CN104324761A - Preparation and applications of porous rare earth organic complex base catalyst - Google Patents
Preparation and applications of porous rare earth organic complex base catalyst Download PDFInfo
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- CN104324761A CN104324761A CN201410524891.0A CN201410524891A CN104324761A CN 104324761 A CN104324761 A CN 104324761A CN 201410524891 A CN201410524891 A CN 201410524891A CN 104324761 A CN104324761 A CN 104324761A
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Abstract
The present invention relates to a preparation method of a porous rare earth organic complex base catalyst, and belongs to the technical fields of material science, nanometer materials, catalysis and the like. According to the present invention, trimesic acid and cerium nitrate are adopted as raw materials, ultrasound is performed to prepare a water stable porous rare earth metal organic framework material Ce-MOF, the Ce-MOF is adopted as a carrier, nanometer Ag is anchored on the surface, and a porous titanium dioxide shell layer is coated to prepare the ternary composite material Ce-MOF@Ag@TiO2. The composite material has the excellent performance of catalytic reduction of unsaturated organic compounds, and has good application prospects in heterogeneous catalytic reduction reactions.
Description
Technical field
The present invention relates to the preparation method and application that a kind of porous rare earth organic coordination compound is catalyst based, be specifically related to a kind of Ce-MOF@Ag@TiO
2the preparation method of catalyst and the organic application of catalytic reduction thereof, belong to the technical fields such as material science, nano material, metal organic complex, chemical industry, catalysis.
Background technology
Metal-organic complex is based on different metal ions and all kinds of rigidity or flexible organic ligand, the base polymer formed by ligand complex effect.Inorganic chemistry and organic chemistry not only integrate by this complex, and the subjects such as inorganic chemistry, crystal chemistry and materials chemistry are connected closely, potential application in catalysis, molecular recognition, photoelectricity, magnetic, Subjective and Objective exchange and molecular conductor, has become one of focus of new material research exploitation.
When Metal-organic complex is formed, except participating in except coordination by metal and organic ligand, also comprise the non-covalent interactions such as hydrogen bond, pi-pi accumulation effect and electrostatic interaction.Therefore, traditional unimolecule complex, due to the periodicity repetitive that the effect of the non-covalent bond such as hydrogen bond and pi-pi accumulation is formed, can not have the frame structure of three dimensions expansion, is referred to as superstructure or supermolecule to space three-dimensional expansion or other.Traditional unimolecule complex and multidimensional complex, be referred to as metal-organic supermolecular or metal-organic framework (Metal-Organic Framework), referred to as MOF.Compared with other porous material, this material specific surface area is large, porosity is high, structure and potential characteristic relation close, in many-sides such as catalysis, absorption, separation, film, sensing, identification, proton conduction, medicament slow releases, show the multifunctionality that other conventional porous materials can not be compared.
The preparation of MOF mainly contains diffusion method and solvent-thermal method.Diffusion method refers to that reactant solution generates a kind of method of target product by processes such as liquid level contact, diffusion, reactions.The method reaction condition is gentleer, application comparatively early, but its deficiency to be preparation manipulation loaded down with trivial details, reaction time is long, is difficult to the controlledly synthesis realizing crystal, and the crystal grown is irregular.Solvent-thermal method be apply the most generally, method the most practical.Specific practice be by slaine, organic ligand and water or other solvent seal in the stainless steel cauldron of inner liner polytetrafluoroethylene, when being heated to uniform temperature (80-300 DEG C), in still, pressure can reach a hundreds of atmospheric pressure, cause chemical compound lot solubilizing reaction in the supercritical state, after maintaining a period of time, slow cooling, reactant mixture obtains the crystal of sizeable systematicness by reactive crystallization.In the synthesis of MOF crystalline material, the crystal of this kind of method synthesis has that crystal structure is good, shape is regular, device therefor is simple, operate the advantages such as easy.But its limitation is that preparation time is also longer, and needs HTHP step, the application in the industrial production of this method is hindered to the challenge etc. of production equipment and high energy consumption.
