CN104959123A - Preparation method and application of novel hierarchical pore composite material - Google Patents
Preparation method and application of novel hierarchical pore composite material Download PDFInfo
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- CN104959123A CN104959123A CN201510417502.9A CN201510417502A CN104959123A CN 104959123 A CN104959123 A CN 104959123A CN 201510417502 A CN201510417502 A CN 201510417502A CN 104959123 A CN104959123 A CN 104959123A
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Abstract
The invention provides a preparation method and application of a novel hierarchical pore composite material. According to the material, a hierarchical pore material is prepared from cotton as a raw material by adopting cellulose nanocrystallines and CTAB as two mold plates, and then the hierarchical pore material is subjected to modifying by using lanthanum nitrate to prepare the novel hierarchical pore composite material. According to the method, the hierarchical pore composite material with the high surface area is prepared by adopting cotton hydrolysis products and the CTAB as the mold plates, the composite material has a continuous controllable hole structure, and further the composite material is subjected to modifying by using the lanthanum nitrate, so that the relatively high adsorption performance is realized, and phosphorus with the low concentration in environments can be adsorbed.
Description
Technical field
The invention belongs to technical field of material, especially a kind of preparation method of new multistage hole composite material and application thereof.
Background technology
The eutrophication in lake has very important association with the content of phosphorus in lake water.Data show: when the concentration of phosphorus is not higher than 0.01mg/l, lake generally serious eutrophication can not occur; When concentration is at 0.02mg/l ~ 1mg/l, under suitable condition will there is more serious eutrophication in lake.Therefore the phosphorus of low concentration also can work the mischief to water body.
Multi-stage porous composite, as a kind of emerging material, such as micropore-mesopore composite, because it has micropore and mesoporous double grading, makes it in some adsorption reactions, show very high adsorption capacity.Micropore provides duct for reactant and selects shape effect, and mesoporous existence makes reactant more easily touch activated centre, promotes the separation and concentration of product.
The method of dephosphorization has multiple, wherein absorption method have simple, convenient, do not produce the unrivaled advantages such as noxious material.Current the dephosphorization adsorbent studying report has a variety of, but ubiquity adsorption capacity is low, the rate of adsorption is slow or the deficiency such as expensive.Recent research finds, mesopore molecular sieve is expected to become a class Novel dephosphorization adsorbent, is the study hotspot in current dephosphorization field.Mesoporous material has pore passage structure, uniform pore diameter and the size adjustable (2 ~ 50nm) of high-sequential arrangement, specific area is large, adsorption capacity is high, the advantage such as Heat stability is good and nontoxicity, and mesoporous material channel surfaces has the features such as the silicone hydroxyl being easy to uniformly modify, therefore, mesoporous material has larger using value in Adsorption of Heavy Metal Ions, organic pollution, radionuclide etc. in field of Environment Protection.The adsorption effect of simple inorganic material in adsorption process is often not fully up to expectations, and organically-modified be give inorganic material functionalization characteristic, thus improve the effective means of adsorbent effect and the rate of adsorption.Along with further developing of studying adsorbent, many researchers start to be devoted to carry out organically-modified to inorganic material, thus prepare functional, the organically-modified inorganic material adsorbent that has again the advantage of inorganic matrix with organo-functional group.
Summary of the invention
For Shortcomings in prior art, the invention provides a kind of preparation method and application thereof of multi-stage porous composite, prepared multi-stage porous composite has the pore passage structure of high-sequential arrangement, uniform pore diameter and size adjustable, specific area is large, adsorption capacity is high, the advantage such as Heat stability is good and nontoxicity, especially has higher adsorption capacity and the rate of adsorption faster for phosphorus.
The present invention realizes above-mentioned technical purpose by following technological means.
