CN106964331A - A kind of photochemical catalyst/porous carbon fiber composite and its preparation method and application - Google Patents
A kind of photochemical catalyst/porous carbon fiber composite and its preparation method and application Download PDFInfo
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- CN106964331A CN106964331A CN201710260150.XA CN201710260150A CN106964331A CN 106964331 A CN106964331 A CN 106964331A CN 201710260150 A CN201710260150 A CN 201710260150A CN 106964331 A CN106964331 A CN 106964331A
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- 239000004917 carbon fiber Substances 0.000 title claims abstract description 111
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 109
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000009987 spinning Methods 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- 238000001523 electrospinning Methods 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
- 230000001699 photocatalysis Effects 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 239000011941 photocatalyst Substances 0.000 claims abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005485 electric heating Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 3
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 208000011580 syndromic disease Diseases 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 13
- 229920002239 polyacrylonitrile Polymers 0.000 description 13
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000826860 Trapezium Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- 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
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/28023—Fibres or filaments
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
Solid high-polymer, is dissolved in organic solvent by a kind of preparation method of photochemical catalyst/porous carbon fiber composite first, forms spinning solution；Then by spinning solution electrostatic spinning, electrospinning precursor is made；By electrospinning precursor after pre-oxidation, carbonization, carbon fiber is obtained；Carbon fiber is activated through KOH, then cleans, dries through 5% HCl solution and distilled water again, obtain porous carbon fiber；Photocatalyst is cleaned through absolute ethyl alcohol, distilled water, dried, obtain photochemical catalyst/porous carbon fiber composite on porous carbon fiber using hydro-thermal method.Photochemical catalyst/porous carbon fiber composite prepared by this method has had two kinds of functions of absorption and catalysis concurrently, because the high specific surface area of carbon fiber can preferably disperse photochemical catalyst, increases light-catalysed contact area；The good electric conductivity of carbon fiber, can also preferably produce light induced electron, improve photocatalysis efficiency.Whole preparation process mild condition, it is simple to operate, suitable for a large amount of productions.
Description
Technical field
The present invention relates to the preparing technical field of composite.
Technical background
In recent years, along with China's industrial expansion, environmental pollution has had a strong impact on the life of the people and body is good for
Health, as one urgent problem to be solved of China.Photocatalysis treatment technology due to that organic pollution can be reduced into inorganic matter,
And reaction rate is fast, the characteristic such as utilization ratio height and non-secondary pollution of light is by extensive concern.Wherein, photocatalysis material how is improved
Expect to turn into the focus of research for the disposal ability of environmental pollution (particularly water pollution).One of which method is by carbon and light
Catalyst is combined, and using the electric conductivity of carbon, improves the performance of photochemical catalyst.For example, Chinese invention patent application
201510827373.0 describe the catalysis material that metal oxide and CNT are combined by a kind of utilization sol-gel process
Preparation method, but sol-gel process complex operation, metal oxide is easily accumulated, and CNT can not provide more
Absorption duct.But this invention, which demonstrates carbon material and photochemical catalyst being combined, can preferably handle organic wastewater, this hair
It is bright to propose a kind of new photochemical catalyst/carbon material composite.Photocatalysis is loaded using simpler hydro-thermal method herein
Agent, carbon carrier uses electrostatic spinning, and method of electrostatic spinning can prepare the carbon fiber of Nano grade, and activate pore-creating by KOH
To strengthen the adsorption capacity of carbon fiber so that this material plays the processing function for pollutant to the full extent.
The content of the invention
It is an object of the invention to provide a kind of photochemical catalyst/porous carbon fiber composite and preparation method thereof, with tradition
Compared applied to graininess, bar-shaped, spherical hydro-thermal method, because the big specific surface area of carbon fiber is applied to the hydro-thermal on carbon fiber
Method can preferably disperse photochemical catalyst, carbon fiber is had two kinds of functions of absorption and catalysis, and whole preparation process condition concurrently
Gently, it is simple to operate, suitable for a large amount of productions.
