CN106397792A - Novel gas-sensitive aerogel material and preparation method thereof - Google Patents
Novel gas-sensitive aerogel material and preparation method thereof Download PDFInfo
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- CN106397792A CN106397792A CN201610216497.XA CN201610216497A CN106397792A CN 106397792 A CN106397792 A CN 106397792A CN 201610216497 A CN201610216497 A CN 201610216497A CN 106397792 A CN106397792 A CN 106397792A
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- cellulose
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- aerogel
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- hydrosol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a novel gas-sensitive aerogel material and a preparation method thereof. The gas-sensitive aerogel provided by the invention is a porous aerogel constructed by cellulose nanofiber and nanometer zinc oxide. The preparation method provided by the invention comprises the following steps: step 1, soaking an aggregation cellulose material into a combined water system; step 2, freezing a mixture composed of the aggregation cellulose and the combined water system to minus 5 to minus 15 DEG C, and carrying out stirring and unfreezing so as to obtain a cellulose hydrosol which is uniformly-dispersed at the molecular level; step 3, subjecting the above-mentioned hydrosol to film casting, then carrying out soaking in an aqueous sodium sulfate solution with a concentration of 16 to 20 wt%, and carrying out sol-gel transition; step 4, carrying out replacement by successively soaking the hydrosol into tertiary butanol with concentrations of 20 to 25%, 45 to 50%, 70 to 75% and 100%; and step 5, subjecting a replaced gel material to freeze vacuum drying so as to obtain the porous aerogel. According to the invention, the cellulose aerogel and the ZnO aerogel are organically combined together, so the sensitivity during detection of ammonia gas is improved.
Description
Invention field
A kind of the present invention relates to technical field of composite materials, more particularly it relates to new air-sensitive aerogel material
And preparation method thereof.
Technical background
Nano-ZnO is the earliest gas sensitive using, with widely used nano SnO2Compare, its operation principle is a mould
The same, but its detection sensitivity compares SnO2Low.In addition also there is low price, easily prepared.However, nanometer
ZnO gas sensor mainly has slug type, thick-film type, three kinds of film-type, almost has response, gas-selectively to all of gas
Difference.When using in life and production, often require that the selectivity that device has had, this just hinders the city of nano-ZnO gas sensitive device
Fieldization, scale, are its future development problem demanding prompt solutions.
Aeroge is a kind of porous material with nanostructured, its porosity up to more than 90%, and density is minimum can be extremely
0.001g/cm3, it is one of solid material the lightest in the world at present.It differs markedly from pore space structure in micron and grade
Porous material, there is great specific surface area.Because its distinctive nanoporous, three-dimensional net structure are so as to have many
Unique performance, especially shows the aspects such as high porosity, low-density, lower thermal conductivity, can be widely applied to heat-barrier material, thoroughly
The fields such as luminescent material, insulating materials, acoustic material, gas barrier.Cellulose rich content, environment friend in nature with it
Good, renewable the features such as, is widely used in the fields such as food, biological medicine, packaging material.In recent years, environment and energy problem's day
Become severe, the high performance material research based on cellulosic material has obtained more widely paying close attention to.In numerous cellulosic materials, fine
The plain aeroge of dimension, because density is low, specific surface area big, is easy to store and is transported, and carries medicine, electronic device, composite etc. biological
Aspect has good application prospect.
Content of the invention
Technical problem to be solved：Nano-ZnO is little due to its particle size, and specific surface area is big, is very potential gas
Quick responsive materials, however, nano-ZnO gas sensor mainly has slug type, thick-film type, three kinds of film-type, almost to all of gas
Body has response, and gas-selectively is poor.Technical scheme：For the problems referred to above, the present invention provides a kind of new air-sensitive aeroge material
Material and preparation method thereof, described a kind of new air-sensitive aerogel material is by cellulose nano-fibrous constructing with nano zine oxide
Become, and there is meso-hole structure, wherein cellulose nano-fibrous a diameter of 20～35nm, the particle diameter of nano zine oxide is 40～
70nm, aperture is 30～50nm, and the permeability of in the air oxygen and nitrogen is 0.005～0.05mL μm of m-2day-1kPa-1, right
In the air concentration is 30～50 × 10-6Ammonia have higher sensitivity, the response time be 1～4S.
