CN106397792B - A kind of novel air-sensitive aerogel material and preparation method thereof - Google Patents
A kind of novel air-sensitive aerogel material and preparation method thereof Download PDFInfo
- Publication number
- CN106397792B CN106397792B CN201610216497.XA CN201610216497A CN106397792B CN 106397792 B CN106397792 B CN 106397792B CN 201610216497 A CN201610216497 A CN 201610216497A CN 106397792 B CN106397792 B CN 106397792B
- Authority
- CN
- China
- Prior art keywords
- air
- cellulose
- sensitive
- preparation
- aerogel material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 kind of novel air-sensitive aerogel materials and preparation method thereof.Air-sensitive aeroge is porous aerogel made of being constructed as cellulose nano-fibrous and nano zine oxide in the present invention.Preparation method of the invention：The first step immerses state of aggregation cellulosic material in combination aqueous systems；Second step by state of aggregation cellulose with combine aqueous systems composition one piece of mixture be refrigerated to -5~-15 DEG C, then stirring thaw obtains the evenly dispersed cellulose hydrosol of molecular level；Third step will bring it about sol-gel transition in above-mentioned hydrosol casting film-forming and immersion 16~20wt% aqueous sodium persulfate solution；4th step, which successively immerses hydrogel in 20~25%, 45~50%, 70~75% and 100% tert-butyl alcohol, replaces；Gel rubber material vacuum freezedrying after displacement is obtained porous aerogel by the 5th step.The present invention combines cellulose aerogels and ZnO aeroge, improves sensitivity when detection ammonia.
Description
Invention field
The present invention relates to technical field of composite materials, more particularly it relates to a kind of novel air-sensitive aerogel material
And preparation method thereof.
Technical background
Nano-ZnO is the gas sensitive used earliest, with widely used nano SnO2It compares, its working principle is that a mould
The same, but its detection sensitivity ratio SnO2It is low.In addition to this also have many advantages, such as cheap, 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 gas
Difference.In use, often requiring that the selectivity that device has had in life and production, this just hinders the city of nano-ZnO gas sensitive device
Fieldization, scale are its future development urgent problems to be solved.
Aeroge is a kind of porous material with nanostructure, and porosity is up to 90% or more, and density is minimum can be extremely
0.001g/cm3, it is most light one of solid material in the world at present.It differs markedly from hole configurations in micron and grade
Porous material, have great specific surface area.Due to its distinctive nanoporous, three-dimensional net structure, many is made it have
Unique performance especially shows high porosity, low-density, lower thermal conductivity etc., can be widely applied to heat-barrier material, thoroughly
The fields such as luminescent material, insulating materials, acoustic material, gas barrier.Rich content, environment are friendly in nature with it for cellulose
The features such as good, renewable, is widely used in the fields such as food, biological medicine, packaging material.In recent years, environment and energy problem day
Become severe, the high performance material based on cellulosic material studies to have obtained more extensive concern.It is fine in numerous cellulosic materials
Plain aeroge is tieed up since density is low, large specific surface area, convenient for storage and transport, carries medicine, electronic device, composite material etc. in biology
Aspect has good application prospect.
Summary of the invention
Technical problems to be solved：Nano-ZnO is since its particle size is small, large specific surface area, 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 gas
Body has response, and gas-selectively is poor.Technical solution：In view of the above-mentioned problems, the present invention provides a kind of novel air-sensitive aeroge material
Material and preparation method thereof, a kind of novel air-sensitive aerogel material constructed by cellulose nano-fibrous and nano zine oxide and
At, and there is meso-hole structure, wherein cellulose nano-fibrous diameter is 20~35nm, the partial size of nano zine oxide is 40~
70nm, aperture are 30~50nm, and the permeability of oxygen and nitrogen is 0.005~0.05mL μm of m in air-2day-1kPa-1, right
Concentration is 30~50 × 10 in air-6Ammonia have higher sensitivity, the response time is 1~4S.
