CN103819598A - Nanometer porous and super-hydrophobic skeleton strong solid acid material and preparing method thereof - Google Patents
Nanometer porous and super-hydrophobic skeleton strong solid acid material and preparing method thereof Download PDFInfo
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Abstract
The invention provides a nanometer porous and super-hydrophobic skeleton strong solid acid material and a preparing method thereof. The preparing method comprises the following steps: a, polymerizing divinyl benzene under a solvothermal condition, wherein benzoyl peroxide is used as an initiator, polymerizing is carried out at a temperature between 80DEG C and 180DEG C for 12-48h, 7-25mL of corresponding solvent is used each time when 2g of divinyl benzene monomer is used, and the mass ratio of the initiator to the divinyl benzene is 0.015-0.0375; b, adding a solvent to the nanometer porous polydivinyl benzene material which is prepared in the step a, and adding a sulfonating agent to carry out sulfonating, wherein carbon tetrachloride or methylbenzene is used as the solvent, trifluoromethane sulfonic acid or fluorosulfuric acid is used as the sulfonating agent, the volume ratio of the solvent to the sulfonating agent is 10:1, the mass ratio of the PDVB (Polydivinyl Benzene) to the sulfonating agent is (5-10):1, and sulfonating is carried out in a range between 80DEG C and 110DEG C for 12-36h.
Description
Technical field
The invention belongs to the technical field of physical chemistry, materials chemistry, relate in particular to a kind of nanoporous, super-hydrophobic skeleton solid strong acid material and preparation method thereof.
Background technology
Acid catalysis is the very important reaction type of catalytic field, especially play a part very important in petrochemical complex and field of fine chemical, and of paramount importance task is to utilize efficient solid acid to substitute traditional liquid acid in acid catalysis field, and then realize the low cost of product, green preparation.Traditional solid acid catalyst has zeolite molecular sieve, metal sulphide oxide compound, and the mesoporous material of acid functionalization, heteropolyacid etc., but its shortcoming is as hydrophilic skeleton structure, lower specific surface area; Zeolitic material is the acid catalyst of the industrial widespread use of a class, applies more widely but its limited aperture etc. have affected it.
Compared with the acid catalyst of traditional inorganic skeleton, the solid-acid material of organic backbone is with its unique skeleton hydrophilicity and hydrophobicity, simply and easily functionalization process, preferably catalytic performance and be subject to studying more and more widely, and the most representative in this class material be storng-acid cation exchange resin as Amberlyst15, Amberlyst35 etc., but its low specific surface area, weak acid site (H
0=-2.2), deficient pore structure and poor skeleton stability and hydrophobicity have affected its widespread use.
The method of the solid acid catalyst of conventionally synthetic organic backbone is the method by sulfonation, but after sulfonation, the specific surface area of material material is very low, pore structure scarcity, and skeleton wetting ability strengthens, and has limited it and has applied widely.。And novel sulfate resin (FDU-14-SO
3h etc.) solve the adverse influence of low specific surface area to catalyzed reaction, but expensive, the skeleton structure of wetting ability and less stable, relatively weak strength of acid can limit it and applies widely.
Summary of the invention
The present invention, in order to overcome the shortcoming of above-mentioned organic backbone solid acid catalyst material, provides a kind of nanoporous, super-hydrophobic skeleton solid strong acid material and preparation method thereof.
In order to realize an object of the present invention, the invention provides the preparation method of a kind of nanoporous, super-hydrophobic skeleton solid strong acid material, comprise the following steps: a. carries out Vinylstyrene polymerization under solvent thermal condition, wherein, benzoyl peroxide is initiator, and polymerization temperature is within the scope of 80-180 ℃, and the usage quantity of the corresponding solvent of every use 2g divinyl benzene monomer is within the scope of 7-25mL, the mass ratio of initiator and Vinylstyrene is 0.015-0.0375, and polymerization time is 12-48h; B. the nanoporous polydivinylbenezene material of preparing in step a, add solvent, add sulfonated reagent to carry out sulfonation, wherein, solvent is tetracol phenixin or toluene, and sulfonated reagent is trifluoromethanesulfonic acid or fluosulfonic acid, the volume ratio of solvent and sulfonated reagent is 10:1, the mass ratio of nanoporous polydivinylbenezene material and sulfonated reagent is 5-10:1, and sulfonation temperature is within the scope of 80-110 ℃, and the sulfonation time is 12h-36h.
