CN106732809A - With the cellulose nano-fibrous aeroge for template preparation and preparation method and application - Google Patents
With the cellulose nano-fibrous aeroge for template preparation and preparation method and application Download PDFInfo
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- CN106732809A CN106732809A CN201611075872.XA CN201611075872A CN106732809A CN 106732809 A CN106732809 A CN 106732809A CN 201611075872 A CN201611075872 A CN 201611075872A CN 106732809 A CN106732809 A CN 106732809A
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- aeroge
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- fibrous
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 52
- 239000001913 cellulose Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title description 10
- 238000012545 processing Methods 0.000 claims abstract description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004108 freeze drying Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000007790 solid phase Substances 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 238000003911 water pollution Methods 0.000 claims abstract description 15
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000010865 sewage Substances 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 235000015165 citric acid Nutrition 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001739 density measurement Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012814 acoustic material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of in the cellulose nano-fibrous method that aeroge is prepared for template, comprise the following steps：S101：It is added to the water cellulose nano-fibrous, ultrasonic wave decentralized processing is carried out after stirring；S102：To butyl titanate, urea and citric acid is added in the product after ultrasonic wave decentralized processing in S101,1h 100h are reacted after stirring；S103：By reacted product centrifugal treating, solid phase is collected；Solid phase is mixed with water, ultrasonic wave decentralized processing is carried out afterwards；S104：By the product freeze-drying after ultrasonic disperse treatment in S103, aeroge is obtained.The present invention provide in the cellulose nano-fibrous method that aeroge is prepared for template, can prepare with big specific surface area, draw ratio high, extremely-low density and with excellent photocatalytic degradation Organic Compound can aeroge, such that it is able to be efficiently applied in the processing procedure of water pollution.
Description
Technical field
The present invention relates to aeroge technical field, and in particular to it is a kind of with it is cellulose nano-fibrous be template prepare airsetting
Glue and preparation method and application.
Background technology
In recent years, the fast development of blast growth and the industry of population has all greatly accelerated the consumption of energy, and to fragility
Environment bring white elephant.How effectively to solve environmental pollution and turned into the mankind currently to face most one of stern challenge.
For example：More and more reported along with water pollution problems, the improvement of water pollution has become modern society one must
The improvement aspect of few topic, especially dirty Organic substance in water.Conventional water pollution processing method is based on activated carbon at present
Pollutant is adsorbed, and the method is only limitted to pollutant transfer and pollution control effect is poor.Therefore, a kind of row is needed badly
Effective artificial treatment polluter method, effectively to solve the current serious water pollution problems for facing.
Cellulose, as natural polymer most ancient, most abundant on the earth, is inexhaustible, is the mankind
Most valuable natural reproducible resource；Its as most common organic polymer in nature, based on its good bio-compatible
Property, degradability and hydrophily, the field such as pharmacy, treatment crude oil leakage, the acoustic material for preparing green have it is very big should
Use prospect.Therefore, if cellulose can be used in the governance process of water pollution, it will largely alleviate severe at present
Water pollution problems.
The content of the invention
For defect of the prior art, the present invention is intended to provide it is a kind of with it is cellulose nano-fibrous be gas prepared by template
Gel and preparation method and application, to prepare with bigger serface, high length-diameter ratio, extremely-low density and urge with excellent light
Change the aeroge of degradation of organic substances performance, such that it is able to be efficiently applied in the processing procedure of water pollution.
Therefore, the present invention provides following technical scheme：
In a first aspect, the present invention provides a kind of in the cellulose nano-fibrous method that aeroge is prepared for template, including with
Lower step：S101：It is added to the water cellulose nano-fibrous, ultrasonic wave decentralized processing is carried out after stirring；S102：To S101
Butyl titanate, urea and citric acid are sequentially added in product after middle ultrasonic wave decentralized processing, 1h- is reacted after stirring
100h；S103：By reacted product centrifugal treating, solid phase is collected；Solid phase and water are pressed 1：100-1：1000 weight is than mixed
Close, ultrasonic wave decentralized processing is carried out afterwards；S104：By the product freeze-drying after ultrasonic disperse treatment in S103, airsetting is obtained
Glue.
