CN109468709A - A kind of graphene doping Co3O4The preparation method of hollow fibre - Google Patents
A kind of graphene doping Co3O4The preparation method of hollow fibre Download PDFInfo
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- CN109468709A CN109468709A CN201811264903.5A CN201811264903A CN109468709A CN 109468709 A CN109468709 A CN 109468709A CN 201811264903 A CN201811264903 A CN 201811264903A CN 109468709 A CN109468709 A CN 109468709A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
A kind of graphene of the present invention adulterates Co3O4The preparation method of hollow fibre, it is characterized in that preparing Co using electrostatic spinning technique and high-temperature heat treatment method3O4Then hollow fibre prepares Co using microwave method3O4/ rGO composite material；The step includes that (1) weighs after DMF and PAN constant temperature stirs to PAN and be completely dispersed in DMF, then weighs Co (CH3COO)2·4H2O is added, and stirring and dissolving obtains spinning solution；(2) solvent is added, stirring is to sufficiently dissolving and be uniformly mixed；(3) it using the liquid inventory during micro-injection pump control electrostatic spinning, is put on electrostatic spinning device and carries out spinning, high-temperature heat treatment obtains Co after spinning is dry3O4Fiber；(4) Co is weighed3O4Fiber and graphite oxide are added ultrasound in deionized water and obtain Co3O4Fiber/graphite oxide disperses solution.Then the present invention uses microwave radiation reaction reduction preparation Co3O4/ rGO composite material, the doping of rGO increases material photon absorbing intensity and improves electron transport ability, to improve composite material photocatalysis performance.
Description
Technical field
The present invention relates to high molecular material and electrochemical technology fields more particularly to a kind of graphene to adulterate Co3O4Hollow fibre
The preparation method of dimension
Background technique
With the growth of population, increased with water amplitude, the scarcity of freshwater resources has been people's asking of having to face
Topic.In the field of purification of water, removing water pollutant includes that heavy metal, organic pollutant and dyestuff are that eager needs solve
One of problem.Although there are many method of present purified water, many processes are excessively cumbersome in this, and treatment effect is undesirable, it is difficult to
Realize standardization discharge.Because of the photocatalytic activity that transition metal oxide has had, so as to which transition metal oxide is transported
The field of purification of water is used, some transition metal oxides can make catalyst, accelerate the degradation of waste in water to realize water
Purification.Co3O4It is grey black or black transition group metallic oxide chip solid, crystal stability is higher, is widely used
In multiple fields, such as effective catalyst, supercapacitor.There are many chemical method for preparing it.As although chemical precipitation method has
Have good application prospect, but will appear in preparation flow precipitating granular size is not easy to control, product impurity is more, reaction not
Many problems such as easy to control；Sol method high production cost, calcining property it is poor, dry after structure change it is big, the above method prepares material
It is difficult to be promoted in the industrial production.
Since electrostatic spinning technique has many advantages, such as at low cost, easy to operate and easy progress mass production, and
The preparation field of the materials such as photocatalysis, solar battery, supercapacitor has potential application prospect, therefore has attracted wide
The interest of big scientific research personnel.Meanwhile polymer/transition oxide the composite fibre and inorganic nano of electrostatic spinning technique preparation
Fibrous material has the advantages that high porosity, large specific surface area and good dispersion.In recent years, electrostatic spinning technique prepares Co3O4
Fibrous material is mainly used in the fields such as flexible device and water process.Chinese patent CN102277642A discloses a kind of thermoplastic
The method that property carboxymethyl cellulose derivative electrostatic spinning prepares fiber, it is characterized in that including: to be dissolved in sodium carboxymethylcellulose
It in water, after swelling, is added initiator ammonium persulfate initiation reaction 0.1~2 hour, adds methyl acrylate and be grafted altogether
Poly- reaction, reacts 0.5~8 hour at 40~85 DEG C；Then it mixed, stand, filtered with reacting rear material with ethyl alcohol, solids
It mixes, stand, filter with acetone again, then solids is dry, thermoplastic cellulose is made；Thermoplastic cellulose is ground into
Powder, then the powder is dissolved in organic solvent and is configured to solution, obtain electrostatic spinning solution；By electrostatic spinning solution through quiet