In one embodiment of the invention, the solvent using in step a is mixed solvent, ethyl acetate, toluene, ethanol, benzene or the acetone of tetrahydrofuran (THF), tetrahydrofuran (THF) and water composition.
In one embodiment of the invention, preparation method also comprises after step a: the nanoporous polydivinylbenezene material of preparing in step a is ground to form to ultrafine powder, degassed processing 10h under 150 ℃ of condition of nitrogen gas.
In one embodiment of the invention, preparation method also comprises after step b: the product of preparing in step b is removed to unreacted sulfonated reagent with washing with acetone, and 80 ℃ dry.
In order to realize another object of the present invention, the present invention also provides a kind of nanoporous, super-hydrophobic skeleton solid strong acid material, take polydivinylbenezene as skeleton, has trifluoromethanesulfonic acid sulfonic acid or fluosulfonic acid group, and aperture is 4-30nm, and specific surface area is 500-700m
2/ g.
In sum, the present invention is by the nanoporous polydivinylbenezene material of the synthetic bigger serface of solvent thermal technology, and this material improves than degree of crosslinking greatly with traditional resin-phase, and then the stability of material also improves greatly.Utilize trifluoromethanesulfonic acid or fluosulfonic acid to carry out sulfonation to this material, can realize the preparation of novel organic backbone solid strong acid material.It is worth mentioning that material has shown excellent swelling behavior in organic solvent, and then make its first swelling rear sulfonation in sulfonation process, when making material keep high stability again, sulfonation is more abundant, has greatly increased the content of sulfonate radical and the degrees of exposure in active centre in sulfonated products.This bill of material has revealed skeleton feature super-hydrophobic, super oleophylic simultaneously, has greatly overcome the defect of traditional organic backbone solid acid catalyst material.In addition, the introducing of trifluoromethanesulfonic acid can improve the acidity (H of material greatly
0<-11.99).These characteristics makes novel solid strong acid prepared by the present invention in the reaction such as catalyzing acyl, esterification, show excellent catalytic performance; be better than conventional solid acid catalyst material as Amberlyst-15 resin, the mesoporous SBA-15 of h-type zeolite and sulfonate radical functionalization etc.
For above and other objects of the present invention, feature and advantage can be become apparent, preferred embodiment cited below particularly, and coordinate accompanying drawing, be described in detail below.
Accompanying drawing explanation
Figure 1A is the nitrogen adsorption isotherm comparison diagram before and after the mesoporous polydivinylbenezene sulfonation prepared of the present invention.
Figure 1B is the pore size distribution curve before and after the mesoporous polydivinylbenezene sulfonation prepared of the present invention.
Fig. 2 is the infrared spectrum of material before and after the mesoporous polydivinylbenezene sulfonation prepared of the present invention.
Fig. 3 is PDVB-SO
2cF
3to the contact angle test pattern of water.
Fig. 4 A is PDVB-SO
2cF
3liquid absorption-oil absorptiveness figure.
Fig. 4 B is PDVB-SO
2cF
3gaseous state absorption-water absorbing properties test pattern.
Fig. 5 is the TG spectrogram of different samples.
Embodiment
The invention provides the preparation method of a kind of nanoporous, super-hydrophobic skeleton solid strong acid material, comprise the following steps: a. carries out Vinylstyrene polymerization under solvent thermal condition, wherein, benzoyl peroxide is initiator, polymerization temperature is within the scope of 80-180 ℃, the usage quantity of the corresponding solvent of every use 2g divinyl benzene monomer is within the scope of 7-25mL, and the mass ratio of initiator and Vinylstyrene is 0.015-0.0375, and polymerization time is 12-48h; B. the nanoporous polydivinylbenezene material of preparing in step a, add solvent, add sulfonated reagent to carry out sulfonation, wherein, solvent is tetracol phenixin or toluene, and sulfonated reagent is trifluoromethanesulfonic acid or fluosulfonic acid, the volume ratio of solvent and sulfonated reagent is 10:1, the mass ratio of nanoporous polydivinylbenezene material and sulfonated reagent is 5-10:1, and sulfonation temperature is within the scope of 80-110 ℃, and the sulfonation time is 12h-36h.
Below enumerate the implementation procedure that multiple specific embodiments carry out description of step a.
Embodiment 1: the mixed solvent with tetrahydrofuran (THF) and water composition carrys out synthesising mesoporous polydivinylbenezene material.