Nano metal is the metal material that a class particle diameter is less than 100nm, for bulk metal material, due to the design feature of the uniquenesses such as its particle size is little, specific area is large, show and upgrade and more excellent characteristic, become indispensable catalyst in catalysis technical field.For improving the catalytic activity of Nano Silver, its preparation for the purpose of the particle obtaining single dispersing, controlled shape, but because of its specific surface energy large, very easily reunite in synthesis and catalytic process, thus cause its catalytic activity to reduce.Solving one of method of nano metal reunion problem is adopt porous carrier load, porous carrier is conducive to the decentralization improving silver on the one hand, especially the consumption of silver can be reduced, reduce catalyst cost, on the other hand, its synergy can be played, improve catalytic activity, improve stability and the service life of extending catalyst.Research and development MOF load-type nanometer metal, and have 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, the preparation method that a kind of porous rare earth organic coordination compound is catalyst based is provided, be specifically related to the composite of a kind of Ce-MOF loading nano silvery cladding titanium dioxide shell, i.e. Ce-MOF@Ag@TiO
2preparation 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.
Two of technical assignment of the present invention is to provide this composite Ce-MOF@Ag@TiO
2purposes, this composite have Ce-MOF, Nano Silver and titanium dioxide synergy, the hydro-reduction for catalysis unsaturated compounds reacts, and consumption is few, and catalytic activity is high.
Technical scheme of the present invention is as follows:
1. the preparation method that a porous rare earth organic coordination compound is catalyst based
(1) Ce-MOF is prepared
To 4.0 mL DMF and 4.0 mL H
2in the mixed solvent of O, add 0.25-0.30 mmol 1,3,5-Benzenetricarboxylic acid, 0.5-0.6mmol six water cerous nitrate, 60 DEG C, the ultrasonic 5-8min of 120W, centrifugation, be that the mixture of the second alcohol and water of 1:1 washs the crystal that obtains 3 times by volume ratio, drying, obtain porous rare earth Function for Organometallic Complex Crystals Ce-MOF, productive rate is 87-90%;
Described Ce-MOF, chemical formula is { [Ce (C
6h
3(COO)
3(H
2o)] (H
2o)
0.5dMF}n, belongs to the porous rare earth metal organic complex of three-dimensional structure; There is in its one-dimentional structure the structure channel that the length of side is about 6.3 × 6.3, occupied by object hydrone and DMF molecule in passage; 200 DEG C of heating, can remove guest molecule;
(2) Ce-MOF@Ag is prepared
Cu-MOF is heated to 200-220 DEG C, and insulation 10-12h, cool to room temperature, adds 0.10mmol/L AgNO
3ethanolic solution 2.0-3.0 mL, lucifuge dipping 12h; Centrifugation, and wash solid with water 3 times; With the UV illumination 10-13h of 100W, centrifugal and wash with water, dry, the obtained surface anchoring Ce-MOF@Ag of nanometer Ag;
Described nanometer Ag, particle diameter 6-9nm;
(3) Ce-MOF@Ag@TiO is prepared
2
Ce-MOF Ag is dispersed in the ethanol of 20mL, adds 20-25mL, ethanolic solution that volume fraction is the butyl titanate of 30%, 30min drips the water of 0.4mL, adds hot reflux 1h, centrifugation, obtained Ce-MOF Ag TiO
2catalyst.
2. the porous rare earth organic coordination compound prepared of preparation method as above is catalyst based, for catalytic reduction 4-nitrophenol, methyl orange, rhodamine B, naphthol green B, bromophenol blue, bromine cresols chlorine or methyl red.
Compared with prior art, the preparation method of trielement composite material of the present invention, its outstanding feature is:
(1) ultrasonic method is used efficiently to prepare Ce-MOF
Due to the immense pressure that ultrasonic cavitation bubble produces, namely powerful shock wave, can accelerate and control the complexation reaction between raw material greatly, the present invention by trimesic acid and cerous nitrate ultrasonic: 1) growth of its crystal is only accomplished within a few minutes, and adopt identical proportioning, heating 150 DEG C, 48h just can obtain crystal, namely ultrasonic method significantly can accelerate the coring and increment of this crystal, and significantly improving of preparation efficiency, greatly reduces production cost; 2) due to cavitation bubble produce immense pressure, the crystal making the Ce-MOF crystalline size of generation more obtained than heating evenly; 3) adopt identical proportioning, heating 150 DEG C, 48h to obtain the productive rate of crystal lower than 75%, and the application's productive rate is 87-90%.
