CN105566674A - Chitin-nanometer-fiber aerogel with high specific surface area and preparing method thereof - Google Patents
Chitin-nanometer-fiber aerogel with high specific surface area and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a chitin-nanometer-fiber aerogel with the high specific surface area. A preparing method includes the steps that a chitin nanometer fiber is prepared with the TEMPO oxidizing method or the mechanical method, and then the superfine nanometer-chitin aerogel is prepared through higher alcohol replacement and drying. According to the chitin-nanometer-fiber aerogel and the preparing method, the preparing process is simple, and the technology is easy to control; a used oxidizing agent is an environment-friendly solvent, safe and nontoxic, the environment-friendly preparing technology is achieved, and cost is reduced; the prepared chitin-nanometer-fiber aerogel is nontoxic, low in density, high in porosity and even in structural unit distribution, and most prominently, the high specific surface area is achieved.
Description
Technical field
The present invention relates to fiber aerogel, chitin nano fiber aerogel being specifically related to a kind of high-specific surface area and preparation method thereof.
Background technology
Chitin nano fiber grain size, between 1 ~ 200nm, is typical monodimension nanometer material.The raw material sources of synthesis chitin nano fiber are extensive, such as arthropods shell, mollusk inner casing and cartilage and mushroom etc.The raw material that present method is chosen be arthropods shell as dried small shrimp, crab shell, mollusk inner casing is as octopus, squid and mushroom cell.These raw materials are biodegradable, toxicological harmless, are that output is only second to the natural polymer of plant cellulose in the world, are the desirable presomas of chitin aerogel.
Chitin aerogel be by the extremely low chitin nano fiber of magnitude assemble in particular procedure each other formed there is porous network structure, and be the polymer solid-state material of dispersion medium with gaseous state.The reference area of chitin nano fiber aerogel material can reach 500 ~ 2000m
2/ g, porosity is up to 80 ~ 99.9%, and hole size changes in 1 ~ 100nm, and density range can at 3 ~ 600kg/m
3between, be solid-state material very light in the world at present.Current chitin fiber aerogel material is mainly through preparing with under type: (1) obtains fiber aerogel by after the fiber gel convection drying of generation; (2) by fibrolysis in various different solvent (as sodium hydroxide solution and ionic liquid etc.), subsequently by non-solvent precipitation regeneration with critically dry prepare highly porous fiber aerogel; (3) from animals and plants, nanofibers can be disassembled on a large scale, carry out assembling with its structural unit and prepare porous aerogel.But aerogel density prepared by first method is large, porosity is low and structure heterogeneity; Reagent used by second method is generally contain fluorous solvent as hexafluoroisopropanol (HEP), Perfluoroacetone semihydrate (HFAS), methanesulfonic by strong acid polar solvent polar aprotic solvent as strong in trichoroacetic acid(TCA) (TCA), dichloro acetic acid (DCA) etc. or strong polarity, after chitin is dissolved, severely degrade can only obtain the extremely low chitin aerogel of molecular weight, and the toxicity of these reagent is comparatively large, causes great pollution to environment.The third method is simple, but the aerogel of preparation is that specific surface area is little, porosity is low equally, thus limits the widespread use of chitin aerogel to a certain extent.
The present invention then combines the third method and has done further improvement to it, first TEMPO Green Oxidant/mechanical process is utilized to prepare chitin nano fiber hydrogel, then utilize higher alcohols to replace and obtain chitin nanofibrils alcogel, in moisture removal process, interfibrous wicking action can form intensive coherent network, thus obtains porosity, chitin nano fiber aerogel that specific surface area is higher.Solve aerogel in preparation process, there is to obtain complex manufacturing technology, the aerogel structure heterogeneity obtained, the problem such as porosity is low, specific surface area is little
A kind of preparation method of chitin aerogel is disclosed in patent document " a kind of preparation method of chitin aerogel " (CN102417606A), but this patent is by the chitin aerogel prepared by chitin alkali/urea dissolution with solvents regeneration, the chitin molecule amount obtained more greatly due to the alkalescence of solvent is extremely low, and solvation process process improves the production cost of chitin aerogel.The more important thing is, only can obtain density by dissolution with solvents manipulation of regeneration large, the chitin aerogel that specific surface area, porosity are low, and structure heterogeneity, complex process is uncontrollable.
