CN107252696B - A kind of preparation method of sisal hemp carbon fiber photochemical catalyst - Google Patents
A kind of preparation method of sisal hemp carbon fiber photochemical catalyst Download PDFInfo
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- CN107252696B CN107252696B CN201710626824.3A CN201710626824A CN107252696B CN 107252696 B CN107252696 B CN 107252696B CN 201710626824 A CN201710626824 A CN 201710626824A CN 107252696 B CN107252696 B CN 107252696B
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- carbon fiber
- sisal hemp
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- molybdenum disulfide
- hemp carbon
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- 244000198134 Agave sisalana Species 0.000 title claims abstract description 92
- 235000011624 Agave sisalana Nutrition 0.000 title claims abstract description 76
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 75
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 57
- 239000002096 quantum dot Substances 0.000 claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 230000004044 response Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 229910001868 water Inorganic materials 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 229910019964 (NH4)2MoS4 Inorganic materials 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000011365 complex material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000012982 microporous membrane Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000002045 lasting effect Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000008187 granular material Substances 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to wastewater treatment catalysis material fields, disclose a kind of preparation method of sisal hemp carbon fiber photochemical catalyst, it is first the porous carbon fiber with very strong adsorption effect by sisal hemp calcining, titanium dioxide nano granule and molybdenum disulfide quantum dot are loaded on porous carbon by sol-gal process, obtain the porous carbon materials of tri compound.Photochemical catalyst not only reduces the forbidden bandwidth of titanium dioxide, enhances the transfer efficiency of electronics, improves the visible light-responded range of catalyst, and modified titanium dioxide optical catalyst has response to wavelength >=460nm visible light；The present invention makes full use of natural sisal hemp, realizes the efficient utilization of resource, meets the Ecological Concept of green.It is the preparation method simple process of chemically modified sisal hemp carbon fiber photochemical catalyst, at low cost, it is suitable for industrialized production.
Description
Technical field
The present invention relates to wastewater treatment catalysis material field more particularly to a kind of preparation sides of sisal hemp carbon fiber photochemical catalyst
Method.
Background technique
Water pollution is always that people pay close attention to most environmental problems, and the kind and discharge amount of waste water are printed in cumulative year after year
Dye waste water has become one of the major polluting sources of water system environment.It is synthesized and prepares and applied to light there are many carbon material at present
Catalytic field includes mesoporous carbon, graphene, carbon nanotube etc..But the large-scale application of photochemical catalyst is considered, with renewable
Biomass be raw material preparation high performance catalysis material, the high value added utilization of biomass not only may be implemented, but also
Effectively reduce the cost of photochemical catalyst.Sisal hemp carbon fiber is product of the sisal fiber after high temperature pyrolysis.
Conductor photocatalysis degradation technique is a kind of environment that cleaning decontamination is most possibly realized using nature sunlight
Friendly technology, oneself pays close attention to more wastewater treatment method as people at present.Two in numerous photocatalysis semiconductor materials
Titania photocatalyst has many advantages, such as that cheap, pollution-free, anti-light corrosion is known as environmental-friendly pollution processing material, ring
It protects and energy-efficient application prospect is widely paid close attention to.Although numerous organic pollutants can be by under the irradiation of ultraviolet light conditions
TiO2Effectively it is degraded to CO2And H2O, but its utilization efficiency is very low under the irradiation of visible light, and ultraviolet light in sunlight
Only 3% or so, affect TiO2Photocatalytic degradation effect.
Molybdenum disulfide is a kind of typical transition metal two-dimensional layer sulfide, and the molybdenum disulfide of single layer is by S-Mo-S atom
Layer is covalently constituted, and is combined between layers by weaker Van der Waals force.With the graphite with two-dimensional layered structure
Alkene is different, and molybdenum disulfide has regulatable bandgap structure.When block-like molybdenum disulfide becomes molybdenum disulfide nano sheet layer, two
The forbidden bandwidth of molybdenum sulfide increases with the reduction of its number of plies.Compared to the graphene of zero band gap, single layer molybdenum disulfide is shown
More excellent physicochemical characteristics has very in fields such as optical device, lithium ion battery, photoelectrocatalysis, supercapacitors
High application prospect has attracted the extensive concern of researcher.Currently, the report about molybdenum disulfide rests on nanometer sheet more
Layer range, for MoS2The report of quantum dot is relatively fewer.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation methods of sisal hemp carbon fiber photochemical catalyst.This
Sisal fiber calcining is first the metal-doped porous charcoal such as silver, copper by invention preparation method, by sol-gal process by dioxy
Change titanium nanoparticle and molybdenum disulfide quantum dot loads on porous carbon, obtains the porous carbon materials of tri compound.Such modification
The optical response range of titanium dioxide is substantially increased, and plays the purpose of degradation of organic substances pollutant.
