CN108246254A - A kind of preparation method and product of the adjustable biomass carbon tunica fibrosa of wetability - Google Patents
A kind of preparation method and product of the adjustable biomass carbon tunica fibrosa of wetability Download PDFInfo
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- CN108246254A CN108246254A CN201810038591.XA CN201810038591A CN108246254A CN 108246254 A CN108246254 A CN 108246254A CN 201810038591 A CN201810038591 A CN 201810038591A CN 108246254 A CN108246254 A CN 108246254A
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- biomass carbon
- tunica fibrosa
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
Abstract
The invention belongs to new chemical materials technical fields, are related to the preparation method and product of membrane material more particularly to a kind of adjustable biomass carbon tunica fibrosa of wetability.Itself and volatile acid are first total to Grape berry, add KMnO by the present invention using modified biomass carbon-fiber film as substrate4, deionized water using hydro-thermal method its surface in situ grow one layer of MnO2Nanometer sheet；Then zinc nitrate hexahydrate and hexa are added in, one layer of nano-ZnO is wrapped up in film surface by hydro-thermal method；Under environment rich or oxygen-enriched environment after high annealing, the adjustable biomass carbon tunica fibrosa of wetability is made in modulation material surface Lacking oxygen defect.Preparation process of the present invention is succinct, and obtained material internal is porous structure, and surface roughness is big, is conducive to suction-operated；The MnO of fiber surface growth in situ2Nanometer sheet can increase the hydrophobicity of carbon fiber, and the ZnO of material surface cladding can utilize the wetability there are controlled material of Lacking oxygen defect, be expected to be applied to water-oil separating as membrane material.
Description
Technical field
The invention belongs to new chemical materials technical fields, are related to membrane material more particularly to a kind of adjustable biomass of wetability
The preparation method and product of carbon-fiber film.
Background technology
Water-oil separating is to administer an important industrial technology of oily waste water and aqueous fluid, the big face of oily waste water water
Extensively, have a large amount of outputs in petroleum industry, process industry, medical industry, food food and drink etc., if handled not in time, to water body,
Soil and air will cause seriously to pollute.Aqueous fluid is had more in present oil exploitation process and marine oil overflow removal process,
Particularly in recent years, most domestic oil field enters middle and later periods exploitation, and water content is higher in extraction fluid, after needing advanced treating
Just it can be used.Current existing oily water separation technique includes：Gravitational separation process, air flotation, coalescence, filtration method, suction
Attached method, flocculence, supercritical ultrasonics technology etc..These methods there are low separation efficiency, are also easy to produce secondary pollution and with high costs etc. ask
Topic, it is difficult to promote and apply.Therefore, efficient, cheap, environmentally friendly and strong applicability the water-oil separating material of exploitation, for water-oil separating
With important research significance.
Biomass cellulose is as renewable resource most abundant on the earth, about 200,000,000,000 tons of annual output.However, these are given birth to
Material fibrils element is not fully utilized, and discarded biological material not only can cause environmental pollution, and also causes money
Source wastes.By carrying out deep processing to biomass cellulose, development function cellulose base composite material is to realize biomass fiber
The approach that element efficiently uses.
Cellulosic material is with safe and non-toxic, cheap, biodegradable, good biocompatibility, wetability is adjustable
And the advantages that chemical stability, it is that ideal water-oil separationg film prepares raw material.If after biomass cellulose is carbonized, it can turn
Become the carbon fibre material with porous structure and high hydrophobicity performance.Biomass carbon tunica fibrosa has strong solvent resistance, good
Permeability and hydrophobicity, can be applied to water-oil separating, there is the irreplaceable advantage of industrial polymer film.
Invention content
In view of the above-mentioned deficiencies in the prior art, the invention discloses a kind of adjustable biomass carbon tunica fibrosas of wetability
Preparation method.