A preparation method for multi-stage porous composite, is characterized in that, comprises the following steps:
(1) extracting degreasing cotton is dissolved in dilute sulfuric acid, mechanical agitation is kept under 45 DEG C of water-baths, take out dilution, centrifugal recovery sediment and be washed with distilled water to cannot centrifugal till, reinstall in bag filter and dialyse, obtaining concentration is 3wt% Cellulose nanocrystal, adds deionized water and is diluted to 0.5wt%;
(2) in round-bottomed flask, add deionized water and ethanol 60ml altogether, wherein, the volume ratio of deionized water and ethanolic solution is 1.5:1 ~ 2.5:1, softex kw (CTAB) 25 ~ 35mg, being stirred to CTAB under 30 DEG C of water-baths is micella state, then adds ammoniacal liquor 400 ~ 600ul, adds step (1) 0.5wt% Cellulose nanocrystal aqueous solution 3.5-4.5ml, add tetraethyl orthosilicate 80 ~ 120ul after 10min, continue 30 DEG C of water-bath 2h;
(3) treat that step (2) reaction terminates, suction filtration, washs three times with deionized water and ethanol, takes out and is positioned over evaporate to dryness in 60 DEG C of baking ovens, and the heating rate of 1-2 DEG C/min is warming up to 530-550 DEG C of calcining 6h, obtains multi-stage porous nano material;
(4) the multi-stage porous nano material that step (3) obtains is placed in ethanol, add six directions water lanthanum nitrate crystal, the mol ratio of lanthanum silicon is 1:5, stirring in water bath 8-12h at 60 DEG C, dry, be warming up to 530-550 DEG C of calcining 6h with the heating rate of 2-3 DEG C/min, obtain multi-stage porous composite.
Preferably, in step (2), the volume ratio of deionized water and ethanolic solution is 2:1.
Preferably, the amount of CTAB is 30mg, and the amount of ammoniacal liquor is the amount of 500ul, the 0.5wt% Cellulose nanocrystal aqueous solution is 4ml, and the amount of tetraethyl orthosilicate is 100ul.
Preferably, in step (3), the temperature of calcining is 540 DEG C.
Preferably, in step (4), the stirring in water bath time is 10h, and the temperature of calcining is 540 DEG C.
Multi-stage porous composite prepared by described preparation method is separated for the selective absorption of heavy phosphate anion.
The present invention mixes lanthanum element in multilevel hole material, there is the pore passage structure of high-sequential arrangement, uniform pore diameter and size adjustable, specific area is large, adsorption capacity is high, the advantage such as Heat stability is good and nontoxicity, especially have higher adsorption capacity and the rate of adsorption faster for phosphorus, the P elements be therefore applied to by this composite in the water body of the low phosphorus such as absorption river, lake has higher practical significance.
Beneficial effect of the present invention:
(1) adopt high-specific-surface mesoporous material, drastically increase the adsorption capacity of material, and preparation process is simple to operation.
(2) use lanthanum nitrate as part, compared with the part that other prices are high, significantly reduce the production cost of material.
(3) the nanostructure composite material absorption utilizing the present invention to obtain can be carried out efficiently several heavy phosphate anion, high-selectivity adsorption is separated.
Accompanying drawing explanation
Fig. 1 is multi-stage porous composite transmission electron microscope picture.The material mixed in obviously in order multi-stage porous and micropore canals structure and duct is demonstrated in figure.
Fig. 2 is multi-stage porous composite scanning electron microscope (SEM) photograph, demonstrates obviously multi-stage porous hole and micropore canals structure in order in figure.
Fig. 3 is the EDS collection of illustrative plates that multi-stage porous composite scanning electron microscope (SEM) photograph is corresponding, demonstrates material surface and successfully mix lanthanum element in figure.
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1:
(1) getting 5.0g absorbent cotton, to be dissolved in 75ml concentration be in the dilution heat of sulfuric acid of 45%, be placed in 45 DEG C of water-bath constant temperature, keep mechanical agitation 2h, dilute 10 times to 675ml, centrifugal under 4500r/min rotating speed, and add distilled water washing to can not centrifugal, dialyse to pH be 2.3, obtaining concentration is 3.5wt% Cellulose nanocrystal, adds deionized water and is diluted to 0.6wt%.