Wherein, it is added to the water cellulose nano-fibrous, ultrasonic wave decentralized processing is carried out after stirring, obtains cellulose
Nanofiber colloidal solution；Butyl titanate, urea and citric acid are subsequently adding, 1h-100h are reacted after stirring, i.e., low
Prepared under warm water heat condition and loaded the cellulose nano-fibrous of nano titanium oxide；Butyl titanate, urea and citric acid
It is preferred that sequentially adding.What afterwards prepared by cleaning has loaded the cellulose nano-fibrous of nano titanium oxide, to remove low-temperature hydrothermal
During ion, solid phase and water are pressed 1：100-1：1000 weight carries out ultrasonic wave decentralized processing afterwards than mixing, will
The cellulose nano-fibrous of nano titanium oxide that loaded after cleaning is dispersed into uniform colloidal solution；Last freeze-drying is obtained
To the cellulose nano-fibrous aeroge for having loaded nano titanium oxide.Specifically, ultrasonic wave decentralized processing is preferably in ultrasound
Carried out in ripple cell crushing instrument.Furthermore, it is necessary to explanation, the water used in the present invention, can be pure water, distilled water, go
Ionized water and ultra-pure water etc..
In further embodiment of the invention, cellulose nano-fibrous and butyl titanate, urea and citric acid
Weight ratio be 1：(0.001-10)：(0.001-10)：(0.001-10).Preferably, the cellulose nano-fibrous and fourth of metatitanic acid four
The weight ratio of ester, urea and citric acid is 1：(0.1-10)：(0.1-10)：(0.1-10).
In further embodiment of the invention, in S101, the condition of ultrasonic wave decentralized processing is：Temperature is 0 DEG C -10
DEG C, the time is 10min-1000min, and ultrasonic power is 100W-500W；In product after ultrasonic wave decentralized processing, cellulose is received
The mass percentage concentration of rice fiber is less than or equal to 10%.
In further embodiment of the invention, in S102, reaction carry out in a kettle., and the reaction temperature
It is 25 DEG C -220 DEG C.Specifically, reactor is preferably autoclave, and the temperature of reaction is preferably 100 DEG C -220 DEG C.
In further embodiment of the invention, in S103, centrifugal treating is specially：Reacted product is existed
5-10min is centrifuged under conditions of 2000-8000rpm.Wherein, reacted product is centrifuged under conditions of 2000-8000rpm
5-10min, i.e. centrifuge washing, the purpose of the step be remove that hydrothermal reaction at low temperature prepares loaded nano titanium oxide
Nano-cellulose nanofiber in ion.Specifically, in practical operation, the number of times of centrifuge washing is preferably 3-5 times.
In further embodiment of the invention, in S103, the condition of ultrasonic wave decentralized processing is：Temperature is 0 DEG C -10
DEG C, the time is 1min-100min, and ultrasonic power is 10W-100W.
In further embodiment of the invention, in S104, the condition of freeze-drying is：Temperature is -80 DEG C -0 DEG C, pressure
Power is 0-50 μ pa, and the time is 1d-7d.Wherein, freeze-drying is carried out in vacuum freeze drier, by vacuum sublimation, is obtained
Aeroge needed for the present invention.
In further embodiment of the invention, in S104, freeze-drying is specially：Product after ultrasonic disperse is processed
Thing is in pre-freeze 10h-15h at -15 DEG C -0 DEG C；Then in temperature it is -80 DEG C -0 DEG C by the product after pre-freeze 10h-15h, pressure is
0-50 μ pa, the time be 1d-7d under conditions of carry out freeze-drying.