The first aspect of the invention：
A kind of photochemical catalyst/porous carbon fiber composite, includes the porous carbon fiber as carrier, and be carried on
The photochemical catalyst on its surface.
Described photochemical catalyst is CeO2Or ZnO.
The second aspect of the invention：A kind of preparation method of photochemical catalyst/porous carbon fiber composite,
Comprise the following steps：
(1) solid high-polymer is dissolved in organic solvent, forms spinning presoma；
(2) by spinning presoma electrostatic spinning, electrospinning precursor is made；
(3) electrospinning precursor is obtained into carbon fiber after pre-oxidation, carbonization；
(4) carbon fiber is activated through KOH, then cleans, dry through 5% HCl solution and distilled water again, obtain porous carbon
Fiber；
(5) utilize hydro-thermal method that photocatalyst, on porous carbon fiber, is cleaned through absolute ethyl alcohol, distilled water, dried,
Obtain photochemical catalyst/porous carbon fiber composite.
Present invention utilization method of electrostatic spinning can be produced largely, and carbon fiber is prepared the characteristics of simple and easy to apply, and utilization activates hand
Carbon fiber is changed into porous carbon fiber by section, and its absorption property is improved with this, then prepares photochemical catalyst/porous by hydro-thermal load
Carbon fibre composite.
Further, high polymer of the present invention is polyacrylonitrile (PAN) or PVP (PVP).PAN or PVP is easy spinning
The high polymer of silk, improves the operability of spinning process.
The organic solvent is absolute ethyl alcohol or dichloromethane (DMF).These solvents can preferably dissolve PAN or PVP,
It is easy to spinning.
The spinning voltage of the electrostatic spinning is 15kV, and it is 20cm to receive distance, and environment temperature is≤40 DEG C, ambient humidity
≤ 30%, spinning flow velocity 2mm/min, the angle of inclination of syringe is 15 °.On this condition, spinning process is easier to operate to,
It is easy into silk.
The environment temperature of the pre-oxidation is 250 DEG C, and the time of pre-oxidation is 2h.It is former to fiber in this temperature and time
Silk pre-oxidation, may be such that macromolecule is converted into resistant to elevated temperatures trapezium structure by cyclodehydrogenation in precursor, to ensure original
Stability of the silk under high temperature cabonization.
The carbonization is in nitrogen (N2) middle progress, heating rate is 5 DEG C/min, the constant temperature 2h under the conditions of temperature is 800 DEG C,
The more abundant phosphorus content of carbonization can be made higher.
The activation condition is carbon fiber and KOH mass ratioes are 3:4, carbon fiber is immersed in 2h in KOH solution, Ran Hou
80 DEG C of drying in baking oven, then the carbon fiber after drying is placed in tube furnace, 800 DEG C are warming up to from room temperature with 10 DEG C/min,
Room temperature is down to after insulation 30min, is activated on this condition, the specific surface area and pore distribution of fiber are more preferable.
Described photochemical catalyst is CeO2, ZnO etc., these are all cheap and easy to get.
The third aspect of the invention：
Described photochemical catalyst/application of the porous carbon fiber composite in for the degraded containing organic wastewater.
Advantages of the present invention and good effect are：
1. the present invention can be produced largely using method of electrostatic spinning, carbon fiber is prepared the characteristics of simple and easy to apply, and utilize activation
Carbon fiber is changed into porous carbon fiber by means, and its absorption property is improved with this, then prepares photochemical catalyst/many by hydro-thermal load
Hole carbon fibre composite.
2. photochemical catalyst/porous carbon fiber composite prepared by this method has had two kinds of functions of absorption and catalysis concurrently, special
It is not by the way that carbon fiber is activated into pore-creating, the adsorption function of carbon fiber is improved to a certain extent, strengthens it to pollutant
Removal effect.
3. because the high specific surface area of carbon fiber can preferably disperse photochemical catalyst, increase light-catalysed contact area；
The good electric conductivity of carbon fiber, can also preferably guide light induced electron, improve photocatalysis efficiency.