By 2g DVB(Vinylstyrene) monomer joins containing in 0.05g benzoyl peroxide initiator and 23mL tetrahydrofuran (THF) and 2mL water mixed solvent, under normal temperature and pressure, stir after 3 hours, 80 ℃ of solvent heat treatment are taken out for 1 day afterwards, uncap, the room temperature dry solvent that volatilizees, can obtain high-specific surface area, enrich the polydivinylbenezene material of meso-hole structure.
Embodiment 2: take tetrahydrofuran (THF) as the synthesising mesoporous polydivinylbenezene material of solvent.
2g DVB monomer is joined containing in 0.05g benzoyl peroxide and 25mL tetrahydrofuran solvent, under normal temperature and pressure, stir after 1 hour, after 100 ℃ of solvent heat treatment 12h, take out, uncap, the room temperature dry solvent that volatilizees, can obtain high-specific surface area, enriches the polydivinylbenezene material of meso-hole structure.The specific surface area of the material obtaining is 550m
2/ g, aperture is 3.7 nanometers.
Embodiment 3: take toluene as the synthesising mesoporous polydivinylbenezene material of solvent.
2g DVB monomer is joined containing in 0.05g benzoyl peroxide and 7mL toluene solvant, under normal temperature and pressure, stir after 1 hour, after 140 ℃ of solvent heat treatment 48h, take out, uncap, the room temperature dry solvent that volatilizees, can obtain high-specific surface area, enriches the polydivinylbenezene material of meso-hole structure.
Embodiment 4: take benzene as the synthesising mesoporous polydivinylbenezene material of solvent.
2g DVB monomer is joined containing in 0.03g benzoyl peroxide and 15mL benzene solvent, stir after 1 hour under normal temperature and pressure, 180 ℃ of solvent heat treatment are taken out for 1 day afterwards, uncap, the room temperature dry solvent that volatilizees, can obtain high-specific surface area, enriches the polydivinylbenezene material of meso-hole structure.
Embodiment 5: take ethyl acetate as the synthesising mesoporous polydivinylbenezene material of solvent.
2g DVB monomer is joined containing in 0.075g benzoyl peroxide and 25mL ethyl acetate solvent, stir after 1 hour under normal temperature and pressure, 140 ℃ of solvent heat treatment are taken out for 1 day afterwards, uncap, the room temperature dry solvent that volatilizees, can obtain high-specific surface area, enriches the polydivinylbenezene material of meso-hole structure.
Embodiment 6: take ethanol as the synthesising mesoporous polydivinylbenezene material of solvent.
2g DVB monomer is joined containing in 0.05g benzoyl peroxide and 20mL alcohol solvent, stir after 1 hour under normal temperature and pressure, 160 ℃ of solvent heat treatment are taken out for 1 day afterwards, uncap, the room temperature dry solvent that volatilizees, can obtain high-specific surface area, enriches the polydivinylbenezene material of meso-hole structure.
Embodiment 7: take acetone as the synthesising mesoporous polydivinylbenezene material of solvent.
2g DVB monomer is joined containing in 0.04g benzoyl peroxide and 18mL acetone solvent, stir after 1 hour under normal temperature and pressure, 90 ℃ of solvent heat treatment are taken out for 1 day afterwards, uncap, the room temperature dry solvent that volatilizees, can obtain high-specific surface area, enriches the polydivinylbenezene material of meso-hole structure.
Below enumerate the implementation procedure that multiple specific embodiments carry out description of step b.PDVB represents mesoporous polydivinylbenezene.
Embodiment 8: selection tetracol phenixin is solvent, trifluoromethanesulfonic acid is that sulfonated reagent carries out sulfonation reaction.
By 2g PDVB(tetrahydrofuran (THF) and water mixed solvent preparation) grind to form ultrafine powder, degassed processing 10h under 150 ℃ of condition of nitrogen gas; Get 50mL tetracol phenixin, after 5mL trifluoromethanesulfonic acid mixes and stirs, add above-mentioned PDVB, strong stirring, temperature is elevated to 90 ℃ of sulfonation 24h, finishes reaction, and product filters, and a large amount of washing with acetones are removed unreacted trifluoromethanesulfonic acid, and 80 ℃ are dry.The material specific surface area obtaining is 700m
2/ g, aperture is 30 nanometers.
Embodiment 9: selection tetracol phenixin is solvent, trifluoromethanesulfonic acid is that sulfonated reagent carries out sulfonation reaction.