Second aspect, the aeroge that the method provided according to the present invention is prepared.The aeroge have bigger serface,
High length-diameter ratio, extremely-low density and with excellent photocatalytic degradation Organic Compound energy, can be efficiently applied to the treatment of water pollution
During, so as to solve increasingly serious water pollution problems.
The third aspect, the aeroge for preparing of method provided according to the present invention is especially degraded dirt in degraded water pollution
Application in terms of Organic substance in water pollution.
The above-mentioned technical proposal that the present invention is provided has advantages below：
(1) applicant has found by carefully research：Use the present invention offer with it is cellulose nano-fibrous be template prepare
, well can be supported on cellulose nano-fibrous titanium dioxide by the method for aeroge, obtain load nano-titanium dioxide
Cellulose nano-fibrous aeroge；Easily reunite in use so as to effectively prevent traditional titanium dioxide, and increase
Plus titanium dioxide size can reduce its specific surface area again, so that the defect that catalysis activity is accordingly reduced.
(2) use the present invention offer in the cellulose nano-fibrous method that aeroge is prepared for template, can prepare
Aeroge with excellent photocatalytic degradation Organic Compound energy, water pollution is administered especially such that it is able to be effectively applied to
It is the Organic Pollution aspect in degraded sewage.
(3) aeroge that the method provided using the present invention is prepared has good pattern, big specific surface area, height
Draw ratio and extremely-low density.
(4) freeze-drying provided using the present invention, it is possible to prevente effectively from aeroge skeleton is collapsed and aeroge
Rupture, obtains bigger serface, high length-diameter ratio, extremely-low density and the airsetting with excellent photocatalytic degradation Organic Compound energy
Glue.
(5) present invention provide preparation method it is simple to operate, be easy to operate and control；And it is with low cost, it is easy to it is extensive
Production.
Brief description of the drawings
Fig. 1 is the flow chart in the cellulose nano-fibrous method that aeroge is prepared for template in the embodiment of the present invention；
Fig. 2 is the macrograph of the aeroge in the embodiment of the present invention；
Fig. 3 is the elementary analysis figure of the aeroge in the embodiment of the present invention；
Fig. 4 is the scanning electron microscope diagram of the aeroge in the embodiment of the present invention；
Fig. 5 is the high power transmission microscopy figure of the aeroge in the embodiment of the present invention；
Fig. 6 is the grain size distribution of the aeroge in the embodiment of the present invention.
Specific embodiment
The embodiment of technical solution of the present invention is described in detail below in conjunction with accompanying drawing.Following examples are only used for
Technical scheme is more clearly illustrated, therefore is only used as example, and protection model of the invention can not be limited with this
Enclose.
Experimental technique in following embodiments, unless otherwise specified, is conventional method.
Test material used in following embodiments, unless otherwise specified, is what is be commercially available from conventional reagent shop.
Quantitative test in following examples, is respectively provided with three repetitions and tests, and data are three average values of repetition experiment
Or mean+SD.
The present invention provide it is a kind of in the cellulose nano-fibrous method that aeroge is prepared for template, as shown in figure 1, including with
Lower step：
S101：It is added to the water cellulose nano-fibrous, ultrasonic wave decentralized processing is carried out after stirring.Wherein, S101
In, the condition of ultrasonic wave decentralized processing is：Temperature is 0 DEG C -10 DEG C, and the time is 10min-1000min, and ultrasonic power is 100W-
500W；In product after ultrasonic wave decentralized processing, cellulose nano-fibrous mass percentage concentration is less than or equal to 10%.
Be added to the water cellulose nano-fibrous, after stirring under conditions of 0 DEG C -10 DEG C ultrasonic wave decentralized processing
10min-1000min, obtains cellulose nano-fibrous colloidal solution.Specifically, ultrasonic wave decentralized processing is preferably thin in ultrasonic wave
Carried out in the broken instrument of born of the same parents.