Technical solution
The preparation process of biomass carbon tunica fibrosa is as follows：
（1）Compound concentration be 1~10 wt% NaOH solutions, preferably 5 wt%, by the NaOH solution of every 100 mL add in 5~15
G, preferably 10 g biomass fiber material meters add in biomass fiber material in NaOH solution；In 60~100 DEG C, preferably 80
DEG C environment in, stir 1~4 h, take out and be cooled to room temperature, distillation water washing to neutrality, obtain biomass fiber after drying
Plain presoma；
（2）Compound concentration is the NaClO of 1~10 wt%, preferably 5 wt%2Solution, and adjust pH to 2~6 preferably with glacial acetic acid
PH is 4, obtains NaClO2Mixed liquor, by every 100 mL NaClO2Mixed liquor adds in the biomass cellulose of 5~15 g, preferably 10 g
Biomass cellulose presoma is added in NaClO by presoma meter2In mixed liquor, in 60~100 DEG C preferably 80 DEG C of environment, stir
It after mixing 1~4 h, takes out and is cooled to room temperature, distillation water washing obtains biomass cellulose to neutrality after drying；
（3）It is added in based on 5~25 g preferably 15 g biomass celluloses by 100 mL deionized waters, it, will after mechanical agitation is uniform
Paste slurry is coated uniformly on mold, and drying obtains biomass cellulose film precursor；Under nitrogen protection, nitrogen flow rate is
30~600 cm3/ min preferably 300 cm3The biomass cellulose film precursor is put into tube furnace, heating rate by/min
For 5~15 DEG C/min preferably 10 DEG C/min, be carbonized 2~6h at 400~1000 DEG C, and preferably 700 DEG C/min carbonization 4h are given birth to
Substance carbon-fiber film.
It is an object of the present invention to disclose a kind of preparation method of the adjustable biomass carbon tunica fibrosa of wetability, wrap
Include following steps：
a）By SiO2Porous sieve is placed in reaction vessel, and biomass carbon tunica fibrosa is placed in SiO2On porous sieve；By biology
Matter carbon-fiber film and volatile acid ratio are counted for 0.2~2 g/mL, and volatile acid is added drop-wise to reaction vessel by preferably 1 g/mL
Bottom, sealed reaction vessel, after 100~160 DEG C are reacted 3~6 h, preferably 130 DEG C 4 h of reaction take out, and distillation water washing is extremely
Neutrality is put into 12~24 h in 50~100 DEG C of baking ovens and dries, and preferably 80 DEG C 16 h of baking obtain preprocessing biomass carbon fiber
Film；
b）By preprocessing biomass carbon-fiber film and KMnO4, deionized water mass ratio be 1:4~8:100~200, preferably 1:
6:100 meters, successively by deionized water, KMnO4, biomass carbon tunica fibrosa be added in reaction vessel, sealed reaction vessel, 120
~180 DEG C reaction 36~60 h, preferably 160 DEG C, 48 h, after room temperature, by modified biomass carbon-fiber film
It takes out, with deionized water and ethyl alcohol, respectively washing three times, is put into 12~24 h in 50~100 DEG C of baking ovens and dries, preferably 80 DEG C are dried 16
H obtains MnO2/ biomass carbon tunica fibrosa；
c）It is preferred by 0.2~1 g preferably 0.4 g zinc nitrate hexahydrates and 0.1~0.5 g is added in every 100 mL deionized waters
0.4 g hexa meters, stirring move into reaction kettle, are put into MnO to being completely dissolved2/ biomass carbon tunica fibrosa, sealing are anti-
It answers kettle, after 80~100 DEG C of reactions preferably 100 DEG C of 6~10 h, 8 h, takes out, cleaned, be then placed in deionized water and ethyl alcohol
12~24 h are dried in 60~100 DEG C of baking ovens, and preferably 80 DEG C 16 h of baking obtain ZnO/MnO2/ biomass carbon tunica fibrosa；
D) by ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 2~6 h of hydrogen annealing is led at 300~500 DEG C,
It is preferred that 400 DEG C of 4 h of annealing, make surface generate Lacking oxygen defect, obtain high hydrophobicity biomass carbon tunica fibrosa；
e）By step c）Gained ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and oxygen is led at 200~400 DEG C
Anneal 2~6 h, preferably 300 DEG C, and anneal 4 h, is passivated Surface Oxygen vacancy defect, obtains Superhydrophilic biomass carbon tunica fibrosa.
The adjustable biomass carbon tunica fibrosa of wetability of the present invention, by modulation material surface Lacking oxygen defect, makes its table
Face has wetting adjustability, even if material surface has high hydrophobicity or Superhydrophilic.
In the more excellent disclosed example of the present invention, the volatile acid is concentrated nitric acid.