The specific technical proposal of the invention is: a kind of preparation method of sisal hemp carbon fiber photochemical catalyst, comprising the following steps:
Step 1: the preparation of sisal hemp carbon fiber: being impregnated sisal fiber with NaOH aqueous solution, be then rinsed with water to neutrality,
It is impregnated again with ammonium dibasic phosphate aqueous solution, pulls out, dries；Sisal fiber of the pretreatment after dry is put into Muffle furnace and is calcined,
Porous sisal hemp carbon fiber is obtained after cooling.
Step 2: the sisal hemp carbon fiber in step 1 is placed on (NH4)2S2O8Ultrasonic in solution, filtering is clear with deionized water
It is immersed in the NaOH solution 4-6min of 95-105g/L after washing, the unreacted (NH in surface is washed with deionized water4)2S2O8。
Step 3: the preparation of molybdenum disulfide quantum dot: by (NH4)2MoS4It is dissolved in water, ultrasonic 10-20min, is added
N2H4As reducing agent, mixture is transferred in ptfe autoclave and carries out hydro-thermal reaction, is cooled to room after reaction
Temperature is dialysed obtained filtrate using the filtering with microporous membrane of 0.22um in water, is finally evaporated solvent, is obtained after dry
Solid extremely molybdenum disulfide quantum dot.
Step 4: sisal hemp carbon fiber and molybdenum disulfide quantum dot being dispersed in deionized water, ultrasonic 25-35min is obtained
Sisal hemp carbon fiber/molybdenum disulfide suspension.
Step 5: the preparation of ternary complex material: first mixing ethyl alcohol with butyl titanate, stirs 10-20min, is formed
Solution A；Sisal hemp carbon fiber/molybdenum disulfide quantum dot solution is mixed with glacial acetic acid again, the solution B of formation；Under stirring,
Solution B is slowly dropped in solution A by 20-30:25-35 by volume, is then placed in 60-80 DEG C of water-bath and is persistently stirred 50-
Taupe gel is made in 70min, obtained gel is put into after drying in 60-80 DEG C of baking oven, is heated to 125-135 DEG C and holds
Continuous 10-15min, obtains beige solid；It is ground, it is compound to obtain sisal hemp carbon fiber/titanium dioxide/molybdenum disulfide nano
Object.
Sisal fiber calcining is first the metal-doped porous charcoals such as silver, copper by preparation method of the present invention, solidifying by colloidal sol
Glue method loads to titanium dioxide nano granule and molybdenum disulfide quantum dot on porous carbon, obtains the porous carbon materials of tri compound.
Molybdenum disulfide quantum dot is introduced, so that TiO2It can organic contamination in effective catalytic degradation sewage in visible-range
Object.And sisal hemp carbon fiber can be very good improve material conductivity and its chemical property, become good electronics by
Body compensates for the easily compound defect of the electron-hole pair of titanium dioxide to a certain extent.Such modification substantially increases two
The optical response range of titanium oxide, and play the purpose of degradation of organic substances pollutant.
Preferably, in step 1, the mass concentration of NaOH aqueous solution is 5wt%, soaking time 20-28 hours, phosphoric acid hydrogen
The mass concentration of two aqueous ammoniums is 5%, and dip time is 20-28 hours.
The pectin in order to remove surface using NaOH aqueous solution soaking, the purpose of ammonium dibasic phosphate aqueous solution dipping be for
Increase the hole count of carbon fiber.
Preferably, calcining in step 1 as step calcination: being first warming up to 200-300 DEG C, keep 25-35min, then heat up
To 800-900 DEG C, 2-3h is kept, rate is 5-6 DEG C/min, leads to inert gas.
The purpose of step calcination is to obtain higher porosity.The porosity of sisal hemp carbon fiber provides not only bigger ratio
Surface area, it is so effective that improve dirt even more in order to which the insertion of titanium dioxide nano granule and molybdenum disulfide quantum dot provides space
Water treatment capacity.