Electric spinning device carries out electrostatic spinning, dry, obtains fiber.Using the present invention, cellulose material solution is efficiently solved
Spinnability, fibre spinnable silk film forming obtained apply to wastewater treatment, film infiltration etc., open cellulose derivative material
The new application of material.Chinese patent CN105214516A discloses a kind of Electrospun nano-fibers of high-throughput, high rejection
The preparation method of ultrafiltration membrane uses bamboo fibre for coating liquid raw material, and polyethyleneglycol diacrylate is crosslinking agent, ammonium persulfate
It is protective agent for initiator and polyethylene glycol, electrostatic spinning technique and spin coating cladding process is used to be prepared into one kind with poly- second two
Alcohol layer is surface layer protective layer, enhancement type nanometer cellulose layer is the second layer, electrostatic spinning layer is third layer, non-woven fabrics is bottom
Total four-layer structure composite water handle filter membrane.Nanofibre hyperfiltration membrane made from the method for the present invention not only aperture it is small,
Stability is high, and service life is long, resistance tocrocking is good, also has the advantages that flux is high, rejection effect is good.Water-treated
Co in journey3O4Fibrous material, which exists, to be easy to reunite, and photo-generated carrier is easy again compound etc. problem, therefore only relies on the light of ontology
Catalytic capability has significant limitation.Graphene (rGO) is known as new century most excellent one of carrier of photocatalyst, rGO
Doping can increase material photon absorbing intensity and improve electron transport ability, to improve composite material photocatalysis performance herein
Co is prepared using electrostatic spinning technique and high-temperature heat treatment method3O4Hollow fibre, then using microwave radiation reaction reduction preparation
Co3O4/ rGO composite material；And photocatalyst degradation of dye methylene blue, study composite material photocatalysis performance.Experiment knot
Fruit shows: Co can be improved in the doping of graphene3O4Optical absorption intensity, during light-catalyzed reaction, since graphene is excellent
Good electric conductivity increases Co3O4Electric conductivity, the light induced electron of reaction process are easier to separate, and effectively inhibit photoproduction electric
Son-hole is compound, improves Co3O4The photocatalysis performance of material.
Summary of the invention
Existing in the prior art in water treatment procedure to overcome, Co3O4 fibrous material, which exists, to be easy to reunite, photoproduction
Carrier is easy Complex Problem again, prepares Co using electrostatic spinning technique and high-temperature heat treatment method the present invention provides a kind of3O4
Hollow fibre, then using microwave radiation reaction reduction preparation Co3O4The doping of/rGO composite material, rGO can increase material
Photon absorbing intensity and raising electron transport ability, to improve composite material photocatalysis performance.
A kind of graphene doping Co3O4The preparation method of hollow fibre is to utilize electrostatic spinning technique and high-temperature heat treatment method
Prepare Co3O4Then hollow fibre reacts reduction preparation Co using with microwave radiation3O4/ rGO composite material；It is described to prepare stone
Black alkene adulterates Co3O4The step of hollow fibre includes that (1) weighs N,N-dimethylformamide (DMF) and polyacrylonitrile (PAN) perseverance
It after temperature stirring is completely dispersed in DMF to PAN, then weighs Co (CH3COO) 24H2O and is added in above-mentioned solution, stir to complete
Fully dissolved obtains spinning solution；(2) it is added lytic agent into resulting spinning solution, stirring is to sufficiently dissolving and be uniformly mixed；
(3) spinning liquid is transferred in syringe, the liquid inventory during electrostatic spinning is controlled using micro-injection pump, is put into
Spinning is carried out on electrostatic spinning device, obtained spinning be dried be placed in Muffle furnace carry out high-temperature heat treatment obtain Co3O4
Fiber；(4) Co is weighed3O4Fiber and graphite oxide dispersion are added ultrasound in deionized water and obtain Co3O4Fiber/graphite oxide
Then alkene dispersion liquid moves into dispersion liquid in microwave reaction instrument, graphene doping is prepared in microwave radiation reaction reduction
Co3O4Hollow fibre.
Preferably, the DMF is recycled from industrial wastewater by extraction and distillation under vacuum, by the work containing DMF
Extractant o-sec-butyl phenol is added in industry waste water, adds diluent hexamethylene and n-octyl alcohol, 30 DEG C of thermostatted waters in extractant
Bath；It goes to suck water phase after the completion of layering, oil is mutually evaporated under reduced pressure, the steam steamed is collected by condensing tube condensation
It is DMF into liquid-collecting bottle.