Another object of the present invention is, the wetability according to made from the above method is adjustable biomass carbon tunica fibrosa,
By modified biomass carbon-fiber film and MnO2Nanometer sheet, nano-ZnO are formed, the modified biomass carbon-fiber film and MnO2Nanometer
The mass ratio 100 of piece, nano-ZnO:1~5:1~5；A diameter of 8~15 μm of the modified biomass carbon fiber, length is more than
1 mm has good flexibility；The MnO2A diameter of 200~the 400nm of nanometer sheet, length are 1~1.5 μm；The nanometer
ZnO film thickness is 20~60 nm.
High hydrophobic and absorption property, the MnO of the material combination biomass carbon fiber2The hydrophobicity and ZnO of nanometer sheet exist
Lacking oxygen defect, there is controllable wetability.
It is measured by water contact angle, when the adjustable biomass carbon tunica fibrosa of wetability shows as high hydrophobicity, water contact angle
It is 130 °~150 °；When showing as Superhydrophilic, contact angle is 0 °.
Advantageous effect
Itself and volatile acid are first total to Grape berry, add KMnO by the present invention using modified biomass carbon-fiber film as substrate4、
Deionized water grows one layer of MnO using hydro-thermal method in its surface in situ2Nanometer sheet；Then zinc nitrate hexahydrate and six methylenes are added in
Urotropine wraps up one layer of nano-ZnO by hydro-thermal method in film surface；Under environment rich or oxygen-enriched environment after high annealing, adjust
Become material surface Lacking oxygen defect and the adjustable biomass carbon tunica fibrosa of wetability is made.Preparation process of the present invention is succinct, obtained
Material internal is porous structure, and surface roughness is big, is conducive to suction-operated；The MnO of fiber surface growth in situ2Nanometer sheet can
Increase the hydrophobicity of carbon fiber, the ZnO of material surface cladding can utilize the wetability there are controlled material of Lacking oxygen defect, have
It hopes and is applied to water-oil separating as membrane material.
Description of the drawings
The scanning electron microscope (SEM) photograph of product under Fig. 1, different multiplying, wherein, the amplification factor that the amplification factor of A is 1600, B is
6000；
Water contact angle when Fig. 2, product are regulated to super hydrophilic；
Water contact angle when Fig. 3, product are regulated to high hydrophobic.
Specific embodiment
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited in following embodiments.
Embodiment 1
A kind of preparation method of the adjustable biomass carbon tunica fibrosa of wetability, includes the following steps：
a）By SiO2Porous sieve is placed in reaction vessel, and biomass carbon tunica fibrosa is placed on SiO2On porous sieve；By biomass
Carbon-fiber film and concentrated nitric acid ratio are that 1 g/mL is counted, and concentrated nitric acid is added drop-wise to reaction container bottom, sealed reaction vessel, 120 DEG C
It after 6 h of lower reaction, takes out, distillation water washing to neutrality, is put into 24 h in 50 DEG C of baking ovens and dries, obtain preprocessing biomass carbon
Tunica fibrosa.
b）By preprocessing biomass carbon-fiber film and KMnO4, deionized water mass ratio be 1: 4:100 meters successively will
Deionized water, KMnO4, biomass carbon tunica fibrosa be added in reaction vessel, sealed reaction vessel, in 150 DEG C of environment, instead
Answer 24 h；After room temperature, modified biomass carbon-fiber film is taken out, with deionized water and ethyl alcohol respectively washing three
It is secondary, it is put into 24 h in 50 DEG C of baking ovens and dries, obtain MnO2/ biomass carbon tunica fibrosa.
c）By being added in every 100 mL deionized waters based on 0.8 g zinc nitrate hexahydrates and 0.4 g hexas, stir
To after being completely dissolved, solution is moved in reaction kettle, is put into MnO2/ biomass carbon tunica fibrosa seals reaction kettle, 80 DEG C of reactions
It after 10 h, takes out, is cleaned with deionized water and ethyl alcohol, be then placed in 24 h in 60 DEG C of baking ovens and dry, obtain ZnO/MnO2 /
Biomass carbon tunica fibrosa.
