CN109225183A - A kind of carbon dots are titania-doped/carbon composite fibre and preparation method thereof - Google Patents
A kind of carbon dots are titania-doped/carbon composite fibre and preparation method thereof Download PDFInfo
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- CN109225183A CN109225183A CN201811106886.2A CN201811106886A CN109225183A CN 109225183 A CN109225183 A CN 109225183A CN 201811106886 A CN201811106886 A CN 201811106886A CN 109225183 A CN109225183 A CN 109225183A
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- carbon
- titanium dioxide
- fibre
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 239000000835 fiber Substances 0.000 title claims abstract description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 27
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 12
- 239000004917 carbon fiber Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 210000000498 stratum granulosum Anatomy 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- -1 glycidyl ester Chemical class 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 239000002657 fibrous material Substances 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 231100001234 toxic pollutant Toxicity 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- XSMJZKTTXZAXHD-UHFFFAOYSA-N ethene;2-methylprop-2-enoic acid Chemical group C=C.CC(=C)C(O)=O XSMJZKTTXZAXHD-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000000264 sodium ferrocyanide Substances 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/58—
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of carbon dots it is titania-doped/carbon composite fibre and preparation method thereof.The composite fibre is formed by the carbon dots doping titanium dioxide nano stratum granulosum package internal carbon fibers of outer layer tubulose, the carbon dots doping titanium dioxide nano stratum granulosum of the composite material outer layer ensures composite material specific surface area with higher, and kernel carbon fiber is as conductive structure, be conducive to the separation and conduction of titanium dioxide photoproduction carrier, to improve the photocatalytic degradation efficiency of titanium dioxide, it is entrained in TiO2Carbon in nano particle is voluntarily to generate in preparation process.Complex fiber material large specific surface area prepared by the present invention, photoelectric properties are good, the toxic pollutant that can be used in catalytic degradation water body.
Description
Technical field
The invention belongs to the preparation technical fields of scavenging material, and in particular to and a kind of carbon dots are titania-doped/and carbon is compound
Fiber and preparation method thereof.
Background technique
With the fast development of human society, people's lives quality is improved constantly, and at the same time, environment is by broken
The problem of bad and pollution, also increasingly sharpens, and curbing environmental pollution has become whole world common concern and urgently to be solved one asks greatly
Topic.Nano semiconductor catalysis material is due to that can be widely used in improvement and protection environment by the mankind with degradable organic pollutant.
Compared with some other method for solving organic pollutant such as chemical oxidization method, high temperature incineration method, physisorphtion, using nanometer
The method that conductor photocatalysis material carries out photocatalytic degradation has high-efficient, energy consumption is low, applied widely, secondary pollution is few etc.
Advantage.
Titanium dioxide (TiO2) chemical property is stable, is not susceptible to that photoetch, low in cost, light-catalyzed reaction is living after illumination
Property it is high and to biological nontoxic, a kind of semiconductor light-catalyst for currently most having application potential is acknowledged as, past tens
It is rapidly developed in year, is widely used in sewage treatment, air cleaning, automatically cleaning construction material, solar battery, biography
Sensor etc..A large number of studies show that TiO2Photocatalytic activity in addition to crystal habit structure mutually outside the Pass, also with its specific surface
Product, to the doping of other elements, related with the factors such as compound and catalyst carrier the structure of other materials and property.Cause
This, realizes TiO using method appropriate2The controllable preparation of composite material is very necessary.For example, CN107029693A is disclosed
A kind of carbon dots titania-doped compound micro-pipes and preparation method thereof.It is template using spinning fibre, at sulfuric acid sulfonation
Reason.One layer of TiO is coated in fiber surface by sol-gal process again2.Finally by calcination processing, spinning material is carbonized, shape
At the titania-doped compound micro-pipe of carbon dots.Carbon dots ingredient can provide direct electric pathway for photo-generated carrier, it is ensured that quickly
Electron transport rate, reduce the recombination reaction that occurs in light-catalyzed reaction, thus improve the light of titanium dioxide nano material
Catalytic activity and photoelectric conversion efficiency.Furthermore tubular structure has biggish specific surface area, considerably increases and organic pollutant
Contact area.The composite material has and has higher catalytic degradation ability, but single tubular structure limitation to uns-dimethylhydrazine
Titanium dioxide photoproduction carries the conduction velocity of electronics, is unfavorable for the further promotion of catalytic degradation ability, and due to electrostatic spinning
Method preparation fibrous template cost is excessively high, is unfavorable for realizing industrialized production.