Preferably, in step 2, (NH4)2S2O8The concentration of solution is 100-200g/L, ultrasonic time 1-2h.
(the NH with oxidation is immersed in by the porous carbon fiber formed after calcining sisal hemp4)2S2O8In solution into
Row ultrasonic treatment can make porous carbon surface be oxidized generation hydroxyl, ester group and carboxyl, these reactive functional groups and deposit
To the bonded most important of next step and titanium dioxide nano granule.The presence of chemical bond improves electron transfer rate, effectively
The separative efficiency of electron-hole pair must be improved.
Preferably, hydrothermal temperature is 150-200 DEG C, reaction time 6-9h in step 3；Filtrate dialysis time
It is 3-5 days.
For molybdenum disulfide quantum dot is compared with curing molybdenum sheet, molybdenum disulfide quantum dot not only has bigger specific surface area,
Significant edge effect, while there is the unique optical property of quantum dot, keep it more with potential applications in field of the present invention.
Preferably, in step 3, (NH4)2MoS4Mass ratio with water is 1:95-105.
Preferably, in step 4, sisal hemp carbon fiber, molybdenum disulfide quantum dot, deionized water mass ratio be 1:0.5:
(20-40).
Preferably, the volume ratio of ethyl alcohol and butyl titanate is 10:1 in solution A in step 5；Sisal hemp carbon in solution B
The volume ratio of fiber/molybdenum disulfide quantum dot solution and glacial acetic acid mixed liquor is 10:1.
Preferably, the drop rate of solution B is 1-1.5mL/ seconds in step 5.
It is compared with the prior art, the beneficial effects of the present invention are:
1, sisal hemp carbon fiber is product of the sisal fiber after high temperature pyrolysis.In sisal hemp carbon fiber containing potassium, silicon, calcium, magnesium,
The element abundant such as copper, silver can be very good to improve light-catalysed effect.Sisal hemp Carbon fibe after overactivation, compares table
Area is up to 1200m2/ g or more, is far longer than the activated carbon of general coconut husk, bamboo charcoal and other common matrix, thus has
Excellent absorption and catalytic performance has absorption, degradation to nocuousness dyestuffs a variety of in water quality, heavy metal ion and germ.
Therefore sisal hemp carbon itself play the role of to photocatalysis it is positive.The pore structure abundant and can have that the present invention is generated after firing using it
Sisal hemp carbon fiber is used for photochemical catalyst by the transmission electronics of effect.Sisal hemp carbon fiber makees photochemical catalyst, not only can be by biological material
It recycles, due to its considerable absorption property and electronic transmission performance, moreover it is possible to efficient degradable organic pollutant.
2, (the NH with oxidation is immersed in by the porous carbon formed after calcining sisal fiber4)2S2O8In solution
It is ultrasonically treated, porous carbon surface can be made to be oxidized and generate hydroxyl, ester group and carboxyl, these reactive functional groups
In the presence of to the bonded most important of next step and titanium dioxide nano granule.
3, the present invention introduces the molybdenum disulfide quantum dot with bigger serface, can make compound rear TiO2Visible
It can organic pollutant in effective catalytic degradation sewage in optical range.
4, the maximum feature of the present invention is that the sisal hemp carbon fiber catalysis material for designing and preparing has photo and thermal stability
Good, large specific surface area, visible light are wide (wavelength >=460nm) using wavelength, while having very high visible light photocatalysis active
The advantages that, it can be used as the catalyst of photocatalytic degradation of organic matter pollutant.
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment 1
A kind of preparation method of sisal hemp carbon fiber photochemical catalyst, comprising the following steps:
Step 1: the preparation of sisal hemp carbon fiber: sisal fiber being impregnated 20 hours with the NaOH aqueous solution of 5wt%, is then used
Water is rinsed to neutrality, then is impregnated 20 hours with the ammonium dibasic phosphate aqueous solution of 5wt%, is pulled out, is dried；After pretreatment drying
Sisal fiber is put into step calcination in Muffle furnace: being first warming up to 200 DEG C, keeps 35min, then be warming up to 800 DEG C, keeps 3h, speed
Rate is 5 DEG C/min, leads to inert gas.Porous sisal hemp carbon fiber is obtained after calcining is cooling.