A kind of preparation method of the hydrogel with wound repair effect comprises the following steps：
1) state of aggregation cellulosic material is immersed in combination aqueous systems, combination aqueous systems by 5～8wt% NaOH, 0.5
～1.8wt% sodium zincate, 4～10wt% thiocarbamide and water composition；
2) state of aggregation cellulose is refrigerated to -5～-15 DEG C with one piece of mixture combining aqueous systems composition, then stirs
Defrosting obtains the molecular level homodisperse cellulose hydrosol；
3) by above-mentioned hydrosol casting film-forming and immerse in 16～20wt% aqueous sodium persulfate solution and bring it about sol-gel
Change；
4) hydrogel is immersed successively displacement in 20～25%, 45～50%, 70～75% and 100% tert-butyl alcohol；
5) gel rubber material after displacement is put into precooling 10～15min in -5～-10 DEG C of environment, then place in liquid nitrogen
Quickly cooling 15～30min, finally at -30～-40 DEG C, is vacuum dried under the conditions of 5～30Pa and is obtained.
Compared with the prior art relatively, marked improvement is had using technical solution of the present invention, and beneficial effect can be obtained：The present invention
Cellulose aerogels and ZnO aeroge are combined, using the interfacial interaction between cellulose and ZnO, reaches
Following effect：A) prepare that particle diameter is less and decentralization preferable ZnO particle (see accompanying drawing 1)；B) cellulose aerogels are permissible
Preferably intercept oxygen and the nitrogen of in the air, therefore, when detecting the ammonia of in the air, its sensitivity can be significantly improved.
Brief description
Fig. 1 is ESEM (SEM) image of the new air-sensitive aerogel material described in this patent.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is further illustrated.
Embodiment 1
The first step immerses cellulose cotton pulp in combination aqueous systems, combines aqueous systems by 5wt% NaOH,
0.5wt% sodium zincate, 4wt% thiocarbamide and water composition；Second step by state of aggregation cellulose and combines the mixture that aqueous systems form
One piece is refrigerated to -5 DEG C, and then stirring defrosting obtains the molecular level homodisperse cellulose hydrosol；3rd step is by above-mentioned water
Plastisol cast film forming simultaneously immerses in 16wt% aqueous sodium persulfate solution and brings it about sol-gel transition；4th step by hydrogel according to
Replace in the tert-butyl alcohol of secondary immersion 20%, 45%, 70% and 100%；Gel rubber material after replacing is put into -5 DEG C of rings by the 5th step
Precooling 10min in border, then places into quickly cooling 15min in liquid nitrogen, finally at -30 DEG C, is vacuum dried and is obtained under the conditions of 5Pa.
In prepared aeroge, cellulose nano-fibrous a diameter of 20nm, the particle diameter of nano zine oxide are 40nm, aperture
For 30nm, the permeability of in the air oxygen and nitrogen is 0.005mL μm of m-2day-1kPa-1, it is 50 × 10 in the air concentration-6
Ammonia have higher sensitivity, the response time be 1S.
Embodiment 2
The first step immerses cellulose bamboo pulp in combination aqueous systems, combines aqueous systems by 8wt% NaOH,
1.8wt% sodium zincate, 10wt% thiocarbamide and water composition；Second step by state of aggregation cellulose and combines the mixture that aqueous systems form
One piece is refrigerated to -15 DEG C, and then stirring defrosting obtains the molecular level homodisperse cellulose hydrosol；3rd step is by above-mentioned water
Plastisol cast film forming simultaneously immerses in 20wt% aqueous sodium persulfate solution and brings it about sol-gel transition；4th step by hydrogel according to
Replace in the tert-butyl alcohol of secondary immersion 25%, 50%, 75% and 100%；Gel rubber material after replacing is put into -10 DEG C of rings by the 5th step
Precooling 15min in border, then places into quickly cooling 30min in liquid nitrogen, finally at -40 DEG C, is vacuum dried and is obtained under the conditions of 30Pa.
In prepared aeroge, cellulose nano-fibrous a diameter of 35nm, the particle diameter of nano zine oxide are 70nm, aperture
For 50nm, the permeability of in the air oxygen and nitrogen is 0.05mL μm of m-2day-1kPa-1, it is 50 × 10 in the air concentration-6's
Ammonia has higher sensitivity, and the response time is 4S.