By 2g PDVB(tetrahydrofuran (THF) and water mixed solvent preparation) grind to form ultrafine powder, degassed processing 10h under 150 ℃ of condition of nitrogen gas; Get 50mL tetracol phenixin, after 5mL trifluoromethanesulfonic acid mixes and stirs, add above-mentioned PDVB, strong stirring, temperature is elevated to 80 ℃ of sulfonation 12h, finishes reaction, and product filters, and a large amount of washing with acetones are removed unreacted trifluoromethanesulfonic acid, and 80 ℃ are dry.The material specific surface area obtaining is 660m
2/ g, aperture is 21.6 nanometers.
Embodiment 10: selection toluene is solvent, trifluoromethanesulfonic acid is that sulfonated reagent carries out sulfonation reaction.
Be solvent preparation by 2g PDVB(tetrahydrofuran (THF)) grind to form ultrafine powder, degassed processing 10h under 150 ℃ of condition of nitrogen gas; Get 50mL toluene, after 5mL trifluoromethanesulfonic acid mixes and stirs, add above-mentioned PDVB, strong stirring, temperature is elevated to 110 ℃ of sulfonation 12h, finishes reaction, and product filters, and a large amount of washing with acetones are removed unreacted trifluoromethanesulfonic acid, and 80 ℃ are dry.The material specific surface area obtaining is 500m
2/ g, aperture is 4 nanometers.
Embodiment 11: selection toluene is solvent, fluosulfonic acid is that sulfonated reagent carries out sulfonation reaction.
Be solvent preparation by 2g PDVB(ethyl acetate) grind to form ultrafine powder, degassed processing 10h under 150 ℃ of condition of nitrogen gas; Get 50mL toluene, after 5mL fluosulfonic acid mixes and stirs, add above-mentioned PDVB, strong stirring, temperature is elevated to 100 ℃ of sulfonation 36h, finishes reaction, and product filters, and a large amount of washing with acetones are removed unreacted fluosulfonic acid, and 80 ℃ are dry.
Table 1:PDVB-SO
2cF
3(the mesoporous polydivinylbenezene material after sulfonate radical functionalization) contrasts with the structural parameter of common solid acid catalyst material.
ameasure by ultimate analysis
bmeasure by acid base titration
cadopt Barrett-Joyner-Halenda(BJH) model determination pore size distribution
The mesoporous polydivinylbenezene of trifluoromethanesulfonic acid functionalization of the present invention has highly acid active centre (H compared with storng-acid cation exchange resin (Amberlyst15)
0, and Amberl <-11.99)
yst15 is (H
0=-2.2).
Table 2 is PDVB-SO
2cF
3catalytic activity data in esterification and acylation reaction and with other traditional catalyst as Amberlyst15, SBA-15-SO
2cF
3and zeolitic material contrast.
athis sample has been recycled 5 times
bstirring velocity is approximately 60rpm.
cthe SBA-15-SO of 0.4g
2cF
3catalyzer
Listed reaction conditions in table 2: the esterification condition of acetic acid and hexalin: 0.2g catalyzer, 11.5mL hexalin, 17.5mL Glacial acetic acid mixes rear 100 ℃ of reaction 5h to be finished, and dodecane is interior mark.
Benzene and Benzoyl chloride acylation reaction condition: 0.2g catalyzer, 51.6mmol benzene, 80 ℃ of reaction 10h of 8.6mmol Benzoyl chloride finish, and dodecane is interior mark.
Toluene and Benzoyl chloride acylation reaction condition: 0.1g catalyzer, 51.6mmol toluene, 100 ℃ of reaction 10h of 8.6mmol Benzoyl chloride finish, and dodecane is interior mark.
Methyl-phenoxide and Benzoyl chloride acylation reaction condition: 0.1g catalyzer, 25.8mmol benzene, 85 ℃ of reaction 10h of 4.3mmol Benzoyl chloride finish, and dodecane is interior mark.More than reacting stirring velocity is 900rpm.
In above-mentioned reaction with PDVB-SO
2cF
3during for catalyzer, reaction conversion ratio is followed successively by: 84.8,86.7,97.8,98.8%; PDVB-SO
2cF
3have super-hydrophobic skeleton structure, hydrophobic performance is conducive to promote molecular balance forward to move in acid catalysis process, thereby improves catalytic reaction activity and efficiency.