(2) catalytic activity is high
The present invention have selected porous metals organic frame complex Ce-MOF loading nano silvery, because this MOF porous framework exists a large amount of unsaturated site, so, very easily adsorb Ag
+, when using ultraviolet lighting, by Ag
+be reduced into nano silver particles, due to the restriction effect of this metal organic complex framework, effectively can avoid the reunion of Nano Silver; The shell titanium dioxide at its Surface coating, this composite is water insoluble, DMF, ethyl acetate, acetone, benzene, toluene, chloroform, carbon tetrachloride etc., places one month in air at room temperature, and characterize through XRD, its loose structure is not destroyed; In addition, ternary component synergy makes this composite, and have higher catalytic activity, not only efficient catalytic Reduction of Aromatic Nitro Compounds becomes aromatic amine, and, all right efficient catalytic reduction methyl orange, rhodamine B, naphthol green B, bromophenol blue, bromine cresols chlorine or methyl red.
(3) prospects for commercial application is good
Aromatic nitro compound is the important intermediate of synthetic dyestuffs, pigment, explosive and other fine chemicals, extensively be present in the industrial wastewaters such as dyestuff, medicine, agricultural chemicals, explosive, belong to difficult for biological degradation organic compound, directly discharge is large to bio-toxicity, polluted water region, destroys ecological.In addition, azo-compound waste water is not treated directly enters 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 derivatives of producing in natural water thereof, there is carcinogenic, teratogenesis, mutagenic three-induced effect, have tremendous influence to aquatic ecological environment.Therefore, before azo material waste water enters water body, effective process is carried out to it very necessary.Aromatic nitro compound high efficiency catalytic reduction can be aromatic amine compounds by the application's 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, for further bioprocessing industry waste water creates condition; Compared with precious metals platinum catalyst, the cost of this catalyst significantly reduces; Compared with Raney's nickel catalyst, this catalyst preparation process is simple, easy to operate, and cost of material is lower; 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 confined to embodiment, the change that this field professional does technical solution of the present invention, all should belong in protection scope of the present invention.
Embodiment 1
The preparation method of a kind of Ce-MOF: to 4.0 mL DMF and 4.0 mL H
2in the mixed solvent of O, add 0.25 mmol 1,3,5-Benzenetricarboxylic acid, 0.5mmol six water cerous nitrate, 60 DEG C, the ultrasonic 5min of 120W, centrifugation, be that the mixture of the second alcohol and water of 1:1 washs the crystal that obtains 3 times by volume ratio, dry, obtain porous rare earth Function for Organometallic Complex Crystals Ce-MOF, productive rate is 87%, and chemical formula is { [Ce (C
6h
3(COO)
3(H
2o)] (H
2o)
0.5dMF}n, belongs to the porous rare earth metal organic complex of three-dimensional structure; There is in its one-dimentional structure the structure channel that the length of side is about 6.3 × 6.3, occupied by object hydrone and DMF molecule in passage; 200 DEG C of heating, can remove guest molecule.
Embodiment 2
The preparation method of a kind of Ce-MOF: to 4.0 mL DMF and 4.0 mL H
2in the mixed solvent of O, add 0.30 mmol 1,3,5-Benzenetricarboxylic acid, 0.6mmol six water cerous nitrate, 60 DEG C, the ultrasonic 8min of 120W, centrifugation, be that the mixture of the second alcohol and water of 1:1 washs the crystal that obtains 3 times by volume ratio, dry, obtain porous rare earth Function for Organometallic Complex Crystals Ce-MOF, productive rate is 90%, and chemical formula, structure and character are with embodiment 1.
Embodiment 3
The preparation method of a kind of Ce-MOF: to 4.0 mL DMF and 4.0 mL H
2in the mixed solvent of O, add 0.27 mmol 1,3,5-Benzenetricarboxylic acid, 0.55mmol six water cerous nitrate, 60 DEG C, ultrasonic 7 min of 120W, centrifugation, be that the mixture of the second alcohol and water of 1:1 washs the crystal that obtains 3 times by volume ratio, dry, obtain porous rare earth Function for Organometallic Complex Crystals Ce-MOF, productive rate is 88%, and chemical formula, structure and character are with embodiment 1.