Summary of the invention
It is an object of the invention to propose a kind of carbon dots with unique microstructures it is titania-doped/carbon composite fibre
And preparation method thereof.
Realizing the technical solution of the object of the invention is: a kind of carbon dots are titania-doped/carbon composite fibre, and this is compound
Fiber is formed by the carbon dots doping titanium dioxide nano stratum granulosum package internal carbon fibers of outer layer tubulose.The composite material outer layer
Carbon dots doping titanium dioxide nano stratum granulosum ensures composite material specific surface area with higher, and kernel carbon fiber is used as and leads
Electric structure, is conducive to the separation and conduction of titanium dioxide photoproduction carrier, to improve the photocatalytic degradation efficiency of titanium dioxide.
It is entrained in TiO2Carbon in nano particle is voluntarily to generate in preparation process.
Further, carbon content is 5 ~ 12.5 wt%, content of titanium dioxide in carbon dots doping titanium dioxide nano stratum granulosum
For 87.5 ~ 95 wt%.
Further, content of the carbon in carbon dots doping titanium dioxide nano stratum granulosum in entire composite fibre is
1~5 wt%。
A kind of carbon dots are titania-doped/preparation method of carbon composite fibre, specific steps are as follows:
(1) at a certain temperature, polyacrylonitrile fibre is immersed in hydrolysis process in strong acid, washing, alcohol are washed；
(2) polyacrylonitrile fibre that processing obtains in step (1) is immersed in the mixed of titanate esters or titanate esters and organic solvent
It closes in solution after a certain period of time, then is placed in water or aqueous mixed solution and impregnates certain time, it is spare after dry；
(3) sample that step (2) obtains is warming up to 400 ~ 800 DEG C under inert gas protection, is calcined 2 ~ 2.5 hours, to temperature
Degree is down to room temperature and obtains composite material.
Further, in step (1), the main component of the polyacrylonitrile fibre is polyacrylonitrile or polymethyl
Nitrile, and the co-polymer of one or more of monomers can be contained, wherein these monomers include acrylonitrile, methacrylonitrile, methyl
Methyl acrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, two
Methacrylic acid glycol ester, vinyl acetate, N, N- dimethacrylamide, methacrylic acid, acrylic acid, methacrylic acid
Ethylene oxidic ester, styrene, divinylbenzene.
Further, in step (1), the length of polyacrylonitrile fibre is not particularly limited, preferably 1 ~ 3cm, and diameter is without special
It limits, preferably 1 ~ 20 μm.
Further, in step (1), polyacrylonitrile fibre is immersed in strong acid and hydrolyzes, and hydrolysis degree can be by adjusting
Concentration, hydrolysis temperature and the hydrolysis time control of acid, and then control the thickness and internal carbon fibers of the titania-doped layer of carbon dots
Diameter, strong acid used can be sulfuric acid, hydrochloric acid, and concentration is 0.1~10.0 mol/L, and hydrolysis temperature is 20 DEG C ~ 140 DEG C,
It is preferred that 120 DEG C ~ 140 DEG C, when selecting 120 DEG C ~ 140 DEG C, the hydrolysis process time is 1 ~ 1.5 hour, and temperature is lower, required time
It is longer.
Further, in step (2), titanate esters include the metatitanic acids alkane such as tetraethyl titanate, isopropyl titanate, butyl titanate
The mixture of one or more of oxygroup ester.
Further, in step (2), organic solvent includes the mixed of one or more of alcohols such as methanol, ethyl alcohol, propyl alcohol
Close object.
