CN105214727A - A kind of polystyrene-based CuBTC composite catalyst of dumb-bell shape and preparation method - Google Patents
A kind of polystyrene-based CuBTC composite catalyst of dumb-bell shape and preparation method Download PDFInfo
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Abstract
The invention provides polystyrene-based CuBTC composite catalyst of a kind of dumb-bell shape and preparation method thereof.This preparation method comprises with the dumb-bell shape polystyrene microsphere through oversulfonate process for carrier, and repeated loading mantoquita and trimesic acid prepare the step of the polystyrene-based CuBTC composite catalyst of dumb-bell shape.Present invention also offers the polystyrene-based CuBTC composite catalyst of dumb-bell shape that said method prepares.The present invention successfully synthesizes dumb-bell shape PSCuBTC complex microsphere first, there is larger specific area, good dispersiveness and tiny nano level active component CuBTC shell, this composite have that catalytic activity is high, specific area is large, active component CuBTC good dispersion and its particle diameter and the advantage such as shell thickness is adjustable.In addition, this preparation method is simple, reaction condition is gentle, energy consumption is less, is suitable for amplifying producing and applying.
Description
Technical field
The present invention relates to polystyrene-based CuBTC composite catalyst of a kind of dumb-bell shape and preparation method thereof, belong to compound catalyze material preparing technical field.
Background technology
Metal-organic framework materials (Metal-organicframeworks, MOFs) be a kind of there is bigger serface, high porosity, chemistry can modify and the novel porous materials of structure Diversity, they have broad application prospects in the field such as atmosphere storage, adsorbing separation.Especially, the advantages such as the diversity of the crystallinity of the height that MOFs material itself has, uniform catalytic center and skeleton structure and function are that other catalyst do not possess, so itself or a kind of heterogeneous catalysis material had a great attraction.In known MOFs material, CuBTC (BTC is trimesic acid) has the string bag structure of the pore passage structure of three-dimensional orthogonal and the open in the face of duct of uniqueness, larger specific area and pore volume, also has undersaturated metal active centres, in many catalytic reaction processes, illustrate excellent catalytic performance, cause the extensive research of scientific worker.
In general, compared to block materials, nano material often shows higher catalytic activity and better selective owing to having the special performances such as skin effect, small-size effect, macro quanta tunnel effect and quantum confined effect.The CuBTC of the method synthesis that current employing is fairly simple is usually at micron order, and wanting to obtain nanoscale CuBTC then will by the more complicated such as template, harshness and the course of reaction consumed energy.
Polystyrene (PS) microballoon is a kind of extraordinary organic carrier, advantages such as having good dispersion, surface is easy to functionalization, synthesis technique is simple, be with low cost.And there is the PS microballoon of special dumbbell shape pattern, its specific area is larger, after sulfonation process is carried out on its surface, is more suitable for the further load active component of carrier material as catalyst.
Therefore, how effectively to utilize the excellent properties of this good carrier of dumb-bell shape polystyrene microsphere, the nanoscale CuBTC adopting fairly simple and method that is low energy consumption to obtain more small scale will have very important significance.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of special appearance Polymers CuBTC composite catalyst and preparation method thereof, its carrier is dumb-bell shape polystyrene (PS) microballoon of sulfonation, surface is by the coated tiny nano level metal organic framework compounds CuBTC of method of layer assembly, form dumb-bell shape catalyst with core-casing structure PSCuBTC, there is the application of the oxidation reaction of catalysis acetalation and alcohol.
For achieving the above object, the invention provides the preparation method of the polystyrene-based CuBTC composite catalyst of a kind of dumb-bell shape, it comprises with the dumb-bell shape polystyrene microsphere through oversulfonate process for carrier, repeated loading mantoquita and trimesic acid, prepare the step of the polystyrene-based CuBTC composite catalyst of dumb-bell shape.
Above-mentioned dumb-bell shape polystyrene microsphere can conventionally prepare, and its grain size is micron-sized, and longitudinal size (or claiming longitudinal diameter) is at 4-7 μm, and lateral dimension (or claiming trans D) is at 3-5 μm.