Summary of the invention
The object of the invention is to solve dissolution with solvents manipulation of regeneration solvent for use corrodibility in existing chitin aerogel preparation process large, price is high, toxicity is large, complex process is difficult to control, and the chitin aerogel porosity obtained is low, specific surface area is little waits deficiency, chitin nano fiber aerogel providing a kind of high-specific surface area and preparation method thereof.
Preparation process of the present invention is simple, technology controlling and process is easy, oxygenant used belongs to environment-friendly solvent, safety non-toxic, realizes green preparation process, again reduces cost, and prepared chitin nano fiber aerogel is nontoxic, density is low, and porosity is high, and what structural unit distribution was homogeneous and the most outstanding is have higher specific surface area.The chitin nanofibrils aerogel material of preparation can be widely used in absorption, photochemical catalysis, lithium cell, the aspects such as ultracapacitor, this preparation method avoids and uses ion solvent process chitin simultaneously, greatly reduces cost, effectively avoids the severe contamination that organic solvent brings.Obtain the cheap Biological resources of the aerogel efficiency utilization of high-specific surface area by the chitin nano fiber hydrogel of TEMPO oxidation preparation through alcohol displacement, improve its use value, also for the Green High Performance application of chitin provides new thinking and countermeasure.
Technical scheme of the present invention is:
A chitin nano fiber aerogel for high-specific surface area, the method utilizing TEMPO to be oxidized or mechanical means prepare chitin nano fiber, are then replaced by higher alcohols, and drying obtains nano-chitosan aerogel.
A preparation method for the chitin nano fiber aerogel of high-specific surface area, is realized by following steps:
(1) by the method preparation 0.01 ~ 1wt% dispersion liquid of chitin biomass slurry by dispersion treatment, described chitin biomass slurry is: the arthropods shell after bleaching or mollusk inner casing, cartilage or mushroom;
(2) get above-mentioned dispersion liquid and add buffered soln, at magnetic stirring apparatus 300 ~ 1000rpm, under normal temperature and pressure, stir 10 ~ 30min;
(3) add TEMPO and NaClO, after being uniformly dispersed, then add NaClO
2, TEMPO:NaClO:NaClO
2mol ratio is 1:10:50 ~ 400, is heated to 60 ~ 80 DEG C, reaction 1 ~ 4h, stirs lower reaction, then adds ethanol termination reaction; Or add TEMPO and NaBr, after being uniformly dispersed, then add NaClO, TEMPO:NaBr:NaClO mol ratio is 1:10:20 ~ 100, regulates dispersion liquid pH to be 10 ± 0.5, be heated to 60 ~ 90 DEG C by NaOH solution, reaction 1 ~ 8h, stirs lower reaction, then adds ethanol termination reaction;
(4) the dispersion liquid deionized water that step (3) obtains is rinsed repeatedly to neutrality, then with ultrasonic instrument by this dispersion liquid supersound process 30 ~ 180min;
(5) displacement is carried out to chitin hydrogel higher alcohols and can obtain chitin alcogel, namely the alcogel obtained is obtained chitin nano fiber aerogel after drying.
Preferably, the arthropods in described step (1) refers to the animal containing chitin, includes but not limited to shrimp, crab, insect; Described mollusk includes but not limited to fish, cuttlefish; Described bleaching refers to that the method utilizing chemical oxidation is bleached.
Preferably, the method for described step (1) dispersion treatment refers to: mechanical mill, or by high-pressure homogeneous/mechanical glue mill/defibrator process process/high speed shear/large power supersonic dispersion.
Preferably, after described step (1) is disposed, deposit at dispersion liquid being placed in 4 DEG C.
Preferably, the buffered soln described in described step (2) is phosphate buffer soln or acetate buffer solution; Being 6 ~ 7 by phosphate buffer soln control pH, is 4 ~ 5 by acetate buffer solution control pH.