Preferably, the DMF and PAN is stirred under conditions of environment temperature is 70 DEG C with magnetic stirring apparatus 800r/min
Mix 3h so that PAN is completely dispersed in DMF；Co (CH is being added into above-mentioned solution3COO)24H2O under the conditions of 70 DEG C, is used
Magnetic stirring apparatus 800r/min stirs 2h, is completely dissolved to obtain spinning solution；DMF, PAN and Co (CH3COO)2·4H2O matter
Amount is than being 9:1:1.
Preferably, Co (the CH3COO)2·4H2O is prepared using plasma exchange process, is adsorbed using ion exchange column
CoCl2Solution, ion exchange column is interior to fill weak-acid cation-exchange resin, and after the completion of absorption wash with distilled water, removal is set
Remaining unadsorbed CoCl in rouge2, then with spirit of vinegar resin layer is sufficiently washed, until using AgNO3Inspection does not measure in cleaning solution
Cl ion until, the resin after washing is eluted with acetic acid, obtain the mixture of cobalt acetate and acetic acid, finally be evaporated in vacuo
Crystallize cobalt acetate processed and recovery of acetic acid.
Preferably, the solvent is one of methylene chloride, chloroform and dioxane, by magnetic stirring apparatus
800r/min is stirred evenly.
Preferably, the feeding speed of the micro-injection pump is 0.025-0.059mL/min.
Preferably, the condition of the spinning is electrostatic spinning device voltage 16KV, temperature is 20 DEG C, polar plate interval 18cm,
Spinning flow velocity 1mL/h.
Preferably, the dry 12h of spinning made of described is placed in Muffle furnace with nitrogen as protection gas, 1 DEG C/min
Rate be warming up to 450 DEG C of high-temperature heat treatment 2h, obtain Co3O4Fiber.
Preferably, the preparation of the graphite oxide, uses H first2SO4And NaNO3Graphite is impregnated, graphite is carried out slotting
Layer, is then added K2FeO4Graphite is aoxidized, the H2SO4、NaNO3、K2FeO4It is 1:5:5 according to mass ratio, after reaction
Graphite oxide dispersion is formed, microwave radiation reduction method is finally used, reducing agent vitamin is added in graphite oxide dispersion
C, reduction obtain graphene point.
Preferably, the Co3O4Fiber and graphene oxide dispersion are mixed according to the ratio of 35:3, magnetic stirrer
800r/min stirs 30min, forms composite solution and moves back in microwave reaction kit, the lower 180 DEG C of incubation water heatings reaction 5 of high pressure
Minute, cooled to room temperature, with secondary deionized water and dehydrated alcohol mixing centrifuge washing 3 times, finally under 65 DEG C of constant temperature
Vacuum drying obtains graphene doping Co for 24 hours3O4Hollow fibre.
Compared with prior art, the beneficial effects of the present invention are:
(1) DMF is recycled from industrial wastewater by extraction and distillation under vacuum, because DMF has very strong dissolution energy
Power is widely used in the industrial circles such as medicine, pesticide, food additives, leather, thereby produces Industry Waste largely containing DMF
Water recycles preparation DMF in this way, solvent needed for can not only obtaining experiment, moreover it is possible to play the role of purifying waste water；
Extractant o-sec-butyl phenol is selected because the boiling point of the solvent is higher than DMF, organic phase extracted only needs to steam DMF i.e.
It can be recycled.
(2) DMF and PAN stirs 3h with magnetic stirring apparatus 800r/min under conditions of environment temperature is 70 DEG C, can be with
So that PAN is completely dispersed in DMF, Co (CH is being added3COO)2·4H2O, under the conditions of 70 DEG C, with magnetic stirring apparatus 800r/
Min stirs 2h, is completely dissolved to obtain spinning solution, DMF, PAN and Co (CH3COO)2·4H2O mass ratio is 9:1:1, can be with
So that solvent reaction is complete.