According to specific embodiment of the invention scheme, preferably, said method comprises the following steps:
Step one: dumb-bell shape polystyrene microsphere is distributed among the concentrated sulfuric acid and obtains sulfonating reaction mixture, in this sulfonating reaction mixture, the concentration of polystyrene microsphere is 0.1-10wt.%, sulfonating reaction 1-24h is carried out under 15-50 DEG C and stirring condition, be separated, then with deionized water and ethanol washing, sulfonated polystyrene microballoon after drying, is obtained;
Step 2: sulfonated polystyrene microballoon is distributed in the ethanolic solution of appropriate mantoquita, leave standstill reaction 5-30min, centrifugation, with ethanol washing 2-5 time, then adds the ethanolic solution of appropriate trimesic acid, reaction 10-60min, then centrifugation, with ethanol washing 2-5 time, obtains solid product, wherein, the mass ratio of sulfonated polystyrene microballoon, mantoquita, trimesic acid is 25-500:1:1-3;
Step 3: repeat step 2 to the solid product obtained in step 2, carries out repeated loading, obtains the polystyrene-based CuBTC composite catalyst of described dumb-bell shape.
In the above-mentioned methods, preferably, the number of times of the repeated loading in step 3 is 10-60 time.
In the above-mentioned methods, preferably, the mantoquita in step 2 is the soluble inorganic salt of copper; More preferably, described mantoquita comprises the combination of one or more in Schweinfurt green, copper nitrate, copper sulphate and basic copper sulfate etc.
In the above-mentioned methods, preferably, in step 2, the concentration of the ethanolic solution of mantoquita is 1-15mmol/L; More preferably, the ethanolic solution of this mantoquita is prepared with absolute ethyl alcohol.
In the above-mentioned methods, preferably, in step 2, the concentration of the ethanolic solution of trimesic acid is 1-10mmol/L; More preferably, the ethanolic solution of this trimesic acid is prepared with absolute ethyl alcohol.
In the above-mentioned methods, preferably, in step one, the concentration of the concentrated sulfuric acid is 70-98wt.%.
According to specific embodiment of the invention scheme, preferably, above-mentioned preparation method can comprise following concrete steps:
Step 1: take a certain amount of dumb-bell shape PS microballoon and be distributed to and fill in the there-necked flask of the concentrated sulfuric acid, PS microballoon concentration is 0.1-10wt.%, sulfonating reaction 1-24h under 15-50 DEG C of stirring condition, centrifugal means are adopted to be separated, then with deionized water and ethanol washing, sulfonated polystyrene microballoon after drying, is obtained;
Step 2: taking the concentration that the sulfonation PS microballoon prepared in a certain amount of step 1 is distributed to certain volume is in the ethanolic solution of the mantoquita of 1-15mmol/L, reaction 5-30mim is left standstill after being uniformly dispersed, centrifugation, with ethanol washing 2-5 time, then the ethanolic solution of the trimesic acid of the 1-10mmol/L of certain volume is added, 10-60min is reacted after being uniformly dispersed, then centrifugation, with ethanol washing 2-5 time, the mass ratio of sulfonation PS microballoon and mantoquita and trimesic acid is 25-500:1:1-3;
Step 3: by the solid product of washes clean in step 2, adds the ethanolic solution of mantoquita and the ethanolic solution of trimesic acid successively according to the addition of step 2 and reaction condition, carries out repeated loading, obtain the polystyrene-based CuBTC composite catalyst of dumb-bell shape.
Above-mentioned preparation method provided by the present invention prepares dumb-bell shape PS microballoon by dispersin polymerization in conjunction with the method for seed swelling, then the sulfonation PS microballoon that sulfonation process obtains surface modification is carried out to it, the sulfonic group of microsphere surface can adsorb the copper ion in soluble copper salting liquid effectively, and then forms the nanoscale organometallic skeletal compound-material CuBTC of more small scale further with trimesic acid coordination.By the number of times of adjustment mantoquita and the concentration of organic ligand trimesic acid, addition and load, particle diameter and the shell thickness of CuBTC effectively can be regulated.
Present invention also offers the polystyrene-based CuBTC composite catalyst of a kind of dumb-bell shape, it is prepared by above-mentioned preparation method.Preferably, the longitudinal size (or claiming longitudinal diameter) of this dumb-bell shape polystyrene-based CuBTC composite catalyst is 4-12 μm, and lateral dimension (or claiming trans D) is 3-10 μm, and shell thickness is 0.5-5 μm.