D) by ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 6 h of hydrogen annealing is led at 300 DEG C, is made
Its surface generates Lacking oxygen defect and obtains high hydrophobic biological matter carbon-fiber film；
e）Alternatively, leading to 6 h of oxygen annealing at 200 DEG C, make Lacking oxygen defect passivation, obtain Superhydrophilic biomass carbon fiber
Film.By modulation material Lacking oxygen defect, make its surface that there is wetting adjustability.
It is measured by water contact angle, when the adjustable biomass carbon tunica fibrosa of wetability shows as high hydrophobicity, water contact angle
It is 140 °；When showing as Superhydrophilic, contact angle is 0 °.
Embodiment 2
A kind of preparation method of the adjustable biomass carbon tunica fibrosa of wetability, includes the following steps：
a）By SiO2Porous sieve is placed in reaction vessel, and biomass carbon tunica fibrosa is placed on SiO2On porous sieve；By biomass
Carbon-fiber film and concentrated nitric acid ratio are that 1.2 g/mL are counted, and concentrated nitric acid is added drop-wise to reaction container bottom, sealed reaction vessel, 130
It after 4 h are reacted at DEG C, takes out, distillation water washing to neutrality, is put into 20 h in 60 DEG C of baking ovens and dries, obtain preprocessing biomass
Carbon-fiber film.
b）By preprocessing biomass carbon-fiber film and KMnO4, deionized water mass ratio be 1: 5:120 meters successively will
Deionized water, KMnO4, biomass carbon tunica fibrosa be added in reaction vessel, sealed reaction vessel, in 140 DEG C of environment, instead
Answer 50 h.After reaction kettle cooled to room temperature, modified biomass carbon-fiber film is taken out, is respectively washed with deionized water and ethyl alcohol
It washs three times, is put into 20 h in 60 DEG C of baking ovens and dries, obtain MnO2/ biomass carbon tunica fibrosa.
c）By being added in every 100 mL deionized waters based on 0.6 g zinc nitrate hexahydrates and 0.3 g hexas, stir
To after being completely dissolved, solution is moved in reaction kettle, is put into MnO2/ biomass carbon tunica fibrosa seals reaction kettle.90 DEG C of environment
In, after reacting 8 h, take out, clean with deionized water and ethyl alcohol, be then placed in 70 DEG C of baking ovens 20 h drying, obtain ZnO/
MnO2/ biomass carbon tunica fibrosa.
D) by ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 3 h of hydrogen annealing is led at 400 DEG C, is made
Its surface generates Lacking oxygen defect and obtains high hydrophobic biological matter carbon-fiber film；
e）Alternatively, leading to 3 h of oxygen annealing at 300 DEG C, make Lacking oxygen defect passivation, obtain Superhydrophilic biomass carbon fiber
Film.By modulation material Lacking oxygen defect, make its surface that there is wetting adjustability.
It is measured by water contact angle, when the adjustable biomass carbon tunica fibrosa of wetability shows as high hydrophobicity, water contact angle
It is 135 °；When showing as Superhydrophilic, contact angle is 0 °.
Embodiment 3
A kind of preparation method of the adjustable biomass carbon tunica fibrosa of wetability, includes the following steps：
a）By SiO2Porous sieve is placed in reaction vessel, and biomass carbon tunica fibrosa is placed on SiO2On porous sieve；By biomass
Carbon-fiber film and concentrated nitric acid ratio are that 1.4 g/mL are counted, and concentrated nitric acid is added drop-wise to reaction container bottom, sealed reaction vessel, 125
It after 5 h are reacted at DEG C, takes out, distillation water washing to neutrality, is put into 18 h in 70 DEG C of baking ovens and dries, obtain preprocessing biomass
Carbon-fiber film.
b）By preprocessing biomass carbon-fiber film and KMnO4, deionized water mass ratio be 1: 6 :140 meters, successively
By deionized water, KMnO4, biomass carbon tunica fibrosa be added in reaction vessel, sealed reaction vessel, in 150 DEG C of environment,
React 48 h.After reaction kettle cooled to room temperature, modified biomass carbon-fiber film is taken out, it is each with deionized water and ethyl alcohol
Washing three times, is put into 16 h in 70 DEG C of baking ovens and dries, obtain MnO2/ biomass carbon tunica fibrosa.
c）By being added in every 100 mL deionized waters based on 0.4 g zinc nitrate hexahydrates and 0.2 g hexas, stir
To after being completely dissolved, solution is moved in reaction kettle, is put into MnO2/ biomass carbon tunica fibrosa seals reaction kettle.100 DEG C of rings
It in border, after reacting 6 h, takes out, is cleaned with deionized water and ethyl alcohol, be then placed in 16 h in 80 DEG C of baking ovens and dry, obtain ZnO
/MnO2/ biomass carbon tunica fibrosa.