Step 2: the sisal hemp carbon fiber in step 1 is placed on the (NH that concentration is 100g/L4)2S2O8Ultrasound 2h in solution,
Filtering, is immersed in the NaOH solution 6min of 95g/L, it is unreacted that surface is washed with deionized water after being cleaned with deionized water
(NH4)2S2O8。
Step 3: the preparation of molybdenum disulfide quantum dot: 1:95 in mass ratio is by (NH4)2MoS4It is dissolved in water, ultrasound
N is added in 20min2H4As reducing agent, mixture is transferred in ptfe autoclave and carries out hydro-thermal reaction, hydro-thermal reaction
Temperature is 150 DEG C, reaction time 9h；It is cooled to room temperature, using the filtering with microporous membrane of 0.22um, will obtain after reaction
Filtrate dialyse in water 3 days, finally evaporate solvent, the solid extremely molybdenum disulfide quantum dot obtained after dry.
Step 4: sisal hemp carbon fiber and molybdenum disulfide quantum dot being dispersed in deionized water, ultrasonic 25min obtains sisal hemp
Carbon fiber/molybdenum disulfide suspension.Wherein, sisal hemp carbon fiber, molybdenum disulfide quantum dot, deionized water mass ratio be 1:
0.5:20。
Step 5: ethyl alcohol first the preparation of ternary complex material: being mixed to (ethyl alcohol and butyl titanate with butyl titanate
Volume ratio be 10:1), stir 10min, formed solution A；Again by sisal hemp carbon fiber/molybdenum disulfide quantum dot solution and glacial acetic acid
Mixing (volume ratio of sisal hemp carbon fiber/molybdenum disulfide quantum dot solution and glacial acetic acid mixed liquor is 10:1), the solution B of formation；
Under stirring, solution B was added drop-wise in solution A by 20:25 by 1mL/ seconds drop rates by volume, was then placed in 60 DEG C
70min is persistently stirred in water-bath, taupe gel is made, and obtained gel is put into after drying in 60 DEG C of baking ovens, is heated to
125 DEG C of lasting 15min, obtain beige solid；It is ground, it is multiple to obtain sisal hemp carbon fiber/titanium dioxide/molybdenum disulfide nano
Close object.
Embodiment 2
A kind of preparation method of sisal hemp carbon fiber photochemical catalyst, comprising the following steps:
Step 1: the preparation of sisal hemp carbon fiber: sisal fiber being impregnated 24 hours with the NaOH aqueous solution of 5wt%, is then used
Water is rinsed to neutrality, then is impregnated 24 hours with the ammonium dibasic phosphate aqueous solution of 5wt%, is pulled out, is dried；After pretreatment drying
Sisal fiber is put into step calcination in Muffle furnace: 250 DEG C is first warming up to, keeps 30min, then be warming up to 850 DEG C, keeps 2.5h,
Rate is 5.5 DEG C/min, leads to inert gas.Porous sisal hemp carbon fiber is obtained after calcining is cooling.
Step 2: the sisal hemp carbon fiber in step 1 is placed on the (NH that concentration is 150g/L4)2S2O8It is ultrasonic in solution
1.5h, filtering, is immersed in the NaOH solution 5min of 100g/L, surface unreacted is washed with deionized water after being cleaned with deionized water
(NH4)2S2O8。
Step 3: the preparation of molybdenum disulfide quantum dot: 1:100 in mass ratio is by (NH4)2MoS4It is dissolved in water, ultrasound
N is added in 15min2H4As reducing agent, mixture is transferred in ptfe autoclave and carries out hydro-thermal reaction, hydro-thermal reaction
Temperature is 180 DEG C, reaction time 8h；It is cooled to room temperature, using the filtering with microporous membrane of 0.22um, will obtain after reaction
Filtrate dialyse in water 4 days, finally evaporate solvent, the solid extremely molybdenum disulfide quantum dot obtained after dry.