(3)Co(CH3COO)2·4H2O is prepared using plasma exchange process, adsorbs CoCl using ion exchange column2Solution,
Weak-acid cation-exchange resin is filled in ion exchange column, which has exchange capacity height, volume change small, mechanical strong
Degree is high, chemical stability is good, antipollution, the advantages that anti-oxidant, exchange velocity is fast, regeneration efficiency is high；With distillation after the completion of absorption
Water cleaning, removes remaining unadsorbed CoCl in resin2, should be Cl-It can be with CoCl+Form be adsorbed on resin, use
Water can not elute, so resin layer is sufficiently washed with spirit of vinegar, until using AgNO3Examining the Cl ion not measured in cleaning solution is
Only, the resin after washing is eluted with acetic acid, obtains the mixture of cobalt acetate and acetic acid, vinegar finally is made with vacuum evaporating crystalization
Sour cobalt and acetate solution can be recycled.
(4) solvent is one of methylene chloride, chloroform and dioxane, because being added during electrostatic spinning
Evaporation rate rises after solvent, and jet stream is dry, the cured time shortens, have little time to be sufficiently tensile it is just cured so that Nanowire
The average diameter of dimension and the distribution of fibre diameter become larger, and the incorporation for subsequent graphene provides convenience.
(5) feed of the micro-injection pump can make the spinning time of electrostatic Electrospun controllable, different by selecting
Solvent adjusts suitable feeding speed according to respective evaporation rate.Spinning, which is put into Muffle furnace after being made, carries out high warm
Processing forms Co3O4Fiber can make its Structured cured, and make Co3O4Fiber is easier to doped graphene molecule.
(6)H2SO4And NaNO3Graphite is impregnated, the Van der Waals force between graphite flake graphite can be made in acid condition is reduced,
Intercalation is carried out to graphite, interlamellar spacing is increased, avoids the use of potassium chlorate, do not have mephitical generation and risk of explosion, then
K is added2FeO4Graphite is aoxidized, replaces potassium permanganate as oxidant using potassium ferrate, it is water-soluble to obtain graphite oxide
The solution that liquid, resulting graphite oxide solution and potassium permanganate oxidation method obtain is in chemical composition, single layer rate, size and defect
All keep almost the same on degree, however oxidation product is iron ion, it is more environmentally-friendly compared to the manganese ion that potassium permanganate is formed, and
And the oxidation of potassium ferrate is more rapid, improves the steamed stuffed bun by small bamboo food steamer of preparation, reduces whole cost.
(7)Co3O4Fiber and graphite oxide dispersion are configured to double solvents by stirring, pass through microwave reaction instrument
In the effect of high pressure and high temperature, make Co3O4Fiber and graphene dispersing solution merge well, and using reduction reaction, cooling is washed
It washs to obtain and ultimately forms complete graphene-doped doping Co3O4Hollow fibre improves the performance of composite material.
Detailed description of the invention
Fig. 1 is Co3O4SEM picture under low resolution；
Fig. 2 is Co3O4SEM picture at high resolutions；
Fig. 3 is Co3O4The SEM picture of/rGO-1 under low resolution；
Fig. 4 is Co3O4The SEM picture of/rGO-1 at high resolutions；
Fig. 5 is Co3O4The SEM picture of/rGO-2 under low resolution；
Fig. 6 is Co3O4The SEM picture of/rGO-2 at high resolutions；
Fig. 7 is Co3O4The SEM picture of/rGO-3 under low resolution；
Fig. 8 is Co3O4The SEM picture of/rGO-3 at high resolutions；
Fig. 9 is Co3O4The SEM picture of/rGO-4 under low resolution；
Figure 10 is Co3O4The SEM picture of/rGO-4 at high resolutions；
Figure 11 is Co3O4Hollow fibre nitrogen adsorption-desorption labyrinth and graph of pore diameter distribution；
Figure 12 is Co3O4With Co3O4The Raman spectrogram of/rGO composite material；
Figure 13 is Co3O4With Co3O4/ rGO composite material XRD spectra；
Figure 14 is Co3O4With Co3O4The UV-visible absorption spectrum of/rGO composite material；
Figure 15 is (a) Co3O4The ultraviolet-ray visible absorbing peak of/rGO-4 composite material photocatalytic degradation of dye methylene blue with
The relational graph in reaction time；
Figure 16 is Co3O4And the Co of doping different proportion GO3O4/ rGO composite material rate of photocatalytic oxidation figure；
Figure 17 is Co3O4/ rGO photocatalytic degradation schematic diagram.