S102：To butyl titanate, urea and citric acid is added in the product after ultrasonic wave decentralized processing in S101, stir
Reaction 1h-100h after uniform.Wherein, the cellulose nano-fibrous weight ratio with butyl titanate, urea and citric acid is 1：
(0.001-10)：(0.001-10)：(0.001-10)；Reaction carry out in a kettle., and the reaction temperature for 25 DEG C-
220℃.In this step, butyl titanate, urea and citric acid are sequentially added, using reactor, in 25 DEG C -220 DEG C of bar
1h-100h is reacted under part, i.e., is prepared under the conditions of low-temperature hydrothermal and has been loaded the cellulose nano-fibrous of nano titanium oxide.Tool
Body ground, reactor is preferably autoclave.
S103：By reacted product centrifugal treating, solid phase is collected；Solid phase and water are pressed 1：100-1：1000 weight ratio
Mixing, carries out ultrasonic wave decentralized processing afterwards.Wherein, centrifugal treating is specially：By reacted product in 2000-8000rpm
Under conditions of 5-10min is centrifuged；The condition of ultrasonic wave decentralized processing is：Temperature is 0 DEG C -10 DEG C, and the time is 1min-100min,
Ultrasonic power is 10W-100W.
In this step, what prepared by cleaning has loaded the cellulose nano-fibrous of nano titanium oxide, by reacted product
Thing is centrifuged 5-10min, i.e. centrifuge washing under conditions of 2000-8000rpm, and the purpose of the step is to remove hydrothermal reaction at low temperature
Ion in the nano-cellulose nanofiber for having loaded nano titanium oxide for preparing.Specifically, in practical operation,
The number of times of centrifuge washing is preferably 3-5 times.Solid phase after centrifuge washing is taken, and 1 is pressed with water：100-1：1000 weight ratio mixing,
Afterwards temperature be 0 DEG C -10 DEG C, power be 10W-100W under conditions of use ultrasonic wave decentralized processing 1min-100min, Ji Jiangqing
The cellulose nano-fibrous of nano titanium oxide that loaded after washing is dispersed into uniform colloidal solution.
S104：By the product freeze-drying after ultrasonic disperse treatment in S103.Wherein, the condition of freeze-drying is：Temperature
It it is -80 DEG C -0 DEG C, pressure is 0-50 μ pa, and the time is 1d-7d.
In this step, the cellulose nano-fibrous airsetting for having loaded nano titanium oxide is prepared by freeze-drying
Glue.In order to avoid its inner skeleton structure is collapsed in aeroge preparation process, traditionally using the method for supercritical drying.
But, although supercritical fluid can avoid being coagulated in drying process as a kind of fluid that can effectively eliminate capillary force
The contraction of glue skeleton, but the high cost of supercritical drying and the dangerous large-scale production that significantly limit aerogel material
Using.Therefore, the present invention uses freeze-drying dry aerogels, can obtain each under conditions of properties of aerogels is not damaged
The relatively good aeroge of aspect property.
Preferably, in S104, freeze-drying is specially：Product after ultrasonic disperse is processed is in pre-freeze at -15 DEG C -0 DEG C
10h-15h；Then by the product after pre-freeze 10h-15h temperature be -80 DEG C -0 DEG C, pressure be 0-50 μ pa, the time is 1d-7d
Under conditions of carry out freeze-drying.Product after ultrasonic disperse is processed is in pre-freeze 10h-15h at -10 DEG C -0 DEG C；Then will be pre-
Freeze 10h-15h after product temperature be -80 DEG C -0 DEG C, pressure be 0-50 μ pa, the time be 1d-7d under conditions of freezed
Dry, it is possible to prevente effectively from the rupture collapsed with aeroge of aeroge skeleton, so as to obtain with bigger serface, major diameter high
Than, extremely-low density and with excellent photocatalytic degradation Organic Compound can aeroge.
Illustrated with reference to specific embodiment.