Above-mentioned composite catalyst provided by the present invention (special appearance Polymers CuBTC composite catalyst) may be used for the course of reaction such as oxidation, acetalation of catalytic alcohol, and the quick recovery of catalyst is realized by centrifugation, reach good and recycle effect.
Present invention also offers the application of the polystyrene-based CuBTC composite catalyst of above-mentioned dumb-bell shape in the oxidation reaction of catalytic alcohol; Preferably, the condition of the oxidation reaction of alcohol is: the consumption of the polystyrene-based CuBTC composite catalyst of dumb-bell shape is 30-150mg, 2,2, the consumption of 6,6-tetramethyl piperidine-1-oxygen radical is 0.2-2mmol, and the consumption of acetonitrile is 2-10mL, the consumption of phenmethylol is 1-5mmol, and reaction temperature is 60-80 DEG C.
Present invention also offers the application of the polystyrene-based CuBTC composite catalyst of above-mentioned dumb-bell shape in catalysis acetalation; Preferably, the condition of acetalation is: the consumption of the polystyrene-based CuBTC composite catalyst of dumb-bell shape is 20-100mg, and the consumption of ethanol is 3-20mL, and the consumption of benzaldehyde is 1-5mmol, and the consumption of nitrobenzene is 1-5mmol, and reaction temperature is 20-60 DEG C.
Dumb-bell shape polystyrene (PS) microballoon that the preparation method of the polystyrene-based CuBTC composite catalyst of dumb-bell shape provided by the invention adopts can be prepared by the method for dispersin polymerization in conjunction with seed swelling, first sulfonation modifying process is carried out to microsphere surface, then by the coated tiny nano level metal organic framework compounds CuBTC of method of layer assembly, dumb-bell shape catalyst with core-casing structure PSCuBTC is formed.
The present invention successfully synthesizes dumb-bell shape PSCuBTC complex microsphere first, there is larger specific area, good dispersiveness and tiny nano level active component CuBTC shell, this composite have that catalytic activity is high, specific area is large, active component CuBTC good dispersion and its particle diameter and the advantage such as shell thickness is adjustable.
In addition, preparation method provided by the present invention is fairly simple, reaction condition is gentle, energy consumption is less, is suitable for amplifying producing and applying.
The PSCuBTC complex microsphere of special appearance is applied to different catalytic reaction processes by the present invention first, and catalytic performance is excellent.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the dumb-bell shape PS microballoon without sulfonation process prepared by embodiment 1.
Fig. 2 is the stereoscan photograph of the dumb-bell shape nucleocapsid structure PSCuBTC composite catalyst of the small nanocrystal of area load CuBTC prepared by embodiment 1.
Detailed description of the invention
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide the polystyrene-based CuBTC composite catalyst of a kind of dumb-bell shape, it is prepared by following steps:
Step 1: take a certain amount of dumb-bell shape PS microballoon (its stereoscan photograph as shown in Figure 1) and be distributed in the there-necked flask filling the concentrated sulfuric acid (concentration is 98wt%), obtain sulfonating reaction mixture, in the mixture, the concentration of PS microballoon is 1wt.%, sulfonating reaction 12h under 20 DEG C and stirring condition, adopt centrifugal means to be separated, then with deionized water and ethanol washing, after drying, obtain dumb-bell shape sulfonated polystyrene microballoon;
Step 2: taking the concentration that the dumb-bell shape sulfonation PS microballoon prepared in a certain amount of step 1 is distributed to certain volume is in the ethanolic solution of the Schweinfurt green of 2mmol/L, reaction 10min is left standstill after being uniformly dispersed, centrifugation, 3 times are washed with ethanol, then the concentration adding certain volume is the ethanolic solution of the trimesic acid of 2mmol/L, 20min is reacted after being uniformly dispersed, then centrifugation, obtain solid product, 3 times are washed with ethanol, wherein, the mass ratio of sulfonation PS microballoon, Schweinfurt green and trimesic acid is 100:1:1;
Step 3: by the solid product of washes clean in step 2, the ethanolic solution of Schweinfurt green and the ethanolic solution of trimesic acid is added successively according to the addition of step 2 and reaction condition, repeated loading 20 times, obtain the polystyrene-based CuBTC composite catalyst of dumb-bell shape, the stereoscan photograph of this composite catalyst as shown in Figure 2, particle size is: longitudinal diameter is 6.5 μm, and trans D is 4.4 μm, and shell thickness is 1.3 μm.