Specific embodiment
Below in conjunction with drawings and examples, the present invention will be described in further detail.It should be appreciated that described herein
Specific examples are only used to explain the present invention, is not intended to limit the present invention.
Embodiment 1:
A kind of graphene doping Co3O4The preparation method of hollow fibre is to utilize electrostatic spinning technique and high-temperature heat treatment method
Prepare Co3O4Then hollow fibre reacts reduction preparation Co using with microwave radiation3O4/ rGO composite material；It is described to prepare stone
Black alkene adulterates Co3O4The step of hollow fibre includes that (1) weighs N,N-dimethylformamide (DMF) and polyacrylonitrile (PAN) perseverance
It after temperature stirring is completely dispersed in DMF to PAN, then weighs Co (CH3COO) 24H2O and is added in above-mentioned solution, stir to complete
Fully dissolved obtains spinning solution；(2) it is added lytic agent into resulting spinning solution, stirring is to sufficiently dissolving and be uniformly mixed；
(3) spinning liquid is transferred in syringe, the liquid inventory during electrostatic spinning is controlled using micro-injection pump, is put into
Spinning is carried out on electrostatic spinning device, obtained spinning be dried be placed in Muffle furnace carry out high-temperature heat treatment obtain Co3O4
Fiber；(4) Co is weighed3O4Fiber and graphite oxide dispersion are added ultrasound in deionized water and obtain Co3O4Fiber/graphite oxide
Then alkene dispersion liquid moves into dispersion liquid in microwave reaction instrument, graphene doping is prepared in microwave radiation reaction reduction
Co3O4Hollow fibre.
Laboratory apparatus: surface sweeping Electronic Speculum microscope, x-ray diffractometer, Raman spectrometer, electrostatic spinning device, light reaction instrument,
Ultraviolet-visible light photometer, vacuum oven, Muffle furnace, electric heating constant-temperature blowing drying box, ultrasonic washing instrument, N2Absorption-
Specific-surface area detection instrument is desorbed.
Experiment reagent: polyacrylonitrile (PAN), n,N-Dimethylformamide (DMF), cobalt acetate, dehydrated alcohol, GO solution,
Methylene blue.
Under ultraviolet light, degradation of dye methylene blue solution is tested come the photocatalysis of test sample by photocatalysis
Performance.The sample for weighing 0.02g doping different proportion respectively is put into 50mL methylene blue solution (10mg/L), dark reaction
30min reaches adsorption-desorption balance.300W mercury lamp light source is opened, light-catalyzed reaction is carried out under ultraviolet light.Every
30min takes a certain amount of methylene blue solution, and centrifuge separation takes supernatant, after the completion of sampling.By sampling sequence with it is ultraviolet-can
See that spectrophotometric measures supernatant uv-visible absorption spectra, writes down maximum peak absorption intensity and calculate the degradation of methylene blue
Rate.It factually tests the data obtained and makees uv absorption spectra and degradation efficiency figure, analyze the photocatalysis performance of several samples.
Fig. 1-Figure 10 is Co3O4And Co3O4/ rGO composite material low power and high power SEM figure are respectively by Fig. 3,5,7 and 9
Co3O4/rGO-1、Co3O4/rGO-2、Co3O4/ rGO-3 and Co3O4The low power SEM picture of/rGO-4, can be clearly from figure
See that the graphene of sheet is doped to Co3O4Middle formation Co3O4/ rGO composite material.Fig. 4,6,8 and 10 are respectively Co3O4/rGO-
1、Co3O4/rGO-2、Co3O4/ rGO-3 and Co3O4The high power SEM picture of/rGO-4, it can be seen that rGO is wrapped in Co3O4Fiber,
Form a kind of loose porous Co3O4/ rGO composite structure.