4. method of electrostatic spinning and hydro-thermal method that this method is used are all simple and easy to do and can largely produce, from warp
In Ji, preparation cost can be reduced, the economic benefit of process is improved.
5. tradition is applied to graininess, bar-shaped, spherical hydro-thermal method and easily causes packing phenomenon, due to the big ratio of carbon fiber
The hydro-thermal method that surface area is applied on carbon fiber can preferably disperse photochemical catalyst, so as to improve its photocatalysis effect.
Brief description of the drawings
Fig. 1 is the preparation flow figure of photochemical catalyst/porous carbon fiber composite.
Fig. 2 is that photochemical catalyst is CeO using PAN as high polymer2The photochemical catalyst of preparation/porous carbon fiber composite
SEM schemes.
Fig. 3 is that photochemical catalyst is CeO using PVP as high polymer2The photochemical catalyst of preparation/porous carbon fiber composite
SEM schemes.
Fig. 4 is CeO prepared by conventional hydrothermal method2Particle and CeO2The photochemical catalyst of preparation/porous carbon fiber composite pair
Than figure.
Fig. 5 is CeO prepared by conventional hydrothermal method2Particle and CeO2Removal of/porous carbon fiber the composite for methyl blue
Rate figure.
Embodiment
Percentage (%) described in description of the invention is in the case of without special instruction, all referring to mass percent.
First, the technique for preparing photochemical catalyst/porous carbon fiber composite：
Embodiment 1:Using PAN as high polymer, photochemical catalyst is CeO2
1st, PAN 1.5g are weighed, is dissolved in 15g DMF, is completely dissolved under magnetic stirring, spinning solution presoma is produced.Will
Spinning solution presoma is installed on spinning on electrospinning device, and spinning voltage is 15kV, and it is 20cm to receive distance, and environment temperature is
≤ 40 DEG C, ambient humidity≤30%, spinning flow velocity 2mm/min, the angle of inclination of syringe is 15 °, is obtained after electrostatic spinning
Obtain PAN precursor.
2nd, PAN precursor is pre-oxidized into 2h with 5 DEG C/min heating rate at 250 DEG C in atmosphere, then in N2In with 5
DEG C/min heating rate is carbonized 2h at 800 DEG C, produces carbon fiber.
3rd, it is 3 by carbon fiber and KOH mass ratioes:4, carbon fiber is immersed in 2h in KOH solution, then in an oven 80 DEG C
Drying, then the carbon fiber after drying is placed in tube furnace, it is warming up to 800 DEG C, the timing of insulation one from room temperature with 10 DEG C/min
Between after be down to room temperature, then cleaned again through 5% HCl solution and distilled water, dry, produce porous carbon fiber.
4th, 0.1g porous carbon fibers are mixed in 0.3g Ce (NO3)3·6H2O and 2.5g CO (NH2)2Mixed solution in, mix
Stirring 10min is closed, mixed liquor is transferred in 100mL stainless steel water thermal synthesis autoclaves, and it is dry in electric heating constant temperature air blast
Isothermal reaction 24h at 160 DEG C in dry case.After reaction terminates, by the carbon fiber ethanol and redistilled water in reactor repeatedly
Cleaning, and dried 12 hours at 60 DEG C, produce CeO2/ porous carbon fiber composite.The SEM figures of resulting materials are shown in Fig. 2.
Embodiment 2:Using PVP as high polymer, photochemical catalyst is CeO2
1st, PVP 1.5g are weighed, is dissolved in 15g DMF, is completely dissolved under magnetic stirring, spinning liquid presoma is produced.It will spin
Silk liquid presoma be installed on spinning on electrospinning device, spinning voltage is 15kV, receive distance be 20cm, environment temperature for≤
40 DEG C, ambient humidity≤30%, spinning flow velocity 2mm/min, the angle of inclination of syringe is 15 °, is obtained after electrostatic spinning
PVP precursor.