Catalytic applications: the oxidation reaction this composite catalyst being used for phenmethylol, reaction condition is: catalyst 50mg, 2,2,6,6-tetramethyl piperidine-1-oxygen radical (TEMPO) 0.5mmol, acetonitrile 5mL, phenmethylol 1mmol, 75 DEG C, reaction 12h, the conversion ratio of phenmethylol and the selective of benzaldehyde are all 100%.
Embodiment 2
Present embodiments provide the polystyrene-based CuBTC composite catalyst of a kind of dumb-bell shape, it is prepared by following steps:
Step 1: take a certain amount of dumb-bell shape PS microballoon and be distributed in the there-necked flask filling the concentrated sulfuric acid (concentration is 98wt%), obtain sulfonating reaction mixture, in the mixture, PS microballoon concentration is 3wt.%, sulfonating reaction 6h under 40 DEG C and stirring condition, adopt centrifugal means to be separated, then with deionized water and ethanol washing, after drying, obtain dumb-bell shape sulfonated polystyrene microballoon;
Step 2: taking the concentration that the dumb-bell shape sulfonation PS microballoon prepared in a certain amount of step 1 is distributed to certain volume is in the ethanolic solution of the copper nitrate of 4mmol/L, reaction 15min is left standstill after being uniformly dispersed, centrifugation, 3 times are washed with ethanol, then the concentration adding certain volume is the ethanolic solution of the trimesic acid of 4mmol/L, 30min is reacted after being uniformly dispersed, then centrifugation, obtain solid product, 3 times are washed with ethanol, wherein, the mass ratio of sulfonation PS microballoon, copper nitrate and trimesic acid is 50:1:1;
Step 3: by the solid product of washes clean in step 2, the ethanolic solution of copper nitrate and the ethanolic solution of trimesic acid is added successively according to the addition of step 2 and reaction condition, repeated loading 30 times, obtain the polystyrene-based CuBTC composite catalyst of dumb-bell shape, particle size is: longitudinal diameter is 7.2 μm, trans D is 5.1 μm, and shell thickness is 2 μm.
Catalytic applications: the oxidation reaction this catalyst being used for phenmethylol, reaction condition is: catalyst 40mg, 2,2,6,6-tetramethyl piperidine-1-oxygen radical (TEMPO) 1mmol, acetonitrile 5mL, phenmethylol 2mmol, 70 DEG C, reaction 13h, the conversion ratio of phenmethylol and the selective of benzaldehyde are all 100%.
Embodiment 3
Present embodiments provide the polystyrene-based CuBTC composite catalyst of a kind of dumb-bell shape, it is prepared by following steps:
Step 1: take a certain amount of dumb-bell shape PS microballoon and be distributed in the there-necked flask filling the concentrated sulfuric acid (concentration is 98wt%), obtain sulfonating reaction mixture, in the mixture, PS microballoon concentration is 10wt.%, sulfonating reaction 2h under 50 DEG C and stirring condition, adopt centrifugal means to be separated, then with deionized water and ethanol washing, after drying, obtain dumb-bell shape sulfonated polystyrene microballoon;
Step 2: taking the concentration that the dumb-bell shape sulfonation PS microballoon prepared in a certain amount of step 1 is distributed to certain volume is in the ethanolic solution of the basic copper sulfate of 5mmol/L, reaction 10min is left standstill after being uniformly dispersed, centrifugation, 3 times are washed with ethanol, then the concentration adding certain volume is the ethanolic solution of the trimesic acid of 5mmol/L, 20min is reacted after being uniformly dispersed, then centrifugation, obtain solid product, 3 times are washed with ethanol, wherein, the mass ratio of sulfonation PS microballoon, basic copper sulfate and trimesic acid is 200:1:1;
Step 3: by the solid product of washes clean in step 2, the ethanolic solution of copper sulphate and the ethanolic solution of trimesic acid is added successively according to the addition of step 2 and reaction condition, repeated loading 25 times, obtain the polystyrene-based CuBTC composite catalyst of dumb-bell shape, particle size is: longitudinal diameter is 8.9 μm, trans D is 6.7 μm, and shell thickness is 3.6 μm.