A kind of preparation method with the hydrogel of wound repair includes the following steps：
1) state of aggregation cellulosic material being immersed in combination aqueous systems, combination aqueous systems are by 5~8wt% sodium hydroxide, and 0.5
~1.8wt% sodium zincate, 4~10wt% thiocarbamide and water composition；
2) by state of aggregation cellulose with combine aqueous systems composition one piece of mixture be refrigerated to -5~-15 DEG C, then stir
Defrosting obtains the evenly dispersed cellulose hydrosol of molecular level；
3) sol-gel will be brought it about in above-mentioned hydrosol casting film-forming and immersion 16~20wt% aqueous sodium persulfate solution
Transformation；
4) hydrogel is successively immersed in 20~25%, 45~50%, 70~75% and 100% tert-butyl alcohol and is replaced；
5) gel rubber material after displacement is put into 10~15min of pre-cooling in -5~-10 DEG C of environment, then placed into liquid nitrogen
15~30min of quickly cooling is dried in vacuo under the conditions of 5~30Pa and is made finally at -30~-40 DEG C.
Compare with the existing technology has marked improvement using technical solution of the present invention, and can obtain beneficial effect：The present invention
Cellulose aerogels and ZnO aeroge are combined, using the interfacial interaction between cellulose and ZnO, are reached
Following effect：A) it is prepared that partial size is smaller and the preferable ZnO particle of dispersion degree (see attached drawing 1)；B) cellulose aerogels can be with
Therefore oxygen and nitrogen in preferable barrier air when detecting the ammonia in air, can significantly improve its sensitivity.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) image of novel air-sensitive aerogel material described in this patent.
Specific embodiment
Technical solution of the present invention is further explained below in conjunction with specific embodiment.
Embodiment 1
The first step immerses cellulose cotton pulp in combination aqueous systems, combination aqueous systems by 5wt% sodium hydroxide,
0.5wt% sodium zincate, 4wt% thiocarbamide and water composition；Second step by state of aggregation cellulose and combine aqueous systems composition mixture
One piece is refrigerated to -5 DEG C, and then stirring, which is thawed, obtains the evenly dispersed cellulose hydrosol of molecular level；Third step is by above-mentioned water
Plastisol cast, which forms a film and immerses in 16wt% aqueous sodium persulfate solution, brings it about sol-gel transition；4th step by hydrogel according to
It is replaced in the tert-butyl alcohol of secondary immersion 20%, 45%, 70% and 100%；Gel rubber material after displacement is put into -5 DEG C of rings by the 5th step
10min is pre-chilled in border, then places into quickly cooling 15min in liquid nitrogen, is finally dried in vacuo and is made under the conditions of -30 DEG C, 5Pa.
Cellulose nano-fibrous diameter is 20nm in aeroge obtained, the partial size of nano zine oxide is 40nm, aperture
For 30nm, the permeability of oxygen and nitrogen is 0.005mL μm of m in air-2day-1kPa-1, it is 50 × 10 to concentration in air-6
Ammonia have higher sensitivity, response time 1S.
Embodiment 2
The first step immerses cellulose bamboo pulp in combination aqueous systems, combination aqueous systems by 8wt% sodium hydroxide,
1.8wt% sodium zincate, 10wt% thiocarbamide and water composition；Second step by state of aggregation cellulose and combine aqueous systems composition mixture
One piece is refrigerated to -15 DEG C, and then stirring, which is thawed, obtains the evenly dispersed cellulose hydrosol of molecular level；Third step is by above-mentioned water
Plastisol cast, which forms a film and immerses in 20wt% aqueous sodium persulfate solution, brings it about sol-gel transition；4th step by hydrogel according to
It is replaced in the tert-butyl alcohol of secondary immersion 25%, 50%, 75% and 100%；Gel rubber material after displacement is put into -10 DEG C of rings by the 5th step
15min is pre-chilled in border, then places into quickly cooling 30min in liquid nitrogen, is finally dried in vacuo and is made under the conditions of -40 DEG C, 30Pa.
Cellulose nano-fibrous diameter is 35nm in aeroge obtained, the partial size of nano zine oxide is 70nm, aperture
For 50nm, the permeability of oxygen and nitrogen is 0.05mL μm of m in air-2day-1kPa-1, it is 50 × 10 to concentration in air-6's
Ammonia has higher sensitivity, response time 4S.
Embodiment 3
The first step immerses cellulose wood pulp in combination aqueous systems, combines aqueous systems by 6wt% sodium hydroxide, 0.8wt%
Sodium zincate, 6wt% thiocarbamide and water composition；Second step by state of aggregation cellulose and combine aqueous systems composition one piece of mixture freezing
To -7 DEG C, then stirring, which is thawed, obtains the evenly dispersed cellulose hydrosol of molecular level；The above-mentioned hydrosol is cast by third step
It forms a film and immerses in 17wt% aqueous sodium persulfate solution and bring it about sol-gel transition；4th step successively immerses hydrogel
22%, it is replaced in 48%, 72% and 100% tert-butyl alcohol；Gel rubber material after displacement is put into -7 DEG C of environment in advance by the 5th step
Then cold 12min places into quickly cooling 20min in liquid nitrogen, be finally dried in vacuo and be made under the conditions of -35 DEG C, 10Pa.