(2) in round-bottomed flask, 36ml deionized water, 24ml ethanol, 25mgCTAB is added, 30min is mixed by force in 30 DEG C of water-baths, add ammoniacal liquor 400ul again, add the 0.6wt% Cellulose nanocrystal 3.5ml after the dilution that step (1) obtains, add tetraethyl orthosilicate 80ul after stirring 10min, continue constant temperature 2h in 30 DEG C of water-baths.
(3) treat step (2) reaction terminate, suction filtration, washs three times with deionized water and ethanol, take out be positioned over evaporate to dryness in 60 DEG C of baking ovens, with 3 DEG C/min be warming up to 530 DEG C calcining 6h, obtain multi-stage porous nano material.
(4) the multi-stage porous nano material that step (3) obtains is placed in ethanol, adding six directions water lanthanum nitrate crystal makes the mol ratio of silicon lanthanum in solution be 1:5, constant temperature in 60 DEG C of water-baths also stirs 10h, dry, with 2 DEG C/min be warming up to 530 DEG C calcining 6h, obtain modification mesoporous silicon membrane material, i.e. multi-stage porous composite.
Embodiment 2:
(1) getting 5.0g absorbent cotton is dissolved in 50% dilution heat of sulfuric acid of 75ml, be placed in 45 DEG C of water-bath constant temperature, keep mechanical agitation 2h, dilute 10 times to 750ml, centrifugal under 5000r/min rotating speed, and add distilled water washing to can not centrifugal, dialyse to pH be 2.4, obtain the Cellulose nanocrystal that concentration is 3wt%, add deionized water and be diluted to 0.5wt%.
(2) in round-bottomed flask, add 40ml deionized water, 20ml ethanol, 30mg softex kw (CTAB), constant temperature in 30 DEG C of water-baths strong agitation 30min, add ammoniacal liquor 500ul again, add the 0.5wt% Cellulose nanocrystal 4ml after the dilution that step (1) obtains, add tetraethyl orthosilicate 100ul after 10min, continue constant temperature 2h in 30 DEG C of water-baths.
(3) treat step (2) reaction terminate, suction filtration, washs three times with deionized water and ethanol, take out be positioned over evaporate to dryness in 60 DEG C of baking ovens, with 2 DEG C/min be warming up to 540 DEG C calcining 6h, obtain multi-stage porous nano material;
(4) the multi-stage porous nano material that step (3) obtains is placed in ethanol, adding six directions water lanthanum nitrate crystal makes the mol ratio of silicon lanthanum be 1:5, stirring in water bath 10h at 60 DEG C, dry, with 2 DEG C/min be warming up to 540 DEG C calcining 6h,, obtain modification mesoporous silicon membrane material, i.e. nanostructured composite adsorbing material.
Fig. 1 is the transmission electron microscope picture of multi-stage porous composite.Obviously order mesoporous and micropore canals structure is demonstrated in figure.
Fig. 2 is multi-stage porous composite scanning electron microscope (SEM) photograph, demonstrates obviously order mesoporous and micropore canals structure in figure.
Fig. 3 is the EDS collection of illustrative plates that multi-stage porous composite scanning electron microscope (SEM) photograph is corresponding, demonstrates material surface and successfully mix lanthanum element in figure.
Above-mentioned nanostructured composite adsorbing material is applied to the phosphate anion in adsorbing separation water sample, and concrete grammar carries out according to following step.
(1) what accurately to take etc. the various phosphate anion of quality is configured to storing solution.
(2) the nanostructured composite adsorbing material getting certain mass adds in the middle of the environmental samples of certain volume, is placed in water bath chader 25 DEG C absorption 6h.
(3) if initial phosphate anion solubility is C
0, the phosphate anion after absorption is C
t, then nanostructured relapses enclosure material adsorption capacity Q
tcalculate with equation (1).
W: the quality of sorbing material, V: the volume of environmental samples, M: the relative atomic mass of phosphate anion.
Concentration in table 1 environmental samples before and after low phosphorus absorption
Concentration value in multi-stage porous composite absorption environmental samples before and after low phosphorus absorption is as shown in table 1, demonstrates this material obvious to the suction-operated of low phosphorus in environment water.