Catalytic applications: this catalyst is used for acetalation, reaction condition is: catalyst 30mg, ethanol 5mL, benzaldehyde 1mmol, nitrobenzene 1mmol, 25 DEG C, and reaction 6h, the conversion ratio of benzaldehyde is 71%, and the selective of benzaldehyde diethyl acetal is 100%.
Embodiment 4
Present embodiments provide the polystyrene-based CuBTC composite catalyst of a kind of dumb-bell shape, it is prepared by following steps:
Step 1: take a certain amount of dumb-bell shape PS microballoon and be distributed in the there-necked flask filling the concentrated sulfuric acid (concentration is 98wt%), obtain sulfonating reaction mixture, in the mixture, PS microballoon concentration is 6wt.%, sulfonating reaction 24h under 25 DEG C and stirring condition, adopt centrifugal means to be separated, then with deionized water and ethanol washing, after drying, obtain dumb-bell shape sulfonated polystyrene microballoon;
Step 2: taking the concentration that the dumb-bell shape sulfonation PS microballoon prepared in a certain amount of step 1 is distributed to certain volume is in the ethanolic solution of the Schweinfurt green of 3mmol/L, reaction 30min is left standstill after being uniformly dispersed, centrifugation, 4 times are washed with ethanol, then the concentration adding certain volume is the ethanolic solution of the trimesic acid of 3mmol/L, 50min is reacted after being uniformly dispersed, then centrifugation, obtain solid product, 4 times are washed with ethanol, wherein, the mass ratio of sulfonation PS microballoon, Schweinfurt green and trimesic acid is 150:1:1;
Step 3: by the solid product of washes clean in step 2, the ethanolic solution of Schweinfurt green and the ethanolic solution of trimesic acid is added successively according to the addition of step 2 and reaction condition, repeated loading 40 times, obtain the polystyrene-based CuBTC composite catalyst of dumb-bell shape, particle size is: longitudinal diameter is 7.6 μm, trans D is 5.5 μm, and shell thickness is 2.4 μm.
Catalytic applications: this catalyst is used for acetalation, reaction condition is: catalyst 50mg, ethanol 5mL, benzaldehyde 1mmol, nitrobenzene 1mmol, 40 DEG C, and reaction 3h, the conversion ratio of benzaldehyde is 83%, and the selective of benzaldehyde diethyl acetal is 100%.
Embodiment 5
Present embodiments provide the polystyrene-based CuBTC composite catalyst of a kind of dumb-bell shape, it is prepared by following steps:
Step 1: take a certain amount of dumb-bell shape PS microballoon and be distributed in the there-necked flask filling the concentrated sulfuric acid (concentration is 98wt%), obtain sulfonating reaction mixture, in the mixture, PS microballoon concentration is 0.5wt.%, sulfonating reaction 10h under 30 DEG C of stirring conditions, adopt centrifugal means to be separated, then with deionized water and ethanol washing, after drying, obtain dumb-bell shape sulfonated polystyrene microballoon;
Step 2: taking the concentration that the dumb-bell shape sulfonation PS microballoon prepared in a certain amount of step 1 is distributed to certain volume is in the ethanolic solution of the copper nitrate of 8mmol/L, reaction 20min is left standstill after being uniformly dispersed, centrifugation, 2 times are washed with ethanol, then the concentration adding certain volume is the ethanolic solution of the trimesic acid of 8mmol/L, 40min is reacted after being uniformly dispersed, then centrifugation, obtain solid product, 2 times are washed with ethanol, wherein, the mass ratio of sulfonation PS microballoon, copper nitrate and trimesic acid is 500:1:1;
Step 3: by the solid product of washes clean in step 2, the ethanolic solution of copper nitrate and the ethanolic solution of trimesic acid is added successively according to the addition of step 2 and reaction condition, repeated loading 50 times, obtain the polystyrene-based CuBTC composite catalyst of dumb-bell shape, particle size is: longitudinal diameter is 8.9 μm, trans D is 6.8 μm, and shell thickness is 3.7 μm.
