal and water washing solid, dry, prepare the surface anchoring Cu-MOF of nanometer Ag, i.e. Cu-MOFAg；The particle diameter of nanometer Ag is about 6.5nm.
Embodiment 10
One prepares Cu-MOFAgTiO2Method: the Cu-MOFAg that embodiment 7, embodiment 8 or embodiment 9 prepare is dispersed in the ethanol of 30mL, add the alcoholic solution 30mL of the butyl titanate that volume fraction is 30%, drip the water of 0.8mL with the time of 30min after, it is heated to reflux 1h, it is centrifuged and with the solid that washing with alcohol obtains, is trielement composite material Cu-MOFAgTiO2。
Embodiment 11
One prepares Cu-MOFAgTiO2Method: the Cu-MOFAg that embodiment 7, embodiment 8 or embodiment 9 prepare is dispersed in the ethanol of 50mL, add the alcoholic solution 50mL of the butyl titanate that volume fraction is 30%, drip the water of 1mL with the time of 30min after, it is heated to reflux 1h, it is centrifuged and with the solid that washing with alcohol obtains, is trielement composite material Cu-MOFAgTiO2。
Embodiment 12
One prepares Cu-MOFAgTiO2Method: the Cu-MOFAg that embodiment 7, embodiment 8 or embodiment 9 prepare is dispersed in the ethanol of 40mL, add the alcoholic solution 40mL of the butyl titanate that volume fraction is 30%, drip the water of 0.9mL with the time of 30min after, it is heated to reflux 1h, it is centrifuged and with the solid that washing with alcohol obtains, is trielement composite material Cu-MOFAgTiO2。
Embodiment 13
-the MOFAgTiO that embodiment 10, embodiment 11 or embodiment 12 are prepared2For catalysis reduction 4-nitrophenol, methyl orange, rhodamine B, naphthol green B, bromophenol blue, bromine cresol chlorine or C.I. 13020..
Catalysis reduction 4-nitrophenol becomes 4-nitroaniline: in the aqueous solution of the 4-nitrophenol of 250mL, 18mmol/L, add 0.23mol sodium borohydride, under magnetic agitation, once add 0.10g catalyst, only needing 20 seconds, 4-nitrophenol 100% is converted into 4-nitroaniline；Second time adds the 4-nitrophenol aqueous solution of 250mL, 18mmol/L, and 25 seconds, 4-nitrophenol 100% was converted into 4-nitroaniline；Third time adds the 4-nitrophenol aqueous solution of 250mL, 18mmol/L, and 40 seconds, 4-nitrophenol 100% was converted into 4-nitroaniline；The 4-nitrophenol aqueous solution that 4th time adds 250mL, 18mmol/L, 1.2min, 4-nitrophenol 100% is converted into 4-nitroaniline.Other condition is identical, it does not have catalyst, 12h, and above-mentioned mixed liquor can not generate 4-nitroaniline.
Catalysis reduction methyl orange, rhodamine B, naphthol green B, bromophenol blue, bromine cresol chlorine or C.I. 13020.: take the indicator solution to be restored of 250mL, 1g/L, add the sodium borohydride of 0.06moL, under magnetic agitation, once add 0.10g catalyst, less than 1min, indicator solution is changed into colourless solution, it was shown that indicator is reduced；Other condition is identical, is added without catalyst, and 12h indicator solution is colour-fast.
Claims (4)
1. the preparation method of a trielement composite material, it is characterised in that preparation process is as follows:
(1) Cu-MOF is prepared
By 1.7-1.8gCu (NO3)2·3H2O, 0.30-0.50g melamine chloro hexahydric acid part H6L、10-20mLDMA、5-10mLDMSO、1-1.5mLH2O and 9-10mLHBF4It is added in the vial of 50mL and mixes, 60 DEG C, the ultrasonic 6-10min of 120W, cooling, will wash with EtOH after solid centrifugation, dry at 75 DEG C, obtain blue Porous Cu-organic polymer crystal Cu-MOF；Described part H6L, preparation process is as follows:
Take the 5-amino p-phthalic acid of 23.0-25.0g, 12.0-15.0g sodium hydroxide and water 200mL, stirring 30min, add cyanuric trichloride 8.0-8.5g, 1,4-dioxane 40-50mL, it is heated to reflux 8-10h, pH=2 is adjusted with hydrochloric acid, sucking filtration with distilled water wash solid 3 times, solid drying is obtained part H6L；Productivity is 95%；Chemical formula is C3N3(NH)3(C6H3)3(COOH)6, molecular formula is C27H18N6O12；
The reaction equation of preparation is as follows:
(2) Cu-MOFAg is prepared
Cu-MOF is heated to 220 DEG C, and insulation 10-12h removes object solvent, is cooled to room temperature, adds 0.35mmol/LAgNO3Alcoholic solution 20-30mL, lucifuge dipping 10-12h；The solid being centrifugally separating to obtain, washes 3 times with water；Use UV illumination 10-15h, centrifugal and water washing solid, dry, prepare the surface anchoring Cu-MOF of nanometer Ag, i.e. Cu-MOFAg；
(3) Cu-MOFAgTiO is prepared2
Cu-MOFAg is dispersed in the ethanol of 30-50mL, add the alcoholic solution 30-50mL of the butyl titanate that volume fraction is 30%, drip the water of 0.8-1mL with the time of 30min after, be heated to reflux 1h, it is centrifuged and with the solid that washing with alcohol obtains, is trielement composite material Cu-MOFAgTiO2。
2. the preparation method of a kind of trielement composite material as claimed in claim 1, described Cu-MOF, chemical formula is [Cu3L(H2O)3]·10H2O 5DMA, is the porous metals organic coordination compound with 3D structure；Structure is uniform-distribution with the cage that internal diameter is 1.2nm, 0.91nm and 1.72nm；Occupied by object hydrone and DMA molecule in cage；220 DEG C of heating, it is possible to elimination object hydrone, described L, chemical formula is C3N3(NH)3(C6H3)3(COO)6。
3. the preparation method of a kind of trielement composite material as claimed in claim 1, described nanometer Ag, particle diameter 5-8nm.
4. the trielement composite material that prepared by preparation method as claimed in claim 1, it is characterised in that for catalysis reduction 4-nitrophenol, methyl orange, rhodamine B, naphthol green B, bromophenol blue, bromine cresol chlorine or C.I. 13020..
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| CN105233871A (en) * | 2015-09-30 | 2016-01-13 | 华东理工大学 | Preparation method of MOFs catalyst Cu(3-bpdh)(TDA) capable of degrading organic dye |
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| CN106582857A (en) * | 2016-12-16 | 2017-04-26 | 昆明理工大学 | Preparation method of metal organic framework for loading nano silver |
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| CN109174007B (en) * | 2018-08-23 | 2021-06-25 | 扬州大学 | Metal organic framework and preparation method and application thereof |
| CN109482241B (en) * | 2018-12-07 | 2021-08-17 | 怀化学院 | TiO2/MOF-5 photocatalyst and preparation method thereof |
| CN111484141B (en) * | 2020-03-17 | 2022-05-20 | 江苏大学 | Degradation method of bromocresol green wastewater |
| CN112391840B (en) * | 2020-10-20 | 2023-02-24 | 西安工程大学 | Method for modifying wool fibers by core-shell hollow-structure MOF material |
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