Figure 11 is Co3O4Hollow fibre nitrogen adsorption-desorption labyrinth and graph of pore diameter distribution.As can be seen from Figure 11
Co3O4Hollow fibre shows apparent IV type isothermal curve, illustrates Co3O4There is a large amount of mesoporous (2-50nm) in surface, in phase
When in the range of pressure P/P0=0.95~1.0, adsorption curve near vertical illustrates to be situated between with the presence of a large amount of macropores (> 50nm)
The diffusion and transfer that the presence of hole and macropore has conducive to dye molecule in photocatalytic process.From graph of pore diameter distribution as can be seen that hole
Co when diameter is at 30nm3O4With maximum pore volume, it is also demonstrated that a large amount of mesoporous presence, this is tied with obtained by adsorption curve
Fruit is consistent.Test obtains Co3O4The specific surface area of hollow fibre can reach 20.8m2/ g, it is known that the adsorption capacity of material and
Photocatalysis performance is stronger.
Figure 12 is Co3O4With Co3O4The Raman spectrogram of/rGO composite material.Compare the peak spectrogram D and the peak G I of rGOD/IGRatio, it is known that there are rGO in composite materials.Co as seen from Figure 123O4And Co3O4The Raman spectrum of/rGO composite material
In A (462cm-1)、B(504cm-1)、C(668cm-1) at show apparent peak, these peaks are Co3O4Raman spectral characteristics
Absorption peak.With pure Co3O4It compares, Co3O4/ rGO-1 and Co3O4There is not the characteristic absorption peak of rGO in/rGO-2, is due to rGO
The too low reason of doping ratio. Co3O4/ rGO-3 and Co3O4/ rGO-4 composite material is in 1346cm-1And 1588cm-1Place occurs
Absorption peak (the 1346cm that absorption peak, the two absorption peaks and rGO are shown-1And 1588cm-1) position is identical, in 1346 cm-1
Place occurs being D band absorption peak, and the peak D represents disordered carbon；In 1588cm-1Place occurs being G band absorption peak, and the peak G represents sp2It is miscellaneous
Change carbon or orderly carbon, it follows that rGO is successfully doped to Co3O4In.
Figure 13 is Co3O4With Co3O4/ rGO composite material XRD spectra compares rGO standard PDF card as seen from Figure 13
Piece (PDF#50-0927) compares the XRD spectra of rGO 2 θ are 22.89 °, 43.32 ° of crystallographic plane diffraction peak is (113), (315)
Know that the GO adulterated is successfully reduced to rGO in the composite；Pure Co3O42 θ be 19.00 °, 31.27 °, 36.84 °,
There is peak at 38.55 °, 44.81 °, 55.66 °, 59.35 ° and 65.23 °, compares Co3O4Standard PDF card (PDF#42-1467)
The respectively Co3O4 crystallographic plane diffraction peak of (111), (220), (311), (222), (400), (422), (511) and (440).Institute
With the Co of different proportion3O4The diffraction maximum of/rGO composite material is similar, and with pure Co3O4Standard diffraction peak it is consistent,
This illustrates rGO doping without changing Co3O4Its original crystal form generates new crystal phase.Because rGO doping ratio is low, and Co3O4
The peak intensity of characteristic peak is stronger, so the characteristic peak of rGO does not occur in composite material XRD spectrum.
Figure 14 is Co3O4With the ultraviolet-visible absorption spectroscopy spectrogram of Co3O4/rGO composite material.As seen from Figure 14,
Within the scope of the absorbing wavelength of 300nm~800nm, with simple Co3O4Absorption spectrum is compared, doping different proportion GO's
Co3O4/ rGO composite material shows stronger absorption peak, it is seen then that Co can be remarkably reinforced in doping rGO3O4Extinction it is strong
Degree, to be conducive to improve its photocatalysis performance.