D) by ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 2 h of hydrogen annealing is led at 500 DEG C, is made
Its surface generates Lacking oxygen defect and obtains high hydrophobic biological matter carbon-fiber film；
e）Alternatively, leading to 2 h of oxygen annealing at 400 DEG C, make Lacking oxygen defect passivation, obtain Superhydrophilic biomass carbon fiber
Film.By modulation material Lacking oxygen defect, make its surface that there is wetting adjustability.
It is measured by water contact angle, when the adjustable biomass carbon tunica fibrosa of wetability shows as high hydrophobicity, water contact angle
It is 145 °；When showing as Superhydrophilic, contact angle is 0 °.
Embodiment 4
A kind of preparation method of the adjustable biomass carbon tunica fibrosa of wetability, includes the following steps：
a）By SiO2Porous sieve is placed in reaction vessel, and biomass carbon tunica fibrosa is placed on SiO2On porous sieve；By biomass
Carbon-fiber film and concentrated nitric acid ratio are that 1.6 g/mL are counted, and concentrated nitric acid is added drop-wise to reaction container bottom, sealed reaction vessel, 135
It after 4 h are reacted at DEG C, takes out, distillation water washing to neutrality, is put into 15 h in 80 DEG C of baking ovens and dries, obtain preprocessing biomass
Carbon-fiber film.
b）By preprocessing biomass carbon-fiber film and KMnO4, deionized water mass ratio be 1: 8 :200 meters, successively
By deionized water, KMnO4, biomass carbon tunica fibrosa be added in reaction vessel, sealed reaction vessel, in 160 DEG C of environment,
React 42 h.After reaction kettle cooled to room temperature, modified biomass carbon-fiber film is taken out, it is each with deionized water and ethyl alcohol
Washing three times, is put into 24 h in 50 DEG C of baking ovens and dries, obtain MnO2/ biomass carbon tunica fibrosa.
c）By being added in every 100 mL deionized waters based on 0.6 g zinc nitrate hexahydrates and 0.4 g hexas, stir
To after being completely dissolved, solution is moved in reaction kettle, is put into MnO2/ biomass carbon tunica fibrosa seals reaction kettle.80 DEG C of environment
In, after reacting 6 h, take out, clean with deionized water and ethyl alcohol, be then placed in 100 DEG C of baking ovens 12 h drying, obtain ZnO/
MnO2/ biomass carbon tunica fibrosa.
D) by ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 3 h of hydrogen annealing is led at 350 DEG C, is made
Its surface generates Lacking oxygen defect and obtains high hydrophobic biological matter carbon-fiber film；
e）Alternatively, leading to 3 h of oxygen annealing at 350 DEG C, make Lacking oxygen defect passivation, obtain Superhydrophilic biomass carbon fiber
Film.By modulation material Lacking oxygen defect, make its surface that there is wetting adjustability.
It is measured by water contact angle, when the adjustable biomass carbon tunica fibrosa of wetability shows as high hydrophobicity, water contact angle
It is 138 °；When showing as Superhydrophilic, contact angle is 0 °.
Embodiment 5
A kind of preparation method of the adjustable biomass carbon tunica fibrosa of wetability, includes the following steps：
a）By SiO2Porous sieve is placed in reaction vessel, and biomass carbon tunica fibrosa is placed on SiO2On porous sieve；By biomass
Carbon-fiber film and concentrated nitric acid ratio are that 1.1 g/mL are counted, and concentrated nitric acid is added drop-wise to reaction container bottom, sealed reaction vessel, 130
It after 4 h are reacted at DEG C, takes out, distillation water washing to neutrality, is put into 16 h in 80 DEG C of baking ovens and dries, obtain preprocessing biomass
Carbon-fiber film.