2nd, PVP precursor is pre-oxidized into 2h with 5 DEG C/min heating rate at 250 DEG C in atmosphere, then in N2In with 5
DEG C/min heating rate is carbonized 2h at 800 DEG C, produces carbon fiber.
3rd, it is 3 by carbon fiber and KOH mass ratioes:4, carbon fiber is immersed in 2h in KOH solution, then in an oven 80 DEG C
Drying, then the carbon fiber after drying is placed in tube furnace, it is warming up to 800 DEG C, the timing of insulation one from room temperature with 10 DEG C/min
Between after be down to room temperature, then cleaned again through 5% HCl solution and distilled water, dry, produce porous carbon fiber.
4th, 0.1g porous carbon fibers are mixed in 0.3g Ce (NO3)3·6H2O and 2.5g CO (NH2)2Mixed solution in, mix
Stirring 10min is closed, mixed liquor is transferred in 100mL stainless steel water thermal synthesis autoclaves, and it is dry in electric heating constant temperature air blast
Isothermal reaction 24h at 160 DEG C in dry case.After reaction terminates, by the carbon fiber ethanol and redistilled water in reactor repeatedly
Cleaning, and dried 12 hours at 60 DEG C, produce CeO2/ porous carbon fiber composite, the SEM figures of resulting materials are shown in Fig. 3.
Embodiment 3:Using PAN as high polymer, photochemical catalyst is ZnO
1st, PAN 1.5g are weighed, is dissolved in 15g DMF, is completely dissolved under magnetic stirring, spinning solution presoma is produced.Will
Spinning solution presoma is installed on spinning on electrospinning device, and spinning voltage is 15kV, and it is 20cm to receive distance, and environment temperature is
≤ 40 DEG C, ambient humidity≤30%, spinning flow velocity 2mm/min, the angle of inclination of syringe is 15 °, is obtained after electrostatic spinning
Obtain PAN precursor.
2nd, PAN precursor is pre-oxidized into 2h with 5 DEG C/min heating rate at 250 DEG C in atmosphere, then with 5 in N2
DEG C/min heating rate is carbonized 2h at 800 DEG C, produces carbon fiber.
3rd, it is 3 by carbon fiber and KOH mass ratioes:4, carbon fiber is immersed in 2h in KOH solution, then in an oven 80 DEG C
Drying, then the carbon fiber after drying is placed in tube furnace, it is warming up to 800 DEG C, the timing of insulation one from room temperature with 10 DEG C/min
Between after be down to room temperature, then cleaned again through 5% HCl solution and distilled water, dry, produce porous carbon fiber.
4th, 0.1g porous carbon fibers are mixed in 0.4g acetic acid zinc solutions, the NaOH for being 0.5mol/L with substance withdrawl syndrome
Solution regulation PH is 10, continues to stir 10min, mixed liquor is transferred in 100mL stainless steel water thermal synthesis autoclaves, and
The isothermal reaction 24h at 160 DEG C in electric heating constant-temperature blowing drying box.After reaction terminates, by the carbon fiber ethanol in reactor
Clean, and dried 12 hours at 60 DEG C repeatedly with redistilled water, produce ZnO/ porous carbon fiber composites.
Embodiment 4:Using PVP as high polymer, photochemical catalyst is ZnO
1st, PVP 1.5g are weighed, is dissolved in 15g DMF, is completely dissolved under magnetic stirring, spinning liquid presoma is produced.It will spin
Silk liquid presoma be installed on spinning on electrospinning device, spinning voltage is 15kV, receive distance be 20cm, environment temperature for≤
40 DEG C, ambient humidity≤30%, spinning flow velocity 2mm/min, the angle of inclination of syringe is 15 °, is obtained after electrostatic spinning
PVP precursor.
2nd, PVP precursor is pre-oxidized into 2h with 5 DEG C/min heating rate at 250 DEG C in atmosphere, then in N2In with 5
DEG C/min heating rate is carbonized 2h at 800 DEG C, produces carbon fiber.