In the acylation reaction process of catalysis toluene and Benzoyl chloride, in the time that stirring velocity is reduced to 60rpm by original 900rpm, PDVB-SO
2cF
3catalytic activity not significantly do not change, change to 97.1% by original 97.8%, mainly owing to PDVB-SO
2cF
3the preferably effectively inner transmission matter resistance in inhibited reaction process of swelling behavior.
PDVB-SO
2cF
3in the acylation reaction of catalysis toluene and Benzoyl chloride, show excellent regenerability; after recycle 5 times activity decreased substantially do not reduce; main owing to stable skeleton structure and active centre, large specific surface area, large specific surface area has increased the anti-poisoning ability of material.
PDVB-SO
2cF
3the hydrophobicity of skeleton has larger impact to the catalytic activity of material, for example general-SO equally
2cF
3functional group's grafting, on PDVB and SBA-15 skeleton, obtains respectively organic hydrophobic framework solid acid and inorganic hydrophilic skeleton solid acid, and material has close specific surface area and pore volume, and PDVB-SO
2cF
3catalytic performance be far superior to SBA-15-SO
2cF
3.
Figure 1A is the nitrogen adsorption isotherm comparison diagram before and after the mesoporous polydivinylbenezene sulfonation prepared of the present invention.Figure 1B is the pore size distribution curve before and after the mesoporous polydivinylbenezene sulfonation prepared of the present invention.In figure, a is curve before sulfonation, and b is curve after sulfonation.As can be seen from the figure, before and after sulfonation, material has the IV type adsorption curve of standard, indicates that material has the existence of meso-hole structure.Pore size distribution is in 20nm left and right, and the adsorptive capacity of material is very large, has abundant meso-hole structure and large specific surface area, and specific surface area is 700m
2/ g.Before and after sulfonation, material has abundant meso-hole structure, aperture homogeneous.
In addition, material prepared by the present invention carries out swelling property test, and selecting acetone and benzene is solvent, find that material has good swelling property, volumetric expansion after lyosorption, after solvent evaporates, the volume of material can recover, and illustrative material has good shape memory function.
Fig. 2 is the infrared spectrum of material before and after the mesoporous polydivinylbenezene sulfonation prepared of the present invention.In figure
arepresent the mesoporous polydivinylbenezene material before sulfonation, b represents the mesoporous polydivinylbenezene material after sulfonation.As can be seen from Figure 2, compare with pure polydivinylbenezene, emerging INFRARED SPECTRUM peak proves that sulfonic acid group is arrived on the skeleton of material by successful grafting.
Fig. 3 is PDVB-SO
2cF
3to the contact angle test pattern of water.As can be seen from Figure 3, material reaches 150 ° for the contact angle of water, illustrates that the solid-acid material of preparing in the present invention has super-hydrophobic constructional feature.This material is to common organism as vegetables oil, and the contact angle of ethanol, toluene etc. is for being less than 10 °, and illustrative material shows oleophylic performance.The hydrophobic lipophilicity of material excellence derives from its full organic backbone and unique nano-porous structure.
Fig. 4 A is PDVB-SO
2cF
3liquid absorption-oil absorptiveness figure.Fig. 4 B is PDVB-SO
2cF
3gaseous state absorption-water absorbing properties test pattern.As we know from the figure, solid strong acid material prepared by the present invention is less than 5% of weight to the adsorptive capacity of water vapor, and the saturated extent of adsorption of acetone, ethanol, normal hexane, toluene etc. is greater than to 10g/g.
Fig. 5 is the TG spectrogram of different samples.PDVB-SO as can be seen from Figure 5
2cF
3thermostability very high, there is excellent skeleton structure stability (543 ℃ to 500 ℃) and acid site stability (385 ℃ to 265 ℃) compared with storng-acid cation exchange resin (Amberlyst15).PDVB-SO
2cF
3thermostability be even better than Nafion NR50 resin (this resin is considered to the most stable industrial ionic exchange resin).