b）By preprocessing biomass carbon-fiber film and KMnO4, deionized water mass ratio be 1: 4 :100 meters, successively
By deionized water, KMnO4, biomass carbon tunica fibrosa be added in reaction vessel, sealed reaction vessel, in 145 DEG C of environment,
React 48 h.After reaction kettle cooled to room temperature, modified biomass carbon-fiber film is taken out, it is each with deionized water and ethyl alcohol
Washing three times, is put into 24 h in 50 DEG C of baking ovens and dries, obtain MnO2/ biomass carbon tunica fibrosa.
c）By being added in every 100 mL deionized waters based on 0.5 g zinc nitrate hexahydrates and 0.2 g hexas, stir
To after being completely dissolved, solution is moved in reaction kettle, is put into MnO2/ biomass carbon tunica fibrosa seals reaction kettle.80 DEG C of environment
In, after reacting 9 h, take out, clean with deionized water and ethyl alcohol, be then placed in 70 DEG C of baking ovens 14 h drying, obtain ZnO/
MnO2/ biomass carbon tunica fibrosa.
D) by ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 4 h of hydrogen annealing is led at 400 DEG C, is made
Its surface generates Lacking oxygen defect and obtains high hydrophobic biological matter carbon-fiber film；
e）Alternatively, leading to 3 h of oxygen annealing at 300 DEG C, make Lacking oxygen defect passivation, obtain Superhydrophilic biomass carbon fiber
Film.By modulation material Lacking oxygen defect, make its surface that there is wetting adjustability.
It is measured by water contact angle, when the adjustable biomass carbon tunica fibrosa of wetability shows as high hydrophobicity, water contact angle
It is 142 °；When showing as Superhydrophilic, contact angle is 0 °.
Embodiment 6
A kind of preparation method of the adjustable biomass carbon tunica fibrosa of wetability, includes the following steps：
a）By SiO2Porous sieve is placed in reaction vessel, and biomass carbon tunica fibrosa is placed on SiO2On porous sieve；By biomass
Carbon-fiber film and concentrated nitric acid ratio are that 0.2~2 g/mL is counted, and concentrated nitric acid is added drop-wise to reaction container bottom, sealed reaction vessel,
It after 3 h are reacted at 140 DEG C, takes out, distillation water washing to neutrality, is put into 16 h in 75 DEG C of baking ovens and dries, obtain pretreatment life
Substance carbon-fiber film.
b）By preprocessing biomass carbon-fiber film and KMnO4, deionized water mass ratio be 1: 7 :180 meters, successively
By deionized water, KMnO4, biomass carbon tunica fibrosa be added in reaction vessel, sealed reaction vessel, in 155 DEG C of environment,
React 36 h.After reaction kettle cooled to room temperature, modified biomass carbon-fiber film is taken out, it is each with deionized water and ethyl alcohol
Washing three times, is put into 14 h in 60 DEG C of baking ovens and dries, obtain MnO2/ biomass carbon tunica fibrosa.
c）By being added in every 100 mL deionized waters based on 0.7 g zinc nitrate hexahydrates and 0.35 g hexas, stir
It mixes to after being completely dissolved, solution is moved in reaction kettle, be put into MnO2/ biomass carbon tunica fibrosa seals reaction kettle.90 DEG C of rings
It in border, after reacting 6 h, takes out, is cleaned with deionized water and ethyl alcohol, be then placed in 15 h in 70 DEG C of baking ovens and dry, obtain ZnO
/MnO2/ biomass carbon tunica fibrosa.
D) by ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 2 h of hydrogen annealing is led at 450 DEG C, is made
Its surface generates Lacking oxygen defect and obtains high hydrophobic biological matter carbon-fiber film；
e）Alternatively, leading to 3 h of oxygen annealing at 300 DEG C, make Lacking oxygen defect passivation, obtain Superhydrophilic biomass carbon fiber
Film.By modulation material Lacking oxygen defect, make its surface that there is wetting adjustability.
It is measured by water contact angle, when the adjustable biomass carbon tunica fibrosa of wetability shows as high hydrophobicity, water contact angle
It is 140 °；When showing as Superhydrophilic, contact angle is 0 °.