Figure 15 is Co3O4The ultraviolet-ray visible absorbing peak of/rGO-4 composite material photocatalytic degradation of dye methylene blue and anti-
Relational graph between seasonable, as seen from Figure 15 over time it is directly proportional to dyestuff methylene blue concentration it is ultraviolet-can
To see that the intensity of absorption peak gradually weakens, illustrates the extension with degradation time, methylene blue concentration gradually decreases in solution,
Co3O4/ rGO-4 has the performance of excellent photocatalytic degradation methylene blue.Figure 16 is Co3O4And doping different proportion
GOCo3O4/ rGO composite material rate of photocatalytic oxidation figure.The Co known to Figure 16 degradation rate figure3O4/ rGO-4 has preferable
Photocatalysis performance.By experimental data and according to absorbance calculation formula, (photocatalysis effect degradation rate D is measured, degradation rate D
It is calculated by reaction front and back absorbance A 0, A, the concentration C 0 of dyestuff, C)
Know Co3O4、Co3O4/rGO-1、Co3O4/rGO-2、Co3O4/ rGO-3 and Co3O4/ rGO-4 is in ultraviolet lighting
After 180min, the degradation rate to dyestuff methylene blue is respectively 16.6%, 18.1%, 22.1%, 30.1% and 62.3%, is said
Bright graphene doping can be improved Co3O4The rate of degradation of methylene blue shows best degradation when doping is 12%
Effect, this is because Co3O4/ rGO composite material is transferred to conduction band process from valence band under the irradiation of mercury lamp, in light induced electron
In, rGO excellent electric conductivity accelerates the rate (Figure 17) that light induced electron is migrated to reaction-ure surface, to improve composite wood
The rate of photocatalytic oxidation of material；The doping of rGO can significantly improve the optical absorption intensity (Figure 17) of material, inhibit photoproduction electricity
Son-hole is compound, improves photocatalysis quantum efficiency, and then improve the photocatalysis performance of material.
Embodiment 2:
A kind of graphene doping Co3O4The preparation method of hollow fibre is to utilize electrostatic spinning technique and high-temperature heat treatment method
Prepare Co3O4Then hollow fibre reacts reduction preparation Co using with microwave radiation3O4/ rGO composite material；It is described to prepare stone
Black alkene adulterates Co3O4The step of hollow fibre includes that (1) weighs N,N-dimethylformamide (DMF) and polyacrylonitrile (PAN) perseverance
It after temperature stirring is completely dispersed in DMF to PAN, then weighs Co (CH3COO) 24H2O and is added in above-mentioned solution, stir to complete
Fully dissolved obtains spinning solution；(2) it is added lytic agent into resulting spinning solution, stirring is to sufficiently dissolving and be uniformly mixed；
(3) spinning liquid is transferred in syringe, the liquid inventory during electrostatic spinning is controlled using micro-injection pump, is put into
Spinning is carried out on electrostatic spinning device, obtained spinning be dried be placed in Muffle furnace carry out high-temperature heat treatment obtain Co3O4
Fiber；(4) Co is weighed3O4Fiber and graphite oxide dispersion are added ultrasound in deionized water and obtain Co3O4Fiber/graphite oxide
Then alkene dispersion liquid moves into dispersion liquid in microwave reaction instrument, graphene doping is prepared in microwave radiation reaction reduction
Co3O4Hollow fibre.
Laboratory apparatus, experiment reagent and experimental procedure are same as Example 1.
The preferred embodiment of the present invention has shown and described in above description, as previously described, it should be understood that the present invention is not office
It is limited to form disclosed herein, should not be regarded as an exclusion of other examples, and can be used for various other combinations, modification
And environment, and can be carried out within that scope of the inventive concept describe herein by the above teachings or related fields of technology or knowledge
Change.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of the present invention, then it all should be in institute of the present invention
In attached scope of protection of the claims.
Claims (10)
1. a kind of graphene adulterates Co3O4The preparation method of hollow fibre, it is characterized in that at using electrostatic spinning technique and high warm
Logos prepares Co3O4Then hollow fibre prepares Co using microwave method3O4/ rGO composite material；It is described to prepare graphene doping
Co3O4The step of hollow fibre include (1) weigh N,N-dimethylformamide (DMF) and polyacrylonitrile (PAN) constant temperature stir to
It after PAN is completely dispersed in DMF, then weighs Co (CH3COO) 24H2O and is added in above-mentioned solution, stirring is to being completely dissolved to obtain the final product
To spinning solution；(2) it is added solvent into resulting spinning solution, stirring is to sufficiently dissolving and be uniformly mixed；(3) spinning liquid is turned
It moves on in syringe, the liquid inventory during electrostatic spinning is controlled using micro-injection pump, is put on electrostatic spinning device and carries out
Spinning, obtained spinning be dried be placed in Muffle furnace carry out high-temperature heat treatment obtain Co3O4Fiber；(4) Co is weighed3O4
Fiber and graphite oxide dispersion are added ultrasound in deionized water and obtain Co3O4Then fiber/graphene oxide dispersion will divide
Dispersion liquid moves into microwave reaction instrument, and graphene doping Co is prepared in microwave radiation reaction reduction3O4Hollow fibre.