Preferably, described step adds TEMPO and NaBr in (3), after being uniformly dispersed, add NaClO again, TEMPO:NaBr:NaClO mol ratio is 1:10:20 ~ 80, regulating dispersion liquid pH to be 10 ± 0.5, being heated to 60 ~ 90 DEG C by having adjusted the dispersion liquid of pH by NaOH solution, reaction 1 ~ 4h, adds mol ratio 50 ~ 1000 times to the dehydrated alcohol termination reaction of NaClO.
Preferably, the ultrasonic instrument described in described step (4) refers to ultrasonic grinder.
Preferably, described step (5) higher alcohols is the alcohol of more than the ternary can dissolved each other with water, includes but not limited to the trimethyl carbinol.Chitin fiber hydrogel is replaced as the lower chitin alcogel of polarity by higher alcohols, higher alcohols is the alcohol of more than the ternary can dissolved each other with water, there is higher melt, be not limited to the trimethyl carbinol, the mesoporous flexible chitin fiber aerogel that structure is homogeneous can be obtained.Need when replacing to stir at normal temperatures, alcoholic solution can be made like this to enter in chitin fiber gel fast, keep the skeleton of chitin fiber gel, for dried aerogel pattern is laid a good foundation.
Preferably, critical point drying or the supercritical drying of drying mode to be drying medium be carbonic acid gas in described step (5), or lyophilize.
Beneficial effect of the present invention:
1, the TEMPO oxygenant used due to the present invention belongs to environment-friendly solvent, and security is high, thus both can not produce toxicity to the chitin nano fiber aerogel of preparation, also can not bring corrosion to plant and instrument.TEMPO can recycle as oxygenant, and applied metal ion can be avoided to be that catalyzer is to environment.
2, because the present invention uses TEMPO to be oxidized or the method process chitin of machinery, avoid and use strong acid or fluorine-containing polar solvent to dissolve chitin, simplify technique, reduce experimental cost, decrease the pollution to environment.
3, the raw material adopted due to the present invention be discarded dried small shrimp, crab shell or some animal shells as cockroach, silkworm chrysalis, not only decrease the added value that environmental pollution also improves biological material.
4, due to the aerogel that the present invention uses higher alcohols replacing water gel, dry method obtains, the displacement for higher alcohols makes the chitin aerogel of acquisition have three-dimensional network crosslinking structure, has typical meso-hole structure.
5, because the present invention uses ultrasonication, destroy more weak hydrogen bond and Van der Waals force between chitin fiber, such that micron-sized chitin fiber is progressively top-down is decomposed into nanofiber.
6, due to the core condensation drying that the present invention uses, ultrasonic device is simply common, does not need to add expensive device.And the higher alcohols displacement liquid fusing point used is lower, does not even need separately to add refrigerating apparatus, therefore tests green preparation process by low cost.
7, the present invention is the chitin nanoporous aerogel utilizing higher alcohols displacement drying to make to have superhigh specific surface area on the basis of TEMPO oxidation or mechanical process process chitin, structure is homogeneous, there is low density, highly porous, high-specific surface area, achieve the optimization of structure.
The chitin nano fiber element aerogel of the high-specific surface area 8, prepared by the present invention not only has high-specific surface area, and can obtain the chitin nanoporous aerogel with intensive fibril network structure by the displacement of higher alcohols.
9, preparation process of the present invention is simple and safe controlled.
What 10, use in process of the present invention is nearly all Green Chemistry reagent, meets green chemical concept.
11, the chitin nanofibrils aerogel prepared of the present invention is of many uses, and can be used for ultracapacitor, the specific demand such as photochemical catalysis and biological medicine, belongs to high value added product.
Chitin nanoporous aerogel prepared by preparation method provided by the invention is the natural chitin of high purity (higher than 99.9%), and its degree of crystallinity is very high, and crystalline indice is greater than 50.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the high-specific surface area chitin nanofibrils aerogel that specific embodiment 1 obtains;
Fig. 2 is the XRD figure of the high-specific surface area chitin nanofibrils aerogel that specific embodiment 2 obtains;
Fig. 3 is the FTIR figure of the high-specific surface area chitin nanofibrils aerogel that specific embodiment 3 obtains;
Fig. 4 is the Raman figure of the high-specific surface area chitin nanofibrils aerogel that specific embodiment 4 obtains;
Fig. 5 is the N2 adsorption desorption graphic representation of the high-specific surface area chitin nanofibrils aerogel that specific embodiment 5 obtains.