3rd, it is 3 by carbon fiber and KOH mass ratioes:4, carbon fiber is immersed in 2h in KOH solution, then in an oven 80 DEG C
Drying, then the carbon fiber after drying is placed in tube furnace, it is warming up to 800 DEG C, the timing of insulation one from room temperature with 10 DEG C/min
Between after be down to room temperature, then cleaned again through 5% HCl solution and distilled water, dry, produce porous carbon fiber.
4th, 0.1g porous carbon fibers are mixed in 0.4g acetic acid zinc solutions, the NaOH for being 0.5mol/L with substance withdrawl syndrome
Solution regulation PH is 10, continues to stir 10min, mixed liquor is transferred in 100mL stainless steel water thermal synthesis autoclaves, and
The isothermal reaction 24h at 160 DEG C in electric heating constant-temperature blowing drying box.After reaction terminates, by the carbon fiber ethanol in reactor
Clean, and dried 12 hours at 60 DEG C repeatedly with redistilled water, produce ZnO/ porous carbon fiber composites.
Embodiment 5:Conventional hydrothermal method prepares CeO2Preparation process
1st, 0.3g Ce (NO are weighed3)3·6H2O and 2.5g CO (NH2)2It is dissolved in deionized water, mixes 10min.
Mixed liquor is transferred in 100mL stainless steel water thermal synthesis autoclaves, and in electric heating constant-temperature blowing drying box at 160 DEG C
Isothermal reaction 24h.After reaction terminates, white reaction sediment in reactor is cleaned repeatedly with ethanol and redistilled water, then
Products therefrom is dried into 12h at 60 DEG C, ground with agate mortar.Finally by white solid powder in tube furnace at 300 DEG C
Calcining at constant temperature 3h, obtains pale yellow powder shape solid, as CeO2。
2nd, the CeO that will be prepared in embodiment 12The CeO that/porous carbon fiber composite is prepared with conventional hydrothermal method2Work compares
Compared with comparing two kinds of CeO by SEM figures2Particle size and distribution situation.As a result Fig. 4 and table 1 below are seen.
The CeO of table 12Particle size and distribution situation
As seen from Figure 4, the CeO prepared by conventional hydrothermal method2Packing phenomenon is serious, and particle size is larger,
By CeO2It is carried on porous carbon fiber, because the big specific surface area of porous carbon fiber can preferably disperse CeO2And particle chi
It is very little to reduce, so it is more beneficial for improving catalytic effect.
Embodiment 6:CeO2Particle, porous carbon fiber, CeO2Processing of/porous carbon fiber the composite for methyl blue
5mg/L methyl blue is prepared as photocatalytic degradation liquid, takes 100mL methyl blue solutions to be put in 250mL every time
In beaker, 40W uviol lamp is installed at the top of beaker, the distance of uviol lamp and beaker is 15cm, under conditions of stirring plus
Enter 0.1g CeO2Particle (porous carbon fiber, CeO2Mixture, the CeO of particle and porous carbon fiber2/ porous carbon fiber composite wood
Material), since the timing connecting uviol lamp power supply every 20min, take suspension, centrifuging and taking supernatant liquor is measured with spectrophotometric
Determine absorbance, calculate degradation rate.
As a result Fig. 5 and table 2 below are seen.
The methyl blue clearance (120min) of table 2
As seen from Figure 5, under no light condition, CeO prepared by conventional hydrothermal method2Particle is and porous without removal effect
The removal effect of carbon fiber is about 30%；Under light conditions, CeO2/ porous carbon fiber composite clearance reaches
70%, hence it is evident that the CeO prepared better than conventional hydrothermal method2Particle.It can be obtained by 20min to 120min curve, CeO2/ porous carbon is fine
Tie up composite slope of a curve substantially tall and big in CeO2Clay ratio silt slope, this explanation CeO2On/porous carbon fiber composite
CeO2There is more preferable catalytic rate for methyl blue waste water, this is mainly due to CeO2Size reduce and carbon fiber and CeO2
Synergy cause；In addition, adding CeO simultaneously in the solution2The treatment effect of particle and porous carbon fiber is still too late
CeO2/ porous carbon fiber composite, CeO is added mainly due to the surface in porous carbon fiber by way of load2Particle
When, it is possible to use the suction-operated reinforcing CeO of porous carbon fiber2Photocatalytic effect.