Further, in step (2), aqueous mixed solution includes one of alcohols such as methanol, ethyl alcohol, propyl alcohol or several
The mixed solution of kind and water.
Further, in step (2), the mass ratio of titanate esters and organic solvent is not particularly limited, preferably 1:1, aqueous
The concentration of water is not particularly limited in mixed solution, preferably 50wt%；Fiber is immersed in the mixed solution of titanate esters and organic solvent
1 ~ 36 hour, preferably 8-12 hours, then be placed in water or aqueous mixed solution and impregnate 10 minutes or more.
Further, in step (3), inert gas is nitrogen or argon gas or helium.
Further, in step (3), heating rate is not particularly limited, preferably 3 ~ 5 DEG C/min.
Compared with prior art, the present invention has the following obvious advantages:
(1) the method for the invention is used, carbon dots obtained are titania-doped/and carbon complex fiber material has conductive carbon fiber
Kernel is tieed up, is conducive to the separation and conduction of titanium dioxide photoproduction carrier, therefore the photocatalytic degradation of titanium dioxide can be improved
Efficiency.
(2) polyacrylonitrile fibre template used in the present invention is commercially produced product, is easy to get, low in cost, is conducive to big
Large-scale production, obtained carbon dots are titania-doped/and not only large specific surface area, photoelectric properties are good for carbon composite fibre composite material,
And chemical activity is high, is conducive to the toxic pollutant in catalytic degradation water body.
(3) preparation process of the present invention is simple, industrialized production easy to accomplish.
(4) present invention prepared by carbon dots it is titania-doped/carbon composite fibre composite material be macro-size material,
Easy to produce, application, recycling and recycling advantageously reduce cost, reduce secondary pollution.
Detailed description of the invention
Fig. 1 be in embodiment 1 carbon dots it is titania-doped/scanning electron microscope (SEM) photograph of carbon composite fibre.
Fig. 2 be in embodiment 2 carbon dots it is titania-doped/scanning electron microscope (SEM) photograph of carbon composite fibre.
Fig. 3 be in embodiment 5 carbon dots it is titania-doped/scanning electron microscope (SEM) photograph of carbon composite fibre.
Fig. 4 be in embodiment 6 carbon dots it is titania-doped/scanning electron microscope (SEM) photograph of carbon composite fibre.
Fig. 5 be in embodiment 1 carbon dots it is titania-doped/XRD diagram of carbon composite fibre.
Fig. 6 be carbon dots of the present invention it is titania-doped/carbon complex structure of filament schematic diagram.
Specific embodiment
The present invention is described in more detail below according to embodiment, but the present invention is not limited to this.
In conjunction with Fig. 6, carbon dots of the present invention are titania-doped/and carbon composite fibre by the carbon dots of outer layer tubulose adulterates two
Titanium dioxide nanoparticle layer package internal carbon fibers form.
Embodiment 1:
Under (1) 120 DEG C of oil bath, polyacrylonitrile fibre is immersed in hydrolysis process 1 hour in 50% sulfuric acid, washing, alcohol are washed；
(2) by the polyacrylonitrile fibre of surface hydrolysis be immersed in butyl titanate and ethyl alcohol mixed solution (butyl titanate with
The mass ratio of ethyl alcohol is 24 hours in 1:1), impregnates half an hour in the mixed solution of ethyl alcohol and distilled water；
(3) sample that step (2) obtains is warming up to 400 DEG C under nitrogen protection with the rate of 3 DEG C/min, keeps the temperature 2 hours, to
Temperature is down to room temperature and obtains titanium dioxide/carbon composite fibre composite material.
Embodiment 2:
Material is prepared according to described in embodiment 1, except that using 1.5 hours hydrolysis process time in step (2).
Embodiment 3:
Material is prepared according to described in embodiment 1, except that using 450 DEG C of calcination temperature in step (3).
Embodiment 4:
Material is prepared according to described in embodiment 1, except that using 500 DEG C of calcination temperature in step (3).
Embodiment 5:
Material is prepared according to described in embodiment 1, except that using 130 DEG C of oil bath temperature in step (1).