Catalytic applications: this catalyst is used for acetalation, reaction condition is: catalyst 80mg, ethanol 5mL, benzaldehyde 1mmol, nitrobenzene 1mmol, 60 DEG C, and reaction 3h, the conversion ratio of benzaldehyde is 87%, and the selective of benzaldehyde diethyl acetal is 100%.
Claims (10)
1. the preparation method of the polystyrene-based CuBTC composite catalyst of dumb-bell shape, it comprises with the dumb-bell shape polystyrene microsphere through oversulfonate process for carrier, repeated loading mantoquita and trimesic acid, prepare the step of the polystyrene-based CuBTC composite catalyst of dumb-bell shape.
2. method according to claim 1, it comprises the following steps:
Step one: dumb-bell shape polystyrene microsphere is distributed among the concentrated sulfuric acid and obtains sulfonating reaction mixture, in this sulfonating reaction mixture, the concentration of polystyrene microsphere is 0.1-10wt.%, sulfonating reaction 1-24h is carried out under 15-50 DEG C and stirring condition, be separated, then with deionized water and ethanol washing, sulfonated polystyrene microballoon after drying, is obtained;
Step 2: sulfonated polystyrene microballoon is distributed in the ethanolic solution of appropriate mantoquita, leave standstill reaction 5-30min, centrifugation, with ethanol washing 2-5 time, then adds the ethanolic solution of appropriate trimesic acid, reaction 10-60min, then centrifugation, with ethanol washing 2-5 time, obtains solid product, wherein, the mass ratio of sulfonated polystyrene microballoon, mantoquita, trimesic acid is 25-500:1:1-3;
Step 3: repeat step 2 to the solid product that step 2 obtains, carries out repeated loading, obtains the polystyrene-based CuBTC composite catalyst of described dumb-bell shape.
3. method according to claim 2, wherein, the number of times of repeated loading in described step 3 is 10-60 time.
4. method according to claim 2, wherein, the mantoquita in described step 2 is the soluble inorganic salt of copper, and preferably, described mantoquita comprises the combination of one or more in Schweinfurt green, copper nitrate, copper sulphate and basic copper sulfate.
5. method according to claim 2, wherein, the concentration of the ethanolic solution of described mantoquita is 1-15mmol/L; Preferably, the ethanolic solution of described mantoquita is prepared with absolute ethyl alcohol.
6. method according to claim 2, wherein, the concentration of the ethanolic solution of described trimesic acid is 1-10mmol/L; Preferably, the ethanolic solution of described trimesic acid is prepared with absolute ethyl alcohol.
7. method according to claim 2, wherein, the concentration of the described concentrated sulfuric acid is 70-98wt.%.
8. the polystyrene-based CuBTC composite catalyst of dumb-bell shape, it is prepared by the preparation method described in any one of claim 1-7; Preferably, the longitudinal size of the polystyrene-based CuBTC composite catalyst of this dumb-bell shape is 4-12 μm, and lateral dimension is 3-10 μm, and shell thickness is 0.5-5 μm.
9. the application of the polystyrene-based CuBTC composite catalyst of dumb-bell shape according to claim 8 in the oxidation reaction of catalytic alcohol; Preferably, the condition of the oxidation reaction of described alcohol is: the consumption of the polystyrene-based CuBTC composite catalyst of dumb-bell shape is 30-150mg, 2,2, the consumption of 6,6-tetramethyl piperidine-1-oxygen radical is 0.2-2mmol, and the consumption of acetonitrile is 2-10mL, the consumption of phenmethylol is 1-5mmol, and reaction temperature is 60-80 DEG C.
10. the application of the polystyrene-based CuBTC composite catalyst of dumb-bell shape according to claim 8 in catalysis acetalation; Preferably, the condition of described acetalation is: the consumption of the polystyrene-based CuBTC composite catalyst of dumb-bell shape is 20-100mg, and the consumption of ethanol is 3-20mL, and the consumption of benzaldehyde is 1-5mmol, the consumption of nitrobenzene is 1-5mmol, and reaction temperature is 20-60 DEG C.
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