Embodiment one
It is a kind of in the cellulose nano-fibrous method that aeroge is prepared for template, comprise the following steps：
S101：In the cellulose nano-fibrous addition 100ml water of 0.1g, will stir after temperature be 5 DEG C, power be
Ultrasonic wave decentralized processing 50min under conditions of 300W.
S102：Sequentially added in product after ultrasonic wave decentralized processing 50min in S101 0.5ml butyl titanates,
0.3g urea and 0.5g citric acids, to stir and react 10h under conditions of being 150 DEG C in temperature in autoclave.
S103：To react after the product after 10h is centrifuged 6min under conditions of 3000rpm and remove liquid phase；In centrifugation 6min
Remove afterwards and add isometric water in the product after liquid phase, be centrifuged 5min under conditions of 2000rpm, collect solid phase；Will
Solid phase presses 1 with water：500 weight than mixing, after temperature be 3 DEG C, power be 60W under conditions of ultrasonic wave decentralized processing
100min。
S104：It it is -50 DEG C in temperature by the product after ultrasonic disperse treatment 100min in S103, pressure is the bar of 0.5 μ pa
Freeze-drying 5d under part；Aeroge needed for finally giving the present invention.The macrograph of the aeroge that Fig. 2 is obtained for the present embodiment.
Embodiment two
It is a kind of in the cellulose nano-fibrous method that aeroge is prepared for template, comprise the following steps：
S101：In the cellulose nano-fibrous addition 90ml water of 0.05g, will stir after temperature be 8 DEG C, power be
Ultrasonic wave decentralized processing 200min under conditions of 500W.
S102：Sequentially added in product after ultrasonic wave decentralized processing 200min in S101 0.2ml butyl titanates,
0.1g urea and 0.5g citric acids, to stir and react 1h under conditions of being 200 DEG C in temperature in autoclave.
S103：To react after the product after 1h is centrifuged 5min under conditions of 3500rpm and remove liquid phase；After 5min is centrifuged
Remove liquid phase after product in add isometric water washing, 3min is centrifuged under conditions of 3000rpm, the washing process
Repeat 5 times, solid phase is collected in last centrifugation；Solid phase and water are pressed 1：100 weight than mixing, after temperature be 0
DEG C, power be 100W under conditions of ultrasonic wave decentralized processing 100min.
S104：It it is -80 DEG C in temperature by the product after ultrasonic disperse treatment 500min in S103, pressure is the bar of 50 μ pa
Freeze-drying 7d under part；Aeroge needed for finally giving the present invention.
Fig. 3 is the elementary analysis figure of the aeroge in the present embodiment, it can be seen that the side provided using the present invention
What method was prepared has loaded the cellulose nano-fibrous aeroge of nano titanium oxide, in the absence of other impurities.
Embodiment three
It is a kind of in the cellulose nano-fibrous method that aeroge is prepared for template, comprise the following steps：
S101：In the cellulose nano-fibrous addition 99ml water of 0.2g, will stir after temperature be 9 DEG C, power be
Ultrasonic wave decentralized processing 10min under conditions of 100W.
S102：2ml butyl titanates, 0.9g are sequentially added in product after ultrasonic wave decentralized processing 10min in S101
Urea and 1g citric acids, to stir and react 100h under conditions of being 125 DEG C in temperature in autoclave.
S103：To react after the product after 100h is centrifuged 10min under conditions of 2000rpm and remove liquid phase；In centrifugation
After 10min remove liquid phase after product in add isometric water washing, 3min is centrifuged under conditions of 3500rpm, should
Washing process repeats 3 times, and solid phase is collected in last centrifugation；Solid phase and water are pressed 1：600 weight than mixing, after
Temperature is 3 DEG C, power is ultrasonic wave decentralized processing 50min under conditions of 10W.
S104：It it is -5 DEG C in temperature by the product after ultrasonic disperse treatment 50min in S103, pressure is the condition of 30 μ pa
Lower freeze-drying 3d；Aeroge needed for finally giving the present invention.