Step 4: sisal hemp carbon fiber and molybdenum disulfide quantum dot being dispersed in deionized water, ultrasonic 30min obtains sisal hemp
Carbon fiber/molybdenum disulfide suspension.Wherein, sisal hemp carbon fiber, molybdenum disulfide quantum dot, deionized water mass ratio be 1:
0.5:30。
Step 5: ethyl alcohol first the preparation of ternary complex material: being mixed to (ethyl alcohol and butyl titanate with butyl titanate
Volume ratio be 10:1), stir 15min, formed solution A；Again by sisal hemp carbon fiber/molybdenum disulfide quantum dot solution and glacial acetic acid
Mixing (volume ratio of sisal hemp carbon fiber/molybdenum disulfide quantum dot solution and glacial acetic acid mixed liquor is 10:1), the solution B of formation；
Under stirring, solution B was added drop-wise in solution A by 25:30 by 1.5mL/ seconds drop rates by volume, was then placed in 70
60min is persistently stirred in DEG C water-bath, taupe gel is made, obtained gel is put into after being dried in 70 DEG C of baking ovens, is reheated
To 130 DEG C of lasting 12min, beige solid is obtained；It is ground, obtains sisal hemp carbon fiber/titanium dioxide/molybdenum disulfide nano
Compound.
Embodiment 3
A kind of preparation method of sisal hemp carbon fiber photochemical catalyst, comprising the following steps:
Step 1: the preparation of sisal hemp carbon fiber: sisal fiber being impregnated 28 hours with the NaOH aqueous solution of 5wt%, is then used
Water is rinsed to neutrality, then is impregnated 28 hours with the ammonium dibasic phosphate aqueous solution of 5wt%, is pulled out, is dried；After pretreatment drying
Sisal fiber is put into step calcination in Muffle furnace: being first warming up to 300 DEG C, keeps 25min, then be warming up to 900 DEG C, keeps 2h, speed
Rate is 6 DEG C/min, leads to inert gas.Porous sisal hemp carbon fiber is obtained after calcining is cooling.
Step 2: the sisal hemp carbon fiber in step 1 is placed on the (NH that concentration is 200g/L4)2S2O8Ultrasound 1h in solution,
Filtering, is immersed in the NaOH solution 4min of 105g/L, it is unreacted that surface is washed with deionized water after being cleaned with deionized water
(NH4)2S2O8。
Step 3: the preparation of molybdenum disulfide quantum dot: 1:105 in mass ratio is by (NH4)2MoS4It is dissolved in water, ultrasound
N is added in 10min2H4As reducing agent, mixture is transferred in ptfe autoclave and carries out hydro-thermal reaction, hydro-thermal reaction
Temperature is 200 DEG C, reaction time 6h；It is cooled to room temperature, using the filtering with microporous membrane of 0.22um, will obtain after reaction
Filtrate dialyse in water 5 days, finally evaporate solvent, the solid extremely molybdenum disulfide quantum dot obtained after dry.
Step 4: sisal hemp carbon fiber and molybdenum disulfide quantum dot being dispersed in deionized water, ultrasonic 35min obtains sisal hemp
Carbon fiber/molybdenum disulfide suspension.Wherein, sisal hemp carbon fiber, molybdenum disulfide quantum dot, deionized water mass ratio be 1:
0.5:40。
Step 5: ethyl alcohol first the preparation of ternary complex material: being mixed to (ethyl alcohol and butyl titanate with butyl titanate
Volume ratio be 10:1), stir 20min, formed solution A；Again by sisal hemp carbon fiber/molybdenum disulfide quantum dot solution and glacial acetic acid
Mixing (volume ratio of sisal hemp carbon fiber/molybdenum disulfide quantum dot solution and glacial acetic acid mixed liquor is 10:1), the solution B of formation；
Under stirring, solution B was added drop-wise in solution A by 30:35 by 1.5mL/ seconds drop rates by volume, was then placed in 80
50min is persistently stirred in DEG C water-bath, taupe gel is made, obtained gel is put into after being dried in 80 DEG C of baking ovens, is reheated
To 135 DEG C of lasting 10min, beige solid is obtained；It is ground, obtains sisal hemp carbon fiber/titanium dioxide/molybdenum disulfide nano
Compound.