Embodiment 7
A kind of preparation method of the adjustable biomass carbon tunica fibrosa of wetability, includes the following steps：
a）By SiO2Porous sieve is placed in reaction vessel, and biomass carbon tunica fibrosa is placed on SiO2On porous sieve；By biomass
Carbon-fiber film and concentrated nitric acid ratio are that 0.8 g/mL is counted, and concentrated nitric acid is added drop-wise to reaction container bottom, sealed reaction vessel, 145
It after 3 h are reacted at DEG C, takes out, distillation water washing to neutrality, is put into 24 h in 50 DEG C of baking ovens and dries, obtain preprocessing biomass
Carbon-fiber film.
b）By preprocessing biomass carbon-fiber film and KMnO4, deionized water mass ratio be 1: 6 :150 meters, successively
By deionized water, KMnO4, biomass carbon tunica fibrosa be added in reaction vessel, sealed reaction vessel, in 130 DEG C of environment,
React 40 h.After reaction kettle cooled to room temperature, modified biomass carbon-fiber film is taken out, it is each with deionized water and ethyl alcohol
Washing three times, is put into 16 h in 70 DEG C of baking ovens and dries, obtain MnO2/ biomass carbon tunica fibrosa.
c）By being added in every 100 mL deionized waters based on 1 g zinc nitrate hexahydrates and 0.5 g hexas, stirring is extremely
After being completely dissolved, solution is moved in reaction kettle, is put into MnO2/ biomass carbon tunica fibrosa seals reaction kettle.85 DEG C of environment
In, after reacting 10 h, take out, clean with deionized water and ethyl alcohol, be then placed in 70 DEG C of baking ovens 16 h drying, obtain ZnO/
MnO2/ biomass carbon tunica fibrosa.
D) by ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 3 h of hydrogen annealing is led at 350 DEG C, is made
Its surface generates Lacking oxygen defect and obtains high hydrophobic biological matter carbon-fiber film；
e）Alternatively, leading to 4 h of oxygen annealing at 250 DEG C, make Lacking oxygen defect passivation, obtain Superhydrophilic biomass carbon fiber
Film.By modulation material Lacking oxygen defect, make its surface that there is wetting adjustability.
It is measured by water contact angle, when the adjustable biomass carbon tunica fibrosa of wetability shows as high hydrophobicity, water contact angle
It is 143 °；When showing as Superhydrophilic, contact angle is 0 °.
With reference to Figure of description 1, the flake porous coarse structure of surface can be observed, these laminated structures are to use water
Hot method is in the MnO of fiber surface growth in situ package ZnO2Nanometer sheet, by leading to hydrogen or oxygen annealing, controllable life to ZnO
The surface wettability of substance carbon-fiber film.With reference to Figure of description 2 and attached drawing 3, the surface profit of provable biomass carbon tunica fibrosa
It is moist really controllable.
The foregoing is merely the embodiment of the present invention, are not intended to limit the scope of the invention, every to utilize this hair
The equivalent structure or equivalent flow shift that bright specification is made directly or indirectly is used in other related technical areas,
Similarly it is included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of the adjustable biomass carbon tunica fibrosa of wetability, which is characterized in that include the following steps：
a）By SiO2Porous sieve is placed in reaction vessel, and biomass carbon tunica fibrosa is placed in SiO2On porous sieve；By biomass
Carbon-fiber film and volatile acid ratio are counted for 0.2~2 g/mL, volatile acid are added drop-wise to reaction container bottom, sealing reaction is held
Device after 100~160 DEG C are reacted 3~6 h, takes out, and distillation water washing is put into 12~24 h in 50~100 DEG C of baking ovens to neutrality
Drying, obtains preprocessing biomass carbon-fiber film；
b）By preprocessing biomass carbon-fiber film and KMnO4, deionized water mass ratio be 1:4~8:100~200, it will go successively
Ionized water, KMnO4, biomass carbon tunica fibrosa be added in reaction vessel, sealed reaction vessel, 120~180 DEG C reaction 36~
After room temperature, modified biomass carbon-fiber film is taken out by 60 h, is respectively washed three times with deionized water and ethyl alcohol,
It is put into 12~24 h in 50~100 DEG C of baking ovens to dry, obtains MnO2/ biomass carbon tunica fibrosa；
c）It is added in based on 0.2~1 g zinc nitrate hexahydrates and 0.1~0.5 g hexas by every 100 mL deionized waters,
Stirring moves into reaction kettle, is put into MnO to being completely dissolved2/ biomass carbon tunica fibrosa seals reaction kettle, 80~100 DEG C of reactions 6
It after~10 h, takes out, is cleaned with deionized water and ethyl alcohol, be then placed in 12~24 h in 60~100 DEG C of baking ovens and dry, obtain
ZnO /MnO2/ biomass carbon tunica fibrosa；
D) by ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 2~6 h of hydrogen annealing is led at 300~500 DEG C, is made
Surface generates Lacking oxygen defect, obtains high hydrophobicity biomass carbon tunica fibrosa；
e）By step c）Gained ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and oxygen is led at 200~400 DEG C
Anneal 2~6 h, is passivated Surface Oxygen vacancy defect, obtains Superhydrophilic biomass carbon tunica fibrosa.