2. a kind of graphene according to claim 1 adulterates Co3O4The preparation method of hollow fibre, DMF described in feature are logical
It crosses extraction and distillation under vacuum is recycled from industrial wastewater, extractant o-sec-butyl will be added in the industrial wastewater containing DMF
Phenol adds diluent hexamethylene and n-octyl alcohol, 30 DEG C of waters bath with thermostatic control in extractant；It goes to suck water phase after the completion of layering, it will
Oil is mutually evaporated under reduced pressure, and it is DMF in liquid-collecting bottle that the steam steamed is collected by condensing tube condensation.
3. a kind of graphene according to claim 1 adulterates Co3O4The preparation method of hollow fibre, DMF described in feature with
PAN stirs 3h under conditions of environment temperature is 70 DEG C, with magnetic stirring apparatus 800r/min, so that PAN is completely dispersed DMF
In；Under the conditions of addition Co (CH3COO) 24H2O into above-mentioned solution, 70 DEG C, 2h is stirred with magnetic stirring apparatus 800r/min,
It is completely dissolved to obtain spinning solution；DMF, PAN and Co (CH3COO) the 24H2O mass ratio is 9:1:1.
4. a kind of graphene according to claim 1 adulterates Co3O4The preparation method of hollow fibre, it is characterised in that described
Co (CH3COO) 24H2O is prepared using plasma exchange process, adsorbs CoCl using ion exchange column2Solution, ion exchange column
Interior filling weak-acid cation-exchange resin after the completion of absorption wash with distilled water removes remaining unadsorbed in resin
CoCl2, then with spirit of vinegar resin layer is sufficiently washed, until using AgNO3Until inspection does not measure the Cl ion in cleaning solution, after washing
Resin eluted with acetic acid, obtain the mixture of cobalt acetate and acetic acid, finally with vacuum evaporating crystalization cobalt acetate and recycle vinegar
Acid.
5. a kind of graphene according to claim 1 adulterates Co3O4The preparation method of hollow fibre, feature is described molten
Agent is one of methylene chloride, chloroform and dioxane, is stirred evenly by magnetic stirring apparatus 800r/min.
6. a kind of graphene according to claim 1 adulterates Co3O4The preparation method of hollow fibre, feature is described micro-
The feeding speed for measuring syringe pump is 0.025-0.059mL/min.
7. a kind of graphene according to claim 1 adulterates Co3O4The preparation method of hollow fibre, it is characterised in that described
The condition of spinning is electrostatic spinning device voltage 16KV, temperature is 20 DEG C, polar plate interval 18cm, spinning flow velocity 1mL/h.
8. a kind of graphene according to claim 1 adulterates Co3O4The preparation method of hollow fibre, it is characterised in that described
The dry 12h of manufactured spinning is placed in Muffle furnace with nitrogen as protection gas, and the rate of 1 DEG C/min is warming up to 450 DEG C of high temperature
It is heat-treated 2h, obtains Co3O4Fiber.
9. a kind of graphene according to claim 1 adulterates Co3O4The preparation method of hollow fibre, it is characterised in that described
The preparation of graphite oxide uses H first2SO4And NaNO3Graphite is impregnated, intercalation is carried out to graphite, K is then added2FeO4To graphite
It is aoxidized, the H2SO4、NaNO3、K2FeO4It is 1:5:5 according to mass ratio, forms graphite oxide dispersion after reaction, uses
Ultrasonication obtains graphene oxide, finally uses microwave radiation reduction method, and reducing agent vitamin is added in graphite oxide
C obtains the graphite oxide dispersion of stable dispersion.
10. a kind of graphene according to claim 1 adulterates Co3O4The preparation method of hollow fibre, Co described in feature3O4
Fiber and with graphene dispersing solution according to 35:3 ratio mix, magnetic stirrer 800r/min stir 30min, formed it is compound molten
Liquid moves back in microwave reaction kit, and lower 180 DEG C of high pressure are reacted 5 minutes, cooled to room temperature, with secondary deionized water and nothing
Water-ethanol mixing centrifuge washing 3 times is finally dried in vacuo under 65 DEG C of constant temperature and obtains graphene doping Co for 24 hours3O4Hollow fibre.
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