Sisal hemp carbon fiber produced by the present invention, specific surface area is up to 1200m2/ g or more, and common normal drinking water
The specific surface area of the cocoanut active charcoal of processing is 1000-1100m2/g；Bamboo charcoal specific surface area is in 150-700m2Between/g.Thus
It knows that its performance is more preferable, is more suitable for being used as the carrier of titanium dioxide and molybdenum disulfide.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (9)
1. a kind of preparation method of sisal hemp carbon fiber photochemical catalyst, it is characterised in that the following steps are included:
Step 1: the preparation of sisal hemp carbon fiber: sisal fiber being impregnated with NaOH aqueous solution, is then rinsed with water to neutrality, then use
Ammonium dibasic phosphate aqueous solution dipping, pulls out, dries；Sisal fiber of the pretreatment after dry is put into Muffle furnace and is calcined, it is cooling
After obtain porous sisal hemp carbon fiber；
Step 2: the sisal hemp carbon fiber in step 1 is placed on (NH4)2S2O8Ultrasonic in solution, filtering is soaked after being cleaned with deionized water
The NaOH solution 4-6min in 95-105g/L is steeped, the unreacted (NH in surface is washed with deionized water4)2S2O8；
Step 3: the preparation of molybdenum disulfide quantum dot: by (NH4)2MoS4It is dissolved in water, ultrasonic 10-20min, N is added2H4As
Mixture is transferred in ptfe autoclave and carries out hydro-thermal reaction, is cooled to room temperature after reaction by reducing agent, uses
0.22 μm of filtering with microporous membrane dialyses obtained filtrate in water, finally evaporates solvent, the solid obtained after dry is i.e.
For molybdenum disulfide quantum dot；
Step 4: sisal hemp carbon fiber and molybdenum disulfide quantum dot being dispersed in deionized water, ultrasonic 25-35min obtains sisal hemp
Carbon fiber/molybdenum disulfide suspension；
Step 5: the preparation of ternary complex material: first mixing ethyl alcohol with butyl titanate, stirs 10-20min, forms solution
A；Sisal hemp carbon fiber/molybdenum disulfide suspension is mixed with glacial acetic acid again, the solution B of formation；Under stirring, by volume
Solution B is slowly dropped in solution A than 20-30:25-35, is then placed in 60-80 DEG C of water-bath and persistently stirs 50-70min,
Taupe gel is made, obtained gel is put into after being dried in 60-80 DEG C of baking oven, is heated to 125-135 DEG C of lasting 10-
15min obtains beige solid；It is ground, obtains sisal hemp carbon fiber/titanium dioxide/molybdenum disulfide nano compound.
2. a kind of preparation method of sisal hemp carbon fiber photochemical catalyst as described in claim 1, which is characterized in that in step 1,
The mass concentration of NaOH aqueous solution is 5wt%, and soaking time 20-28 hours, the mass concentration of ammonium dibasic phosphate aqueous solution was
5%, dip time is 20-28 hours.
3. a kind of preparation method of sisal hemp carbon fiber photochemical catalyst as described in claim 1, which is characterized in that in step 1, forge
Burn is step calcination: being first warming up to 200-300 DEG C, keeps 25-35min, then be warming up to 800-900 DEG C, keep 2-3h, rate is
5-6 DEG C/min, lead to inert gas.
4. a kind of preparation method of sisal hemp carbon fiber photochemical catalyst as described in claim 1, which is characterized in that in step 2,
(NH4)2S2O8The concentration of solution is 100-200g/L, ultrasonic time 1-2h.
5. a kind of preparation method of sisal hemp carbon fiber photochemical catalyst as described in claim 1, which is characterized in that in step 3, water
Thermal response temperature is 150-200 DEG C, reaction time 6-9h；Filtrate dialysis time is 3-5 days.
6. a kind of preparation method of sisal hemp carbon fiber photochemical catalyst as claimed in claim 1 or 5, which is characterized in that step 3
In, (NH4)2MoS4Mass ratio with water is 1: 95-105.
7. a kind of preparation method of sisal hemp carbon fiber photochemical catalyst as described in claim 1, which is characterized in that in step 4, sword
Numb carbon fiber, molybdenum disulfide quantum dot, deionized water mass ratio be 1: 0.5: (20-40).
8. a kind of preparation method of sisal hemp carbon fiber photochemical catalyst as described in claim 1, which is characterized in that molten in step 5
The volume ratio of ethyl alcohol and butyl titanate is 10: 1 in liquid A；Sisal hemp carbon fiber/molybdenum disulfide suspension and ice vinegar in solution B
The volume ratio of acid is 10: 1.
9. a kind of preparation method of sisal hemp carbon fiber photochemical catalyst as claimed in claim 1 or 8, which is characterized in that step 5
In, the drop rate of solution B is 1-1.5mL/ seconds.
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