Example IV
It is a kind of in the cellulose nano-fibrous method that aeroge is prepared for template, comprise the following steps：
S101：In the cellulose nano-fibrous addition 90ml water of 0.05g, will stir after temperature be 8 DEG C, power be
Ultrasonic wave decentralized processing 200min under conditions of 500W.
S102：Sequentially added in product after ultrasonic wave decentralized processing 200min in S101 0.2ml butyl titanates,
0.1g urea and 0.5g citric acids, to stir and react 1h under conditions of being 200 DEG C in temperature in autoclave.
S103：To react after the product after 1h is centrifuged 5min under conditions of 3500rpm and remove liquid phase；After 5min is centrifuged
Remove liquid phase after product in add isometric water washing, 3min is centrifuged under conditions of 3000rpm, the washing process
Repeat 5 times, solid phase is collected in last centrifugation；Solid phase and water are pressed 1：100 weight than mixing, after temperature be 0
DEG C, power be 100W under conditions of ultrasonic wave decentralized processing 100min.
S104：By in S103 ultrasonic disperse treatment 500min after product at -5 DEG C pre-freeze 13h, then temperature for -
80 DEG C, pressure is freeze-drying 7d under conditions of 50 μ pa；Aeroge needed for finally giving the present invention.Fig. 4 is in the present embodiment
Aeroge scanning electron microscope diagram；Fig. 5 is the high power transmission microscopy figure of the aeroge in the present embodiment；Fig. 6 is this
The grain size distribution of the aeroge in embodiment.
In addition, in order to further verify the cellulose Nanowire for having loaded nano titanium oxide that the embodiment of the present invention is obtained
The property of the aeroge of dimension, following test is carried out to it：
(1) specific surface area, draw ratio and density measurement
Specific surface area, draw ratio and density measurement are carried out to the aeroge that embodiment one to example IV is prepared, is had
Volume data is as shown in table 1：
The property list of aeroge in each embodiment of table 1
| Specific surface area (㎡/g) | Draw ratio | Density (mg/cm3) | |
| Embodiment one | 135 | 2500 | 2 |
| Embodiment two | 125 | 3000 | 1 |
| Embodiment three | 105 | 1000 | 4 |
| Example IV | 118 | 4000 | 1 |
As can be seen here, the preparation method that the present invention is provided, can prepare with bigger serface, high length-diameter ratio and surpass
The aeroge of low-density.
(2) degradation property test
Test method：Methylene blue is added to the water, the solution that concentration is 15ppm is configured to, 30ml is then taken and is surveyed
Examination；Specifically, the aeroge for adding 10mg embodiments one to prepare in the solution, using photochemical reaction instrument in 1000W
Uviol lamp under irradiate, the absorbance of solution is detected after 10 minutes using ultraviolet-uisible spectrophotometer, and calculate methylene
Blue degradation rate.Ibid, the degradation rate of each embodiment is specifically as shown in table 2 for method of testing in embodiment two to example IV.
The degradation rate of each embodiment Methylene Blue of table 2
| Embodiment one | Embodiment two | Embodiment three | Example IV | |
| 20min degradation rates/% | 87 | 56 | 98 | 63 |
| 30min degradation rates/% | 97 | 89 | 99.9 | 91 |
As can be seen here, the present invention provide with the cellulose nano-fibrous aeroge prepared for template, can be effective
Degradation of methylene blue；And methylene blue is widely present in sewage as the important pollutant in sewage, therefore, the present invention is obtained
Aeroge can be effective for the treatment of sewage in, particularly for Organic Pollution in sewage of degrading.
Certainly, except situation about enumerating in embodiment one to example IV, at the weight ratio, ultrasound between other raw material components
The temperature and time of reason, temperature and time of freeze-drying etc. are all possible.