Embodiment 3
Cellulose wood pulp is immersed in combination aqueous systems by the first step, and combination aqueous systems are by 6wt% NaOH, 0.8wt%
Sodium zincate, 6wt% thiocarbamide and water composition；Second step by state of aggregation cellulose and combines one piece of freezing of mixture that aqueous systems form
To -7 DEG C, then stirring defrosting obtains the molecular level homodisperse cellulose hydrosol；The above-mentioned hydrosol is cast by the 3rd step
Film forming simultaneously immerses in 17wt% aqueous sodium persulfate solution and brings it about sol-gel transition；Hydrogel is immersed by the 4th step successively
22%th, replace in 48%, 72% and 100% tert-butyl alcohol；Gel rubber material after replacing is put into pre- in -7 DEG C of environment by the 5th step
Cold 12min, then places into quickly cooling 20min in liquid nitrogen, finally at -35 DEG C, is vacuum dried and is obtained under the conditions of 10Pa.
Cellulose nano-fibrous diameter 25nm in prepared aeroge, the particle diameter of nano zine oxide are 50nm, and aperture is
40nm, the permeability of in the air oxygen and nitrogen is 0.009mL μm of m-2day-1kPa-1, it is 40 × 10-6's in the air concentration
Ammonia has higher sensitivity, and the response time is 2S.
Embodiment 4
Cellulose wood pulp is immersed in combination aqueous systems by the first step, and combination aqueous systems are by 6wt% NaOH, 1.5wt%
Sodium zincate, 9wt% thiocarbamide and water composition；Second step by state of aggregation cellulose and combines one piece of freezing of mixture that aqueous systems form
To -9 DEG C, then stirring defrosting obtains the molecular level homodisperse cellulose hydrosol；The above-mentioned hydrosol is cast by the 3rd step
Film forming simultaneously immerses in 18wt% aqueous sodium persulfate solution and brings it about sol-gel transition；Hydrogel is immersed by the 4th step successively
22%th, replace in 44%, 73% and 100% tert-butyl alcohol；Gel rubber material after replacing is put into precooling in -8 DEG C by the 5th step
13min, then places into quickly cooling 20min in liquid nitrogen, is finally vacuum dried under the conditions of -33 DEG C, 18Pa and is obtained.
In prepared aeroge, cellulose nano-fibrous a diameter of 28nm, the particle diameter of nano zine oxide are 60nm, aperture
For 40nm, the permeability of in the air oxygen and nitrogen is 0.025mL μm of m-2day-1kPa-1, it is 45 × 10 in the air concentration-6
Ammonia have higher sensitivity, the response time be 3S.
Embodiment 5
The first step immerses state of aggregation cellulose cotton pulp in combination aqueous systems, combines aqueous systems by 6wt% NaOH,
1.6wt% sodium zincate, 9wt% thiocarbamide and water composition；Second step by state of aggregation cellulose and combines the mixture that aqueous systems form
One piece is refrigerated to -13 DEG C, and then stirring defrosting obtains the molecular level homodisperse cellulose hydrosol；3rd step is by above-mentioned water
Plastisol cast film forming simultaneously immerses in 18wt% aqueous sodium persulfate solution and brings it about sol-gel transition；4th step by hydrogel according to
Replace in the tert-butyl alcohol of secondary immersion 23%, 48%, 73% and 100%；Gel rubber material after replacing is put into -8 DEG C of rings by the 5th step
Precooling 12min in border, then places into quickly cooling 20min in liquid nitrogen, finally at -35 DEG C, is vacuum dried and is obtained under the conditions of 23Pa.
In prepared aeroge, cellulose nano-fibrous a diameter of 28nm, the particle diameter of nano zine oxide are 60nm, aperture
For 40nm, the permeability of in the air oxygen and nitrogen is 0.03mL μm of m-2day-1kPa-1, it is 45 × 10 in the air concentration-6's
Ammonia has higher sensitivity, and the response time is 2S.