Embodiment 4
The preparation method of a kind of Ce-MOF@Ag: Cu-MOF obtained for embodiment 1, embodiment 2 or embodiment 3 is heated to 200 DEG C, insulation 10h, cool to room temperature, adds 0.10mmol/L AgNO
3ethanolic solution 2.0 mL, lucifuge dipping 12h; Centrifugation, and wash solid with water 3 times; With the UV illumination 10-13h of 100W, centrifugal and wash with water, dry, the obtained surface anchoring Ce-MOF@Ag of nanometer Ag; Described nanometer Ag, particle diameter 7nm.
Embodiment 5
The preparation method of a kind of Ce-MOF@Ag: Cu-MOF obtained for embodiment 1, embodiment 2 or embodiment 3 is heated to 220 DEG C, insulation 12h, cool to room temperature, adds 0.10mmol/L AgNO
3ethanolic solution 3.0 mL, lucifuge dipping 12h; Centrifugation, and wash solid with water 3 times; With the UV illumination 10-13h of 100W, centrifugal and wash with water, dry, the obtained surface anchoring Ce-MOF@Ag of nanometer Ag; Described nanometer Ag, particle diameter 6nm.
Embodiment 6
The preparation method of a kind of Ce-MOF@Ag: Cu-MOF obtained for embodiment 1, embodiment 2 or embodiment 3 is heated to 210 DEG C, insulation 11h, cool to room temperature, adds 0.10mmol/L AgNO
3ethanolic solution 2.5 mL, lucifuge dipping 12h; Centrifugation, and wash solid with water 3 times; With the UV illumination 12h of 100W, centrifugal and wash with water, dry, the obtained surface anchoring Ce-MOF@Ag of nanometer Ag; Described nanometer Ag, particle diameter 9nm.
Embodiment 7
A kind of Ce-MOF@Ag@TiO
2preparation method: the Ce-MOF@Ag that embodiment 4, embodiment 5 or embodiment 6 is obtained is dispersed in the ethanol of 20mL, add the ethanolic solution that 20mL volume fraction is the butyl titanate of 30%, 30min drips the water of 0.4mL, add hot reflux 1h, centrifugation, obtained Ce-MOF@Ag@TiO
2catalyst; This Ce-MOF@Ag@TiO
2water insoluble, DMF, ethyl acetate, acetone, benzene, toluene, chloroform, carbon tetrachloride etc., place one month in air at room temperature, and characterize through XRD, its loose structure is not destroyed.
Embodiment 8
A kind of Ce-MOF@Ag@TiO
2preparation method: embodiment 4, embodiment 5 or embodiment 6 are obtained Ce-MOF@Ag and are dispersed in the ethanol of 20mL, add 25mL, ethanolic solution that volume fraction is the butyl titanate of 30%, 30min drips the water of 0.4mL, add hot reflux 1h, centrifugation, obtained Ce-MOF@Ag@TiO
2catalyst; This Ce-MOF@Ag@TiO
2water insoluble, DMF, ethyl acetate, acetone, benzene, toluene, chloroform, carbon tetrachloride etc., place one month in air at room temperature, and characterize through XRD, its loose structure is not destroyed.
Embodiment 9
A kind of Ce-MOF@Ag@TiO
2preparation method: embodiment 4, embodiment 5 or embodiment 6 are obtained Ce-MOF@Ag and are dispersed in the ethanol of 20mL, add 23mL, ethanolic solution that volume fraction is the butyl titanate of 30%, 30min drips the water of 0.4mL, add hot reflux 1h, centrifugation, obtained Ce-MOF@Ag@TiO
2catalyst; This Ce-MOF@Ag@TiO
2water insoluble, DMF, ethyl acetate, acetone, benzene, toluene, chloroform, carbon tetrachloride etc., place one month in air at room temperature, and characterize through XRD, its loose structure is not destroyed.