2. the preparation method of the adjustable biomass carbon tunica fibrosa of wetability according to claim 1, it is characterised in that：Step a）Institute
Volatile acid is stated as concentrated nitric acid.
3. the preparation method of the adjustable biomass carbon tunica fibrosa of wetability according to claim 1, it is characterised in that：Step a）Institute
It is 1 g/mL to state in biomass carbon tunica fibrosa and volatile acid ratio, volatile acid is added drop-wise to reaction container bottom, sealing is anti-
Container is answered, 130 DEG C of 4 h of reaction take out, distillation water washing to neutrality, are put into 16 h in 80 DEG C of baking ovens and dry, are pre-processed
Biomass carbon tunica fibrosa.
4. the preparation method of the adjustable biomass carbon tunica fibrosa of wetability according to claim 1, it is characterised in that：Step b）Institute
It states by preprocessing biomass carbon-fiber film and KMnO4, deionized water mass ratio be 1:6:100 meter, successively by deionized water,
KMnO4, biomass carbon tunica fibrosa be added in reaction vessel, sealed reaction vessel, 160 DEG C reaction 48 h, treat natural cooling
To room temperature, modified biomass carbon-fiber film is taken out, with deionized water and ethyl alcohol, respectively washing three times, is put into 80 DEG C of baking ovens
16 h are dried, and obtain MnO2/ biomass carbon tunica fibrosa.
5. the preparation method of the adjustable biomass carbon tunica fibrosa of wetability according to claim 1, it is characterised in that：Step c）Institute
It states by being added in every 100 mL deionized waters based on 0.4 g zinc nitrate hexahydrates and 0.4 g hexas, stirs to completely molten
Solution moves into reaction kettle, is put into MnO2/ biomass carbon tunica fibrosa, seal reaction kettle, 100 DEG C reaction 8 h after, take out, spend from
Sub- water and ethyl alcohol cleaning are then placed in 16h in 80 DEG C of baking ovens and dry, obtain ZnO/MnO2/ biomass carbon tunica fibrosa.
6. the preparation method of the adjustable biomass carbon tunica fibrosa of wetability according to claim 1, it is characterised in that：Step d）Institute
It states ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 4 h of hydrogen annealing is led at 400 DEG C, surface is made to generate oxygen empty
Position defect, obtains high hydrophobicity biomass carbon tunica fibrosa.
7. the preparation method of the adjustable biomass carbon tunica fibrosa of wetability according to claim 1, it is characterised in that：Step e）Institute
It states step c）Gained ZnO/MnO2/ biomass carbon tunica fibrosa is put into tube furnace, and 4 h of oxygen annealing is led at 300 DEG C,
Surface Oxygen vacancy defect is passivated, obtains Superhydrophilic biomass carbon tunica fibrosa.
8. according to the adjustable biomass carbon tunica fibrosa of wetability made from any the methods of claim 1-7, by modified biomass
Carbon-fiber film and MnO2Nanometer sheet, nano-ZnO are formed.
9. the 8 adjustable biomass carbon tunica fibrosas of wetability are required according to claim, it is characterised in that：The modified biomass
Carbon-fiber film and MnO2The mass ratio 100 of nanometer sheet, nano-ZnO:1~5:1~5；The diameter of the modified biomass carbon fiber
It it is 8~15 μm, length is more than 1 mm, has good flexibility；The MnO2A diameter of 200~the 400nm of nanometer sheet, length
It is 1~1.5 μm；The nano-ZnO thin film thickness is 20~60 nm.
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