Embodiment
Following examples only for illustration of the present invention, but are not used for limiting invention scope of the present invention.The technician of this technical field can make improvement and the adjustment of some non-intrinsically safes according to the content of foregoing invention.
Embodiment 1:
1. utilize phenylethyl alcohol to carry out extracting by 1:2 the shrimp shell 2g of industrial waste and remove some organism, then utilize Glacial acetic acid to regulate pH to add 1wt%NaClO under 4.8 conditions
2, in 80 DEG C of heating 3h bleaching;
2. the shrimp shell after bleaching is formulated as 1wt% dispersion liquid and obtains the thick chitin dispersion liquid of 1wt% by the method for mechanical mill;
3. phosphate buffer soln is added above-mentioned dispersion liquid, regulate dispersion liquid pH to be 6.8,1300rpm on magnetic stirring apparatus, normal temperature and pressure stirs 15min;
4. add TEMPO and NaClO after, after being uniformly dispersed, then add NaClO
2, TEMPO:NaClO:NaClO
2mol ratio is 1:10:100, rapidly container closure is heated to 80 DEG C of reaction 2.5h, adds, 15ml ethanol termination reaction after reaction terminates;
5. the dispersion liquid deionized water obtained is rinsed repeatedly to neutrality, then use ultrasonic grinder (1500W) by ultrasonic for this dispersion liquid 60min;
6. pair hydrogel trimethyl carbinol obtained is replaced, and obtains alcogel, by the alcogel that obtains at-80 DEG C of freezing 2h, namely obtains high-ratio surface chitin nano fiber aerogel after lyophilize.
Embodiment 2:
1. commercially buy the chitin 2g of bleaching, pulverized 80 eye mesh screens, be mixed with the dispersion liquid of 1wt%, deposit at 4 DEG C
2. get the above-mentioned dispersion liquid of 400ml, after stirring, add 360ml phosphate buffer soln, regulate dispersion liquid pH=7.
3. add TEMPO and NaBr after, be uniformly dispersed and add NaClO again, TEMPO:NaBr:NaClO mol ratio is 1:10:25, rapidly container closure is heated to 70 DEG C of reaction 2h, adds 10ml ethanol termination reaction after reaction terminates;
4. the dispersion liquid deionized water obtained is rinsed repeatedly to neutrality, then use ultrasonic grinder (1500W) by ultrasonic for this dispersion liquid 1.5h;
5. pair this dispersion liquid trimethyl carbinol carries out displacement and obtains gel, by the gel that obtains at-20 DEG C of freezing 4h, namely obtains chitin nano fiber aerogel after lyophilize.
Embodiment 3:
1. utilized by the crab shell of industrial waste phenylethyl alcohol to process 6.5h by 1:2 at 80 DEG C, then utilize salt acid for adjusting pH to be add 1wt%NaClO under 4.8 conditions
2at 90 DEG C of heating 2.5h, after cleaning, remaining solid matter glue is worn into the dispersion liquid of 1wt%;
2. get the above-mentioned dispersion liquid of 400ml, phosphate buffer soln is added above-mentioned dispersion liquid, regulate pH=6.5, TEMPO0.064g and NaBr0.4g is added after stirring, after being uniformly dispersed, then add 2mol/LNaClO2ml, utilize 0.5mol/LNaOH to control the pH of dispersion liquid to 10, reaction 1.5h, after add 20ml ethanol termination reaction;
3. the dispersion liquid deionized water obtained is rinsed repeatedly to neutrality, then use ultrasonic grinder (1500W) by ultrasonic for this dispersion liquid 0.5h;
4.. displacement is carried out to this dispersion liquid propyl carbinol and obtain gel, by the gel that obtains at-80 DEG C of freezing 4h, after lyophilize, namely obtain chitin nano fiber aerogel.
Embodiment 4:
1. by the crab shell of bleaching, pulverize, machinery dish end, is mixed with the dispersion liquid of 0.5wt%, deposits at 4 DEG C.
2. get the above-mentioned dispersion liquid of 300ml, after stirring, add 300ml acetate buffer solution, regulate dispersion liquid pH=4.8.