Claims (3)
1. a kind of new air-sensitive aerogel material and preparation method thereof it is characterised in that：Described a kind of new air-sensitive aeroge
Material is constructed by cellulose nano-fibrous and nano zine oxide and is formed, and has meso-hole structure.A kind of described new air-sensitive airsetting
The preparation method of glue material is：State of aggregation cellulosic material is immersed in combination aqueous systems by the first step, combination aqueous systems by 5～
8wt% NaOH, 0.5～1.8wt% sodium zincate, 4～10wt% thiocarbamide and water composition；Second step is by cellulosic material and group
One piece of the mixture of Heshui system composition is refrigerated to -5～-15 DEG C, and then stirring defrosting obtains the homodisperse fibre of molecular level
The plain hydrosol of dimension；3rd step by above-mentioned hydrosol casting film-forming and immerse bring it about in 16～20wt% aqueous sodium persulfate solution molten
Glue-gel conversion；Hydrogel is immersed in 20～25%, 45～50%, 70～75% and 100% tert-butyl alcohol by the 4th step successively
Displacement；Gel rubber material after replacing is put into precooling 10～15min in -5～-10 DEG C of environment by the 5th step, then places into liquid nitrogen
Middle quickly cooling 15～30min, finally at -30～-40 DEG C, is vacuum dried under the conditions of 5～30Pa and is finally obtained.
2. as claimed in claim 1 a kind of new air-sensitive aerogel material and preparation method thereof it is characterised in that：Described airsetting
Cellulose nano-fibrous a diameter of 20～35nm in glue material construction unit, the particle diameter of nano zine oxide is 40～70nm；Institute
The aperture stating aerogel material is 30～50nm.
3. as claimed in claim 1 a kind of new air-sensitive aerogel material and preparation method thereof it is characterised in that：Described airsetting
Glue material is 0.005～0.05mL μm of m to the permeability of in the air oxygen and nitrogen-2day-1kPa-1, barriering effect preferably,
It is 30～50 × 10 therefore in the air concentration-6Ammonia have higher sensitivity, the response time be 1～4S.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446166A (en) * | 2017-09-17 | 2017-12-08 | 赵兵 | A kind of amphoteric cellulose composite of supported nano zinc oxide and preparation method thereof |
| CN107606396A (en) * | 2017-09-11 | 2018-01-19 | 福建农林大学 | A kind of core material of vacuum heat insulation plate, vacuum heat-insulating plate and preparation method thereof |
| CN110092940A (en) * | 2019-05-06 | 2019-08-06 | 南京林业大学 | High oil-absorbing micro-nano fiber aeroge, preparation method and application |
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| CN102941042A (en) * | 2012-10-25 | 2013-02-27 | 北京理工大学 | Graphene/metal oxide hybrid aerogel, preparation method and applications thereof |
| CN103709435A (en) * | 2013-12-19 | 2014-04-09 | 东北林业大学 | Preparation method of light-weight high-intensity cellulose aerogel |
| CN104941538A (en) * | 2015-06-03 | 2015-09-30 | 金承黎 | In-situ composite silicon-based multibasic oxide oxide aerogel material and preparation method thereof |
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- 2016-04-01 CN CN201610216497.XA patent/CN106397792B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941042A (en) * | 2012-10-25 | 2013-02-27 | 北京理工大学 | Graphene/metal oxide hybrid aerogel, preparation method and applications thereof |
| CN103709435A (en) * | 2013-12-19 | 2014-04-09 | 东北林业大学 | Preparation method of light-weight high-intensity cellulose aerogel |
| CN104941538A (en) * | 2015-06-03 | 2015-09-30 | 金承黎 | In-situ composite silicon-based multibasic oxide oxide aerogel material and preparation method thereof |
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| 《APPLIED MATERIALS & INTERFACES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107606396A (en) * | 2017-09-11 | 2018-01-19 | 福建农林大学 | A kind of core material of vacuum heat insulation plate, vacuum heat-insulating plate and preparation method thereof |
| CN107606396B (en) * | 2017-09-11 | 2019-07-05 | 福建农林大学 | A kind of core material of vacuum heat insulation plate, vacuum heat-insulating plate and preparation method thereof |
| CN107446166A (en) * | 2017-09-17 | 2017-12-08 | 赵兵 | A kind of amphoteric cellulose composite of supported nano zinc oxide and preparation method thereof |
| CN110092940A (en) * | 2019-05-06 | 2019-08-06 | 南京林业大学 | High oil-absorbing micro-nano fiber aeroge, preparation method and application |
| CN110092940B (en) * | 2019-05-06 | 2021-10-01 | 南京林业大学 | High-oil-absorption micro-nano fiber aerogel, and preparation method and application thereof |
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