Cellulose nano-fibrous diameter 25nm in aeroge obtained, nano zine oxide partial size be 50nm, aperture is
40nm, the permeability of oxygen and nitrogen is 0.009mL μm of m in air-2day-1kPa-1, it is 40 × 10-6's to concentration in air
Ammonia has higher sensitivity, response time 2S.
Embodiment 4
The first step immerses cellulose wood pulp in combination aqueous systems, combines aqueous systems by 6wt% sodium hydroxide, 1.5wt%
Sodium zincate, 9wt% thiocarbamide and water composition；Second step by state of aggregation cellulose and combine aqueous systems composition one piece of mixture freezing
To -9 DEG C, then stirring, which is thawed, obtains the evenly dispersed cellulose hydrosol of molecular level；The above-mentioned hydrosol is cast by third step
It forms a film and immerses in 18wt% aqueous sodium persulfate solution and bring it about sol-gel transition；4th step successively immerses hydrogel
22%, it is replaced in 44%, 73% and 100% tert-butyl alcohol；Gel rubber material after displacement is put into -8 DEG C by the 5th step to be pre-chilled
Then 13min places into quickly cooling 20min in liquid nitrogen, be finally dried in vacuo and be made under the conditions of -33 DEG C, 18Pa.
Cellulose nano-fibrous diameter is 28nm in aeroge obtained, the partial size of nano zine oxide is 60nm, aperture
For 40nm, the permeability of oxygen and nitrogen is 0.025mL μm of m in air-2day-1kPa-1, it is 45 × 10 to concentration in air-6
Ammonia have higher sensitivity, response time 3S.
Embodiment 5
The first step immerses state of aggregation cellulose cotton pulp in combination aqueous systems, combination aqueous systems by 6wt% sodium hydroxide,
1.6wt% sodium zincate, 9wt% thiocarbamide and water composition；Second step by state of aggregation cellulose and combine aqueous systems composition mixture
One piece is refrigerated to -13 DEG C, and then stirring, which is thawed, obtains the evenly dispersed cellulose hydrosol of molecular level；Third step is by above-mentioned water
Plastisol cast, which forms a film and immerses in 18wt% aqueous sodium persulfate solution, brings it about sol-gel transition；4th step by hydrogel according to
It is replaced in the tert-butyl alcohol of secondary immersion 23%, 48%, 73% and 100%；Gel rubber material after displacement is put into -8 DEG C of rings by the 5th step
12min is pre-chilled in border, then places into quickly cooling 20min in liquid nitrogen, is finally dried in vacuo and is made under the conditions of -35 DEG C, 23Pa.
Cellulose nano-fibrous diameter is 28nm in aeroge obtained, the partial size of nano zine oxide is 60nm, aperture
For 40nm, the permeability of oxygen and nitrogen is 0.03mL μm of m in air-2day-1kPa-1, it is 45 × 10 to concentration in air-6's
Ammonia has higher sensitivity, response time 2S.
Claims (3)
1. a kind of preparation method of air-sensitive aerogel material, it is characterised in that：A kind of air-sensitive aerogel material is by fiber
Plain nanofiber and nano zine oxide are constructed, and have meso-hole structure；A kind of preparation side of the air-sensitive aerogel material
Method is：The first step immerses state of aggregation cellulosic material in combination aqueous systems, combination aqueous systems by 5~8wt% sodium hydroxide,
0.5~1.8wt% sodium zincate, 4~10wt% thiocarbamide and water composition；Second step forms state of aggregation cellulose with aqueous systems are combined
One piece of mixture be refrigerated to -5~-15 DEG C, then stirring thaw obtains the evenly dispersed cellulose hydrosol of molecular level；The
Three steps will bring it about sol-gel transition in above-mentioned hydrosol casting film-forming and immersion 16~20wt% aqueous sodium persulfate solution；
4th step, which successively immerses hydrogel in the tert-butyl alcohol for 25%, 50%, 75% and 100%, replaces；5th step will be after displacement
Gel rubber material is put into 10~15min of pre-cooling in -5~-10 DEG C, then places into 15~30min of quickly cooling in liquid nitrogen, last -30~-
40 DEG C, final be made is dried in vacuo under the conditions of 5~30Pa.
2. a kind of preparation method of air-sensitive aerogel material as described in claim 1, it is characterised in that：The aerogel material
Cellulose nano-fibrous diameter is 20~35nm in construction unit, the partial size of nano zine oxide is 40~70nm；The airsetting
The aperture of glue material is 30~50nm.