3. add TEMPO after to be uniformly dispersed and to add NaClO and NaClO again
2, rapidly container closure is heated to 75 DEG C of reaction 3h, after reaction terminates, adds the ethanol termination reaction of 30mL;
4. the dispersion liquid deionized water obtained is rinsed repeatedly to neutrality, then use ultrasonic bath (1000W) by ultrasonic for this dispersion liquid 2h;
5. pair this dispersion liquid ethanol carries out displacement and obtains gel, by the gel that obtains at-20 DEG C of freezing 4h, namely obtains chitin nano fiber aerogel after lyophilize.
Embodiment 5:
1. cockroach shell or silkworm chrysalis shell are utilized benzene: alcohol mixeding liquid by volume 1:2 carries out extracting and removes some organism, then utilize Glacial acetic acid to regulate pH to add 1wt%NaClO under 4.5 conditions
2in 75 DEG C of heating 1h bleaching;
2. the cockroach shell after bleaching or silkworm chrysalis shell obtain the thick chitin dispersion liquid of 1wt% by high-pressure homogeneous method;
3. acetate buffer solution is added above-mentioned dispersion liquid, regulate dispersion liquid pH=5, magnetic stirring apparatus stirs 10min, Mierocrystalline cellulose is better disperseed;
4. after, add TEMPO and NaBr, be uniformly dispersed and add NaClO again, TEMPO:NaBr:NaClO mol ratio is 1:10:50, pH meter is utilized to regulate pH to be 10, container closure is heated to 80 DEG C of reaction 1h, after reaction terminates, adds 100 times to the ethanol termination reaction of NaClO (mol ratio);
5. the dispersion liquid deionized water obtained is rinsed repeatedly to neutrality, then use ultrasonic grinder (1500W) by ultrasonic for this dispersion liquid 2h;
6. dispersion liquid obtained above is got supernatant liquid by centrifugal treating, obtain chitin nano fiber hydrogel;
7. hydrogel spent glycol obtained above is carried out displacement and obtains chitin nanofibrils alcogel, then by the alcogel that obtains at-80 DEG C of freezing 1h, namely obtain chitin nano fiber aerogel after lyophilize.
Claims (10)
1. a chitin nano fiber aerogel for high-specific surface area, the method that it is characterized in that utilizing TEMPO to be oxidized or mechanical means prepare chitin nano fiber, and then replaced by higher alcohols, drying obtains nano-chitosan aerogel.
2. the preparation method of chitin nano fiber aerogel as claimed in claim 1, is characterized in that being realized by following steps:
(1) by the method preparation 0.01 ~ 1wt% dispersion liquid of chitin biomass slurry by dispersion treatment, described chitin biomass slurry is: the arthropods shell after bleaching or mollusk inner casing, cartilage or mushroom;
(2) get above-mentioned dispersion liquid and add buffered soln, at magnetic stirring apparatus 300 ~ 1000rpm, under normal temperature and pressure, stir 10 ~ 30min;
(3) add TEMPO and NaClO, after being uniformly dispersed, then add NaClO
2, TEMPO:NaClO:NaClO
2mol ratio is 1:10:50 ~ 400, is heated to 60 ~ 80 DEG C, reaction 1 ~ 4h, stirs lower reaction, then adds ethanol termination reaction; Or add TEMPO and NaBr, after being uniformly dispersed, then add NaClO, TEMPO:NaBr:NaClO mol ratio is 1:10:20 ~ 100, regulates dispersion liquid pH to be 10 ± 0.5, be heated to 60 ~ 90 DEG C by NaOH solution, reaction 1 ~ 8h, stirs lower reaction, then adds ethanol termination reaction;
(4) the dispersion liquid deionized water that step (3) obtains is rinsed repeatedly to neutrality, then with ultrasonic instrument by this dispersion liquid supersound process 30 ~ 180min;
(5) displacement is carried out to chitin hydrogel higher alcohols and can obtain chitin alcogel, namely the alcogel obtained is obtained chitin nano fiber aerogel after drying.
3. preparation method according to claim 2, the arthropods that it is characterized in that in step (1) refers to the animal containing chitin, includes but not limited to shrimp, crab, insect; Described mollusk includes but not limited to fish, cuttlefish; Described bleaching refers to that the method utilizing chemical oxidation is bleached.