The present invention provide with it is cellulose nano-fibrous for template prepare aeroge and preparation method and application, can make
It is standby go out with bigger serface, high length-diameter ratio, extremely-low density and with excellent photocatalytic degradation Organic Compound can aeroge,
Such that it is able to be efficiently applied in the processing procedure of water pollution.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area
Art personnel can be tied the feature of the different embodiments or example described in this specification and different embodiments or example
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. a kind of method for preparing aeroge, it is characterised in that comprise the following steps：
S101：It is added to the water cellulose nano-fibrous, ultrasonic wave decentralized processing is carried out after stirring；
S102：To butyl titanate, urea and citric acid is added in the product after ultrasonic wave decentralized processing described in S101, stir
Reaction 1h-100h after uniform；
S103：By the reacted product centrifugal treating, solid phase is collected；The solid phase and water are pressed 1：100-1：1000 weight
Amount carries out ultrasonic wave decentralized processing afterwards than mixing；
S104：By the product freeze-drying after the treatment of ultrasonic disperse described in S103, aeroge is obtained.
2. the method for preparing aeroge according to claim 1, it is characterised in that：
The cellulose nano-fibrous weight ratio with the butyl titanate, the urea and the citric acid is 1：
(0.001-10)：(0.001-10)：(0.001-10).
3. the method for preparing aeroge according to claim 1, it is characterised in that：
In the S101, the condition of the ultrasonic wave decentralized processing is：Temperature is 0 DEG C -10 DEG C, and the time is 10min-1000min,
Ultrasonic power is 100W-500W；In product after the ultrasonic wave decentralized processing, cellulose nano-fibrous mass percentage concentration
Less than or equal to 10%.
4. the method for preparing aeroge according to claim 1, it is characterised in that：
In the S102, the reaction is carried out in a kettle., and the temperature of the reaction is 25 DEG C -220 DEG C.
5. the method for preparing aeroge according to claim 1, it is characterised in that：
In the S103, the centrifugal treating is specially：By the reacted product under conditions of 2000-8000rpm from
Heart 5-10min.
6. the method for preparing aeroge according to claim 1, it is characterised in that：
In the S103, the condition of the ultrasonic wave decentralized processing is：Temperature is 0 DEG C -10 DEG C, and the time is 1min-100min, is surpassed
Acoustical power is 10W-100W.
7. the method for preparing aeroge according to claim 1, it is characterised in that：
In the S104, the condition of the freeze-drying is：Temperature is -80 DEG C -0 DEG C, and pressure is 0-50 μ pa, and the time is 1d-
7d。
8. the method for preparing aeroge according to claim 1, it is characterised in that：
In the S104, the freeze-drying is specially：By the product after ultrasonic disperse treatment in pre-freeze at -15 DEG C -0 DEG C
10h-15h；Then in temperature it is -80 DEG C -0 DEG C by the product after the pre-freeze 10h-15h, pressure is 0-50 μ pa, and the time is
Freeze-drying is carried out under conditions of 1d-7d.
9. the aeroge for being prepared according to the method any one of claim 1-8.
10. the aeroge described in claim 9 is especially degraded in sewage in terms of Organic Pollution in terms of water pollution of degrading
Using.
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| CN107973939A (en) * | 2017-05-23 | 2018-05-01 | 齐鲁工业大学 | A kind of zinc oxide aeroge and preparation method thereof |
| CN110172185A (en) * | 2019-05-08 | 2019-08-27 | 南京林业大学 | A kind of anisotropy nano-cellulose aerogel and preparation method thereof and device |
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| CN107159122A (en) * | 2017-06-30 | 2017-09-15 | 东北林业大学 | A kind of Heteroatom doping type charcoal-aero gel and preparation method thereof |
| CN110172185A (en) * | 2019-05-08 | 2019-08-27 | 南京林业大学 | A kind of anisotropy nano-cellulose aerogel and preparation method thereof and device |
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