Embodiment 6:
Material is prepared according to described in embodiment 5, except that using 450 DEG C of calcination temperature in step (3).
Embodiment 7:
Material is prepared according to described in embodiment 5, except that using 500 DEG C of calcination temperature in step (3).
Embodiment 8:
Material is prepared according to described in embodiment 1, except that the oil bath temperature and 3mol/L of 80 DEG C of use in step (1)
Hydrochloric acid is hydrolyzed.
Embodiment 9:
Material is prepared according to described in embodiment 1, except that using polyacrylonitrile fibre felt in step (1).
Titanium dioxide/carbon composite fibre relevant characterization and performance test
(1) SEM: composite material obtained in appropriate embodiment 1 is taken to be placed in S-4800 in metal ion sputter after metal spraying
Pattern is observed under II field emission scanning electron microscope, as shown in Figure 1.From figure 1 it appears that composite fibre is the double-deck knot
Structure, as shown in fig. 6,10 ~ 12 μm of outer diameter, 4 ~ 5 μm of internal carbon fibers diameter.
(2) SEM: composite material obtained in appropriate embodiment 2 is taken to be placed in S- in metal ion sputter after metal spraying
Pattern is observed under 4800 II field emission scanning electron microscopes, as shown in Figure 2.From figure 2 it can be seen that composite fibre is bilayer
Structure, 10 ~ 12 μm of outer diameter, 3 ~ 4 μm of internal carbon fibers diameter.
(3) SEM: composite material obtained in appropriate embodiment 5 is taken to be placed in S- in metal ion sputter after metal spraying
Pattern is observed under 4800 II field emission scanning electron microscopes, as shown in Figure 3.From figure 3, it can be seen that composite fibre is bilayer
Structure, 8 ~ 12 μm of outer diameter, 4 ~ 5 μm of internal carbon fibers diameter.
(4) SEM: composite material obtained in appropriate embodiment 6 is taken to be placed in S- in metal ion sputter after metal spraying
Pattern is observed under 4800 II field emission scanning electron microscopes, as shown in Figure 4.Figure 4, it is seen that composite fibre is bilayer
Structure, 10 ~ 14 μm of outer diameter, 3 ~ 5 μm of internal carbon fibers diameter.
(5) XRD: taking composite material obtained in appropriate embodiment 1, carries out in D8 Advance polycrystal X ray diffractometer
XRD test, and compared with the polyacrylonitrile fibre of the titanium dioxide and surface hydrolysis calcined under the conditions of, as shown in Figure 5.From figure
5 as can be seen that titanium dioxide contained by composite material is predominantly anatase structured in embodiment 1.Embodiment 2-9 is after same test
It can obtain, titanium dioxide contained by the composite material is predominantly anatase structured.
(6) BET: taking composite material obtained in each embodiment, in Autosorb IQ3 surface analysis and aperture synthesis
Analyzer test, it is known that, the specific surface area of complex fiber material is 45m2/g~50 m2/g。
(7) TGA: taking composite material obtained in each embodiment, tests in 1 TGA thermogravimetric analyzer of Pyris, it is known that,
The titanium dichloride load amount of complex fiber material is 20% ~ 30 wt%.
(8) EDS: taking composite material obtained in each embodiment, in metal ion sputter after metal spraying, is placed in S-4800
Under II field emission scanning electron microscope, EDS test is carried out to the titania-doped layer of the carbon dots to fall off, it is known that, carbon dots doping
Carbon content is 5 ~ 12.5 wt% in titanium dioxide layer, and content of titanium dioxide is 87.5 ~ 95 wt%.The calculation shows that, carbon dots doping
Content of the carbon in entire complex fiber material is 1 ~ 5 wt% in titanium dioxide.
(9) carbon dots it is titania-doped/test of carbon composite fibre density of photocurrent: take 10mg composite material to be carried on 2
On the ito glass of × 3cm, photoelectricity current test is carried out under 500W xenon source using CHI electrochemical workstation (CHI660D),
Used is platinum electrode to electrode, and reference electrode is calomel electrode, and acquired results are as shown in table 1.As shown in Table 1, composite material
Photoelectric conversion efficiency is greatly improved.