4. preparation method according to claim 2, is characterized in that the method for step (1) dispersion treatment refers to: mechanical mill, or by high-pressure homogeneous/mechanical glue mill/defibrator process process/high speed shear/large power supersonic dispersion.
5. preparation method according to claim 2, after it is characterized in that step (1) is disposed, deposits at dispersion liquid being placed in 4 DEG C.
6. preparation method according to claim 2, is characterized in that the buffered soln described in step (2) is phosphate buffer soln or acetate buffer solution; Being 6 ~ 7 by phosphate buffer soln control pH, is 4 ~ 5 by acetate buffer solution control pH.
7. preparation method according to claim 2, it is characterized in that adding TEmolPO and NaBr in step (3), after being uniformly dispersed, add NaClO again, TEMPO:NaBr:NaClO mol ratio is 1:10:20 ~ 80, regulating dispersion liquid pH to be 10 ± 0.5, being heated to 60 ~ 90 DEG C by having adjusted the dispersion liquid of pH by NaOH solution, reaction 1 ~ 4h, adds mol ratio 50 ~ 1000 times to the dehydrated alcohol termination reaction of NaClO.
8. preparation method according to claim 2, is characterized in that the ultrasonic instrument described in step (4) refers to ultrasonic grinder.
9., according to the arbitrary described preparation method of claim 2 to 8, it is characterized in that step (5) higher alcohols is the alcohol of more than the ternary can dissolved each other with water, include but not limited to the trimethyl carbinol.
10. preparation method according to claim 9, is characterized in that drying mode in step (5) to be drying medium is critical point drying or the supercritical drying of carbonic acid gas, or lyophilize.
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| CN106868630A (en) * | 2017-02-10 | 2017-06-20 | 青岛科技大学 | A kind of preparation method of squid bone nanofiber |
| CN108316039A (en) * | 2018-02-11 | 2018-07-24 | 陕西科技大学 | A kind of method that mechanical couplings chemistry alkali soluble method prepares aramid nano-fiber |
| CN108910944A (en) * | 2018-08-30 | 2018-11-30 | 济南大学 | A method of mesoporous TiO 2 is prepared by template of chitin |
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| CN106057485A (en) * | 2016-08-19 | 2016-10-26 | 南京林业大学 | Method for preparing super capacitor aerogel electrode material |
| CN106868630A (en) * | 2017-02-10 | 2017-06-20 | 青岛科技大学 | A kind of preparation method of squid bone nanofiber |
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| CN108316039A (en) * | 2018-02-11 | 2018-07-24 | 陕西科技大学 | A kind of method that mechanical couplings chemistry alkali soluble method prepares aramid nano-fiber |
| CN108316039B (en) * | 2018-02-11 | 2019-09-13 | 陕西科技大学 | A kind of method that mechanical couplings chemistry alkali soluble method prepares aramid nano-fiber |
| CN108910944A (en) * | 2018-08-30 | 2018-11-30 | 济南大学 | A method of mesoporous TiO 2 is prepared by template of chitin |
| CN109897196A (en) * | 2019-02-19 | 2019-06-18 | 南京林业大学 | A kind of nano-chitosan-titanium dioxide-polyacrylamide composite catalyzing hydrogel and its preparation method and application |
| CN109897196B (en) * | 2019-02-19 | 2021-08-10 | 南京林业大学 | Nano chitin-titanium dioxide-polyacrylamide composite catalytic hydrogel and preparation method and application thereof |
| CN111040234A (en) * | 2019-12-16 | 2020-04-21 | 四川大学 | Novel preparation method of hierarchical pore chitin material |
| CN111040234B (en) * | 2019-12-16 | 2021-09-14 | 四川大学 | Preparation method of hierarchical pore chitin material |
| CN115530222A (en) * | 2022-09-19 | 2022-12-30 | 福建农林大学 | Food fresh-keeping pad with slow-release antibacterial and antioxidant functions and preparation method thereof |
| CN115530222B (en) * | 2022-09-19 | 2024-01-26 | 福建农林大学 | Food fresh-keeping pad with slow-release antibacterial and antioxidant functions and preparation method thereof |
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