Embodiment 10
The Ce-MOF@Ag@TiO of embodiment 7, embodiment 8 or embodiment 9 preparation
2, for catalytic reduction 4-nitrophenol, methyl orange, rhodamine B, naphthol green B, bromophenol blue, bromine cresols chlorine or methyl red.
Catalytic reduction 4-nitrophenol becomes 4-nitroaniline: in the aqueous solution of the 4-nitrophenol of 250mL, 18mmol/L, add 0.23 mol sodium borohydride, under magnetic agitation, once add 0.10 g catalyst, only needed for 13 seconds, 4-nitrophenol 100% is converted into 4-nitroaniline; Second time adds the 4-nitrophenol aqueous solution of 250mL, 18mmol/L, and in 15 seconds, 4-nitrophenol 100% is converted into 4-nitroaniline; Add the 4-nitrophenol aqueous solution of 250mL, 18mmol/L for the third time, 1.5min, 4-nitrophenol 100% is converted into 4-nitroaniline; Add the 4-nitrophenol aqueous solution of 250mL, 18mmol/L for 4th time, 5min, 4-nitrophenol 100% is converted into 4-nitroaniline.Other condition is identical, does not have catalyst, 12h, and above-mentioned mixed liquor can not generate 4-nitroaniline.
Catalytic reduction methyl orange, rhodamine B, naphthol green B, bromophenol blue, bromine cresols chlorine or methyl red: the indicator solution to be restored getting 250mL, 1g/L, add the sodium borohydride of 0.06moL, under magnetic agitation, once add 0.10 g catalyst, be less than 1min, indicator solution changes colourless solution into, shows that indicator is reduced; Other condition is identical, does not add catalyst, and 12h indicator solution is colour-fast.
Claims (4)
1. the preparation method that porous rare earth organic coordination compound is catalyst based, is characterized in that, preparation process is as follows:
(1) Ce-MOF is prepared
To 4.0 mL DMF and 4.0 mL H
2in the mixed solvent of O, add 0.25-0.30 mmol 1,3,5-Benzenetricarboxylic acid, 0.5-0.6mmol six water cerous nitrate, 60 DEG C, the ultrasonic 5-8min of 120W, centrifugation, be that the mixture of the second alcohol and water of 1:1 washs the crystal that obtains 3 times by volume ratio, drying, obtain porous rare earth Function for Organometallic Complex Crystals Ce-MOF, productive rate is 87-90%;
(2) Ce-MOF@Ag is prepared
Cu-MOF is heated to 200-220 DEG C, and insulation 10-12h, cool to room temperature, adds 0.10mmol/L AgNO
3ethanolic solution 2.0-3.0 mL, lucifuge dipping 12h; Centrifugation, and wash solid with water 3 times; With the UV illumination 10-13h of 100W, centrifugal and wash with water, dry, the obtained surface anchoring Ce-MOF@Ag of nanometer Ag;
(3) Ce-MOF@Ag@TiO is prepared
2
Ce-MOF@Ag is dispersed in the ethanol of 20mL, add 20-25mL, ethanolic solution that volume fraction is the butyl titanate of 30%, 30min drips the water of 0.4mL, adds hot reflux 1h, centrifugation, obtained porous rare earth organic coordination compound catalyst based Ce-MOF@Ag@TiO
2.
2. the preparation method that a kind of porous rare earth organic coordination compound as claimed in claim 1 is catalyst based, described Ce-MOF, chemical formula is { [Ce (C
6h
3(COO)
3(H
2o)] (H
2o)
0.5dMF}n, belongs to the porous rare earth metal organic complex of three-dimensional structure; There is in its one-dimentional structure the structure channel that the length of side is about 6.3 × 6.3, occupied by object hydrone and DMF molecule in passage; 200 DEG C of heating, can remove guest molecule.
3. the preparation method that a kind of porous rare earth organic coordination compound as claimed in claim 1 is catalyst based, described nanometer Ag, particle diameter 6-9nm.
4. the porous rare earth organic coordination compound prepared of preparation method as claimed in claim 1 is catalyst based, for catalytic reduction 4-nitrophenol, methyl orange, rhodamine B, naphthol green B, bromophenol blue, bromine cresols chlorine or methyl red.
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