(10) carbon dots it is titania-doped/carbon composite fibre tests the degradation property of uns-dimethylhydrazine: according to the Chinese people
Republic's national standard " the measurement amino sodium ferrocyanide spectrophotometry of water quality uns-dimethylhydrazine " measures uns-dimethylhydrazine in water
Content, test result are as shown in table 1.As it can be seen from table 1 the composite material in embodiment 4 has higher drop to uns-dimethylhydrazine
Rate is solved, catalytic degradation effect can reach 90% or more in 4h.
。
Claims (10)
1. carbon dots are titania-doped/carbon composite fibre, which is characterized in that the composite fibre adulterates two by the carbon dots of outer layer tubulose
Titanium dioxide nanoparticle layer package internal carbon fibers form.
2. composite fibre as described in claim 1, which is characterized in that the carbon in carbon dots doping titanium dioxide nano stratum granulosum contains
Amount is 5 ~ 12.5 wt%.
3. composite fibre as described in claim 1, which is characterized in that the carbon member in carbon dots doping titanium dioxide nano stratum granulosum
Content of the element in composite fibre is 1 ~ 5 wt%.
4. carbon dots a method according to any one of claims 1-3 are titania-doped/carbon composite fibre, which is characterized in that it is described compound
Fiber is made by the steps:
(1) polyacrylonitrile fibre is immersed in hydrolysis process in strong acid, washing, alcohol are washed；
(2) polyacrylonitrile fibre that processing obtains in step (1) is immersed in the mixed of titanate esters or titanate esters and organic solvent
It closes in solution, then is placed in water or aqueous mixed solution and impregnates, it is dry；
(3) sample that step (2) obtains is warming up to 400 ~ 800 DEG C under inert gas protection, is calcined 2 ~ 2.5 hours, to temperature
Degree is down to room temperature and obtains composite material.
5. a kind of carbon dots are titania-doped/preparation method of carbon composite fibre, which comprises the steps of:
(1) at a certain temperature, polyacrylonitrile fibre is immersed in hydrolysis process in strong acid, washing, alcohol are washed；
(2) polyacrylonitrile fibre that processing obtains in step (1) is immersed in the mixed of titanate esters or titanate esters and organic solvent
It closes in solution after a certain period of time, then is placed in water or aqueous mixed solution and impregnates certain time, it is dry；
(3) sample that step (2) obtains is warming up to 400 ~ 800 DEG C under inert gas protection, is calcined 2 ~ 2.5 hours, to temperature
Degree is down to room temperature and obtains composite material.
6. method as claimed in claim 5, which is characterized in that the main component of polyacrylonitrile fibre is polyacrylonitrile or poly- first
Base acrylonitrile, and the co-polymer containing one or more of monomers, wherein the monomer includes acrylonitrile, methacrylonitrile, first
Base methyl acrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate,
Ethylene glycol dimethacrylate, vinyl acetate, N, N- dimethacrylamide, methacrylic acid, acrylic acid, metering system
Acid glycidyl ester, styrene, divinylbenzene.
7. method as claimed in claim 5, which is characterized in that strong acid is sulfuric acid or hydrochloric acid, and concentration is 0.1~10.0
Mol/L, hydrolysis temperature are 20 DEG C ~ 140 DEG C.
8. method as claimed in claim 5, which is characterized in that in step (1), hydrolysis temperature is 120 DEG C ~ 140 DEG C, at hydrolysis
Managing the time is 1 ~ 1.5 hour.
9. method as claimed in claim 5, which is characterized in that in step (2), titanate esters include that tetraethyl titanate, metatitanic acid are different
The mixture of one or more of propyl ester, butyl titanate.
10. method as claimed in claim 5, which is characterized in that in step (2), polyacrylonitrile fibre be immersed in titanate esters or
1 ~ 36 hour in the mixed solution of person's titanate esters and organic solvent, then be placed in water or aqueous mixed solution impregnate 10 minutes with
On.
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