3. a kind of preparation method of air-sensitive aerogel material as described in claim 1, it is characterised in that：The aerogel material
Permeability to oxygen in air and nitrogen is 0.005~0.05mL μm of m-2·day-1·kPa-1, it is to concentration in air
30~50 × 10-6Ammonia have higher sensitivity, the response time is 1~4s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610216497.XA CN106397792B (en) | 2016-04-01 | 2016-04-01 | A kind of novel air-sensitive aerogel material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610216497.XA CN106397792B (en) | 2016-04-01 | 2016-04-01 | A kind of novel air-sensitive aerogel material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106397792A CN106397792A (en) | 2017-02-15 |
| CN106397792B true CN106397792B (en) | 2018-11-30 |
Family
ID=58005374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610216497.XA Expired - Fee Related CN106397792B (en) | 2016-04-01 | 2016-04-01 | A kind of novel air-sensitive aerogel material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106397792B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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 |
-
2016
- 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 |
Non-Patent Citations (1)
| Title |
|---|
| Feiya Fu et al..Construction of Cellulose Based ZnO Nanocomposite Films with Antibacterial Properties through One-Step Coagulation.《Applied Materials & Interfaces》.2015,第7卷(第4期),第2597-2606页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106397792A (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106397792B (en) | A kind of novel air-sensitive aerogel material and preparation method thereof | |
| JP7015586B2 (en) | Absorption-insulation integrated photothermal evaporation material and its preparation method and application | |
| CN105845872A (en) | Coating slurry for bonding lithium battery separator and pole piece and preparation method of coating slurry | |
| CN104505484B (en) | A kind of organo-mineral complexing dielectric film, its preparation method and application | |
| Zhao et al. | Enhanced solar evaporation efficiency based on the inserted preheating zone of silver nanowires | |
| CN107746055A (en) | A kind of new method of the preparation of the multi-stage porous carbon nanometer sheet of nitrogen sulphur codope | |
| CN108128768A (en) | The graphene of bionical laminated construction-carbon quantum dot composite heat-conducting film and its preparation | |
| Feng et al. | An efficient torrefaction Bamboo-based evaporator in interfacial solar steam generation | |
| CN109292760A (en) | A method of preparing graphene | |
| CN104295861A (en) | Low-thermal-bridge vacuum insulated panel | |
| CN106710878B (en) | One kind having high energy storage density solid dielectric capacitor and preparation method thereof | |
| Zhu et al. | Wood nanotechnology: a more promising solution toward energy issues: a mini-review | |
| Xu et al. | Preparation and performance of shape-stable phase change materials based on carbonized-abandoned orange peel and paraffin | |
| CN114226190B (en) | Photo-thermal condensation failure resistant super-hydrophobic surface with multi-layer structure and preparation method thereof | |
| CN105754276A (en) | Polymer film material with temperature fluorescence response and preparation method of polymer film material | |
| CN105810444A (en) | Graphene-polypyrrole nanoparticle composite film electrode and preparation method thereof | |
| Zou et al. | Highly safe, durable, adaptable, and flexible fuel cell using gel/sponge composite material | |
| CN105329947A (en) | Preparation method of nano-manganese oxide of flocculent structure | |
| CN202809874U (en) | Anti-scratch and anti-pierce standard temperature and pressure (STP) insulation board | |
| CN105321727A (en) | Preparation method for net-laminated porous carbon/graphene composite electrode material for supercapacitor | |
| CN202466870U (en) | Ultra-thin vacuum heat-isolation heat-insulation plate | |
| CN106098403B (en) | A kind of ultracapacitor, cathode and preparation method thereof | |
| Zhang et al. | Innovative mushroom-like hemp-based evaporators enhanced by biochar for efficient seawater desalination | |
| CN207875042U (en) | A kind of multi-functional PET film | |
| CN204284804U (en) | A kind of vacuum heat-insulating plate of low-thermal-bridge |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181130 Termination date: 20190401 |