Claims (10)
1. a kind of photochemical catalyst/porous carbon fiber composite, it is characterised in that include the porous carbon fiber as carrier,
And it is carried on the photochemical catalyst on its surface.
2. photochemical catalyst according to claim 1/porous carbon fiber composite, it is characterised in that described photocatalysis
Agent is CeO2Or ZnO.
3. the preparation method of photochemical catalyst/porous carbon fiber composite, it is characterised in that comprise the following steps：
(1) solid high-polymer is dissolved in organic solvent, forms spinning presoma；
(2) by spinning presoma electrostatic spinning, electrospinning precursor is made；
(3) electrospinning precursor is obtained into carbon fiber after pre-oxidation, carbonization；
(4) carbon fiber is activated through KOH, then cleans, dry through 5% HCl solution and distilled water again, obtain porous carbon fine
Dimension；
(5) utilize hydro-thermal method that photocatalyst, on porous carbon fiber, is cleaned through absolute ethyl alcohol, distilled water, dried, obtained
Photochemical catalyst/porous carbon fiber composite.
4. preparation method according to claim 1, it is characterised in that：The solid high-polymer is PAN or PVP；It is described to have
Machine solvent is absolute ethyl alcohol or DMF；The spinning voltage of the electrostatic spinning is 15kV, and it is 20cm to receive distance, and environment temperature is
≤ 40 DEG C, ambient humidity≤30%, spinning flow velocity 2mm/min, the angle of inclination of syringe is 15 °.
5. preparation method according to claim 1, it is characterised in that：The pre-oxidizing conditions in atmosphere with 5 DEG C/
Min heating rate aoxidizes 2h at 250 DEG C；The Carbonization Conditions are in N2In with 5 DEG C/min heating rate at 800 DEG C
Be carbonized 2h.
6. preparation method according to claim 1, it is characterised in that：The activation condition is carbon fiber and KOH mass ratioes
For 3:4, carbon fiber is immersed in 2h in KOH solution, then 80 DEG C of drying in an oven, then the carbon fiber after drying is placed in
In tube furnace, room temperature is down to after being warming up to 800 DEG C, held for some time 30min from room temperature with 10 DEG C/min.
7. preparation method according to claim 1, it is characterised in that：Photochemical catalyst is CeO2Or ZnO.
8. preparation method according to claim 1, it is characterised in that：Photochemical catalyst is CeO2, the hydro-thermal method condition is will
0.1g porous carbon fibers are mixed in 0.3g Ce (NO3)3·6H2O and 2.5g CO (NH2)2Mixed solution in, mix 10min,
Mixed liquor is transferred in 100mL stainless steel water thermal synthesis autoclaves, and in electric heating constant-temperature blowing drying box at 160 DEG C
Isothermal reaction 24h；After reaction terminates, the carbon fiber in reactor is cleaned repeatedly with ethanol and redistilled water, and at 60 DEG C
Lower drying 12 hours, produces CeO2/ porous carbon fiber composite.
9. preparation method according to claim 1, it is characterised in that：Photochemical catalyst is ZnO, and the hydro-thermal method condition is will
0.1g porous carbon fibers are mixed in 0.4g acetic acid zinc solutions, and the NaOH solution for being 0.5mol/L with substance withdrawl syndrome regulation PH is
10, continue to stir 10min, mixed liquor is transferred in 100mL stainless steel water thermal synthesis autoclaves, and in electric heating constant temperature drum
Isothermal reaction 24h at 160 DEG C in wind drying box；After reaction terminates, by the carbon fiber ethanol and redistilled water in reactor
Clean, and dried 12 hours at 60 DEG C repeatedly, produce ZnO/ porous carbon fiber composites.
10. photochemical catalyst/porous carbon fiber composite described in claim 1 is in for the degraded containing organic wastewater
Using.
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