In sum, that material prepared by the present invention has is super-hydrophobic, the constitutional features of super oleophylic and excellent thermostability, and said structure feature makes it in acid catalysis process, show excellent catalytic performance and regenerative power.First we synthesized and had the polydivinylbenezene material that enriches meso-hole structure by the method for solvent thermal, this material has extraordinary swelling behavior to majority of organic solvent, we utilize this feature, in conjunction with the abundant pore structure of this material and large specific surface area, successfully synthesize novel stablizing by the new synthesis route of first swelling rear sulfonation, efficient organic backbone solid-acid material, after sulfonation simultaneously, material is keeping bigger serface and is enriching the structure in hole.Utilize the feature of swelling property can successfully introduce a large amount of acid sites.The present invention is according to sulfonated reagent and the difference of sulfonation time, and the sulphur content of the mesoporous polydivinylbenezene material of strongly-acid of preparation changes between 1.5-3.2mmol/g.This solid acid has super-hydrophobic, super oleophylic skeleton, swelling property to organic substrates excellence, large specific surface area, and excellent thermostability and highly acid active centre, mesoporous aperture is adjustable at 4-30nm; Specific surface area is at 500-700m
2/ g scope is adjustable.At catalytic esterification, in acylation reaction, there is high reactivity and excellent reusing, be far superior to conventional solid acid as Amberlyst-15 resin, the mesoporous SBA-15-SO of h-type zeolite and sulfonate radical functionalization
3h etc., meanwhile, after recycle 5 times, activity has only reduced by 1.43%.
Although the present invention is disclosed as above by preferred embodiment; but not in order to limit the present invention, anyly know this skill person, without departing from the spirit and scope of the present invention; can do a little change and retouching, therefore protection scope of the present invention is when being as the criterion depending on claims scope required for protection.
Claims (5)
1. a preparation method for nanoporous, super-hydrophobic skeleton solid strong acid material, is characterized in that, comprises the following steps:
A. Vinylstyrene is carried out under solvent thermal condition to polymerization, wherein, benzoyl peroxide is initiator, polymerization temperature is within the scope of 80-180 ℃, the usage quantity of the corresponding solvent of every use 2g divinyl benzene monomer is within the scope of 7-25mL, the mass ratio of initiator and Vinylstyrene is 0.015-0.0375, and polymerization time is 12-48h;
B. the nanoporous polydivinylbenezene material of preparing in step a, add solvent, add sulfonated reagent to carry out sulfonation, wherein, solvent is tetracol phenixin or toluene, and sulfonated reagent is trifluoromethanesulfonic acid or fluosulfonic acid, the volume ratio of solvent and sulfonated reagent is 10:1, the mass ratio of nanoporous polydivinylbenezene material and sulfonated reagent is 5-10:1, and sulfonation temperature is within the scope of 80-110 ℃, and the sulfonation time is 12h-36h.
2. the preparation method of nanoporous according to claim 1, super-hydrophobic skeleton solid strong acid material, it is characterized in that, the solvent using in step a is mixed solvent, ethyl acetate, toluene, ethanol, benzene or the acetone of tetrahydrofuran (THF), tetrahydrofuran (THF) and water composition.
3. the preparation method of nanoporous according to claim 1, super-hydrophobic skeleton solid strong acid material, it is characterized in that, described preparation method also comprises after step a: the nanoporous polydivinylbenezene material of preparing in step a is ground to form to ultrafine powder, degassed processing 10h under 150 ℃ of condition of nitrogen gas.
4. the preparation method of nanoporous according to claim 1, super-hydrophobic skeleton solid strong acid material, it is characterized in that, described preparation method also comprises after step b: the product of preparing in step b is removed to unreacted sulfonated reagent with washing with acetone, and 80 ℃ dry.
5. a nanoporous of preparing according to the preparation method described in claim 1-4 any one, super-hydrophobic skeleton solid strong acid material, it is characterized in that, described nanoporous, super-hydrophobic skeleton solid strong acid material are take polydivinylbenezene as skeleton, there is trifluoromethanesulfonic acid sulfonic acid or fluosulfonic acid group, aperture is 4-30nm, and specific surface area is 500-700m
2/ g.
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| CN104258906A (en) * | 2014-08-27 | 2015-01-07 | 绍兴文理学院 | Nano porous fixed acid catalyst with organic frame and synthesis method thereof |
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| CN106378189A (en) * | 2016-08-17 | 2017-02-08 | 上海化工研究院 | A catalyst used for synthesizing polyoxymethylene dimethyl ether, a preparing method thereof and applications of the catalyst |
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| CN110639554B (en) * | 2019-09-11 | 2022-06-24 | 湖南师范大学 | Method for preparing ultrahigh-thermal-stability carbon-silicon composite solid superacid and reversibly regulating and controlling thermal stability of ultrahigh-thermal-stability carbon-silicon composite solid superacid |
| CN114471486A (en) * | 2022-01-29 | 2022-05-13 | 蚌埠学院 | Super-hydrophobic silicon dioxide/polydivinylbenzene nano composite material and preparation method thereof |
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