Embodiment 3:
(1) getting 5.0g absorbent cotton is dissolved in 55% dilution heat of sulfuric acid of 75ml, be placed in 45 DEG C of water-baths, keep mechanical agitation 2h, dilute 10 times to 825ml, centrifugal under 5500r/min rotating speed, and add distilled water washing to can not centrifugal, dialyse make pH be adjusted to 2.5, obtain the Cellulose nanocrystal that mass concentration is 2.5%, add deionized water and be diluted to 0.4%.
(2) in round-bottomed flask, add 43ml deionized water, 17ml ethanol, 35mg softex kw (CTAB), strong agitation 30min under 30 DEG C of water-baths, add ammoniacal liquor 600ul again, add the 0.5wt% Cellulose nanocrystal 4.5ml after the dilution that step (1) obtains, add tetraethyl orthosilicate 120ul after 10min, continue 30 DEG C of water-bath 2h.
(3) treat step (2) reaction terminate, suction filtration, washs three times with deionized water and ethanol, take out be positioned over evaporate to dryness in 60 DEG C of baking ovens, with 3 DEG C/min be warming up to 550 DEG C calcining 6h, obtain multi-stage porous nano material;
(4) the multi-stage porous nano material that step (3) obtains is placed in ethanol, add six directions water lanthanum nitrate crystal, the mol ratio of silicon lanthanum is 1:5, stirring in water bath 10h at 60 DEG C, dry, with 2 DEG C/min be warming up to 550 DEG C calcining 6h, obtain modification mesoporous silicon membrane material, i.e. nanostructured composite adsorbing material.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.
Claims (6)
1. a preparation method for multi-stage porous composite, is characterized in that, comprises the following steps:
(1) extracting degreasing cotton is dissolved in dilute sulfuric acid, under 45 DEG C of water-baths, keep mechanical agitation, takes out dilution, centrifugal recovery sediment and be washed with distilled water to cannot centrifugal till, reinstall in bag filter and dialyse, obtaining concentration is 3wt% Cellulose nanocrystal, adds deionized water and is diluted to 0.5wt%;
(2) in round-bottomed flask, add deionized water and ethanol 60ml altogether, wherein, the volume ratio of deionized water and ethanolic solution is 1.5:1 ~ 2.5:1, softex kw (CTAB) 25 ~ 35mg, being stirred to CTAB under 30 DEG C of water-baths is micella state, then adds ammoniacal liquor 400 ~ 600ul, adds step (1) 0.5wt% Cellulose nanocrystal aqueous solution 3.5-4.5ml, add tetraethyl orthosilicate 80 ~ 120ul after 10min, continue 30 DEG C of water-bath 2h;
(3) treat that step (2) reaction terminates, suction filtration, washs three times with deionized water and ethanol, takes out and is positioned over evaporate to dryness in 60 DEG C of baking ovens, and the heating rate of 1-2 DEG C/min is warming up to 530-550 DEG C of calcining 6h, obtains multi-stage porous nano material;
(4) the multi-stage porous nano material that step (3) obtains is placed in ethanol, adds six directions water lanthanum nitrate crystal, the mol ratio of lanthanum silicon is 1:5, stirring in water bath 8-12h at 60 DEG C, dry, be warming up to 530-550 DEG C of calcining 6h with the heating rate of 2-3 DEG C/min, obtain multi-stage porous composite.
2. the preparation method of multi-stage porous composite according to claim 1, is characterized in that: in step (2), the volume ratio of deionized water and ethanolic solution is 2:1.
3. multi-stage porous according to claim 1 checks the preparation method of material, it is characterized in that: the amount of CTAB is 30mg, and the amount of ammoniacal liquor is the amount of 500ul, the 0.5wt% Cellulose nanocrystal aqueous solution is 4ml, and the amount of tetraethyl orthosilicate is 100ul.
4. multi-stage porous according to claim 1 checks the preparation method of material, it is characterized in that: in step (3), the temperature of calcining is 540 DEG C.
5. multi-stage porous according to claim 1 checks the preparation method of material, it is characterized in that: in step (4), the stirring in water bath time is 10h, and the temperature of calcining is 540 DEG C.
6. the multi-stage porous that described in any one of claim 1-5 prepared by preparation method checks material for the phosphate anion in adsorbing separation water.
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Cited By (8)
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| CN105217718A (en) * | 2015-11-03 | 2016-01-06 | 中国人民解放军后勤工程学院 | A kind of method improving mesopore molecular sieve adsorb both hydrophobic organism usefulness |
| CN106390912A (en) * | 2016-09-12 | 2017-02-15 | 江苏大学 | Preparation and application of 2-hydroxymethyl-12-crown 4-ether modified hierarchically-porous silicon material |
| CN106669598A (en) * | 2016-12-21 | 2017-05-17 | 浙江大学 | Novel zeolite adsorbent for removing anionic pollutant in water and preparation method |
| CN106964318A (en) * | 2017-03-17 | 2017-07-21 | 江苏大学 | A kind of mesoporous silicon fiml and its an one step preparation method and purposes |
| CN107216433A (en) * | 2017-05-02 | 2017-09-29 | 江苏大学 | It is a kind of to visualize the preparation method that sulfanilamide (SN) molecular engram detects film |
| CN107383535A (en) * | 2017-08-04 | 2017-11-24 | 上海航天设备制造总厂 | Improve the method for compatibility between Cellulose nanocrystal/polyolefin with HTAB |
| CN107552012A (en) * | 2017-10-24 | 2018-01-09 | 武汉纺织大学 | Composite nanometer particle adsorbent of adsorpting anion organic dyestuff and preparation method thereof |
| CN110227456A (en) * | 2019-06-05 | 2019-09-13 | 华南理工大学 | MOFs derives two-dimensional multistage hole Cu/C composite material and preparation method |
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Cited By (11)
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| CN105217718A (en) * | 2015-11-03 | 2016-01-06 | 中国人民解放军后勤工程学院 | A kind of method improving mesopore molecular sieve adsorb both hydrophobic organism usefulness |
| CN106390912A (en) * | 2016-09-12 | 2017-02-15 | 江苏大学 | Preparation and application of 2-hydroxymethyl-12-crown 4-ether modified hierarchically-porous silicon material |
| CN106390912B (en) * | 2016-09-12 | 2019-04-02 | 江苏大学 | The preparation and application of the modified multi-stage porous silicon materials of 2- methylol -12- crown ether -4 |
| CN106669598A (en) * | 2016-12-21 | 2017-05-17 | 浙江大学 | Novel zeolite adsorbent for removing anionic pollutant in water and preparation method |
| CN106669598B (en) * | 2016-12-21 | 2020-04-10 | 浙江大学 | Zeolite adsorbent for removing anionic pollutants in water and preparation method thereof |
| CN106964318A (en) * | 2017-03-17 | 2017-07-21 | 江苏大学 | A kind of mesoporous silicon fiml and its an one step preparation method and purposes |
| CN106964318B (en) * | 2017-03-17 | 2019-08-02 | 江苏大学 | A kind of mesoporous silicon fiml and its an one step preparation method and purposes |
| CN107216433A (en) * | 2017-05-02 | 2017-09-29 | 江苏大学 | It is a kind of to visualize the preparation method that sulfanilamide (SN) molecular engram detects film |
| CN107383535A (en) * | 2017-08-04 | 2017-11-24 | 上海航天设备制造总厂 | Improve the method for compatibility between Cellulose nanocrystal/polyolefin with HTAB |
| CN107552012A (en) * | 2017-10-24 | 2018-01-09 | 武汉纺织大学 | Composite nanometer particle adsorbent of adsorpting anion organic dyestuff and preparation method thereof |
| CN110227456A (en) * | 2019-06-05 | 2019-09-13 | 华南理工大学 | MOFs derives two-dimensional multistage hole Cu/C composite material and preparation method |
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