CN110433789A - A method of photocatalysis biology carbon composite is prepared using Eichhornia crassipes accumulation nano zine oxide - Google Patents
A method of photocatalysis biology carbon composite is prepared using Eichhornia crassipes accumulation nano zine oxide Download PDFInfo
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- CN110433789A CN110433789A CN201910700898.6A CN201910700898A CN110433789A CN 110433789 A CN110433789 A CN 110433789A CN 201910700898 A CN201910700898 A CN 201910700898A CN 110433789 A CN110433789 A CN 110433789A
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- zine oxide
- nano zine
- eichhornia crassipes
- photocatalysis
- carbon composite
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- 240000003826 Eichhornia crassipes Species 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000009825 accumulation Methods 0.000 title claims abstract description 19
- 239000003610 charcoal Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000012805 post-processing Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- 235000015097 nutrients Nutrition 0.000 claims description 18
- 230000015556 catabolic process Effects 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 239000004098 Tetracycline Substances 0.000 claims description 10
- 229960002180 tetracycline Drugs 0.000 claims description 10
- 229930101283 tetracycline Natural products 0.000 claims description 10
- 235000019364 tetracycline Nutrition 0.000 claims description 10
- 150000003522 tetracyclines Chemical class 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 241000894007 species Species 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000003643 water by type Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 54
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 13
- 241000196324 Embryophyta Species 0.000 description 12
- 239000011787 zinc oxide Substances 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000002525 ultrasonication Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 210000003934 vacuole Anatomy 0.000 description 1
Classifications
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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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- C02F1/30—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A90/40—Monitoring or fighting invasive species
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Abstract
The present invention relates to a kind of methods using Eichhornia crassipes accumulation nano zine oxide preparation photocatalysis biology carbon composite, specific step is as follows: 1) taking the Eichhornia crassipes being grown in nature lake, it cleans to be placed in the culture solution containing nano zine oxide with distilled water and cultivate, culture 15~45 days after take out Eichhornia crassipes clean, then drying, crush it is spare；2) smashed Eichhornia crassipes is calcined under an inert atmosphere, cooling post-processing obtains nano zine oxide-charcoal optic catalytic composite material.The present invention is using Eichhornia crassipes as charcoal source, Eichhornia crassipes overflows in many eutrophic waters in recent years as alien species, the present invention is to turn waste into wealth, realize the resource utilization of Eichhornia crassipes, and it can suitably reduce the forbidden bandwidth of nano zine oxide semiconductor, so that material is easier to be excited by ultraviolet lamp, its photocatalytic effect is improved.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of to be prepared using Eichhornia crassipes accumulation nano zine oxide
The method of photocatalysis biology carbon composite.
Background technique
Tetracycline antibiotics are due to cheap, and in China, usage amount is huge.Excreta can be passed through after tetracycline use
Mode enter in city planting ductwork, then be discharged into sewage treatment plant, and most of sewage treatment plant is not directed to Fourth Ring at present
The treatment process of plain class antibiotic.Therefore, tetracycline can follow sewage effluents to flow into natural water area, generate to water environment dirty
Dye.
Nano zine oxide is used as photochemical catalyst due to the features such as its particle size is small, large specific surface area, high chemical activity.In
Under ultraviolet light, nano zine oxide can be stimulated and generate the very high free radical of oxidisability, these free radicals can be with complexity
Hardly degraded organic substance reaction is to achieve the purpose that degradation removes this type organic.But nano zine oxide is easily reunited, after reunion
Its nano effect and photocatalytic effect are all remarkably decreased, this application for also resulting in nano zine oxide is extremely restricted.
Charcoal refer to biological material limit oxygen (or anaerobic) and in the case where relative low temperature (700 DEG C of usual <) into
The pyrogenous origin a kind of solid material of row has the characteristics that infusibility, stabilization, porous, height aromatization, is rich in carbon.Due to system
The raw material of standby charcoal is different, and in preparation process, the limitation of surface functional group and chemical property is difficult to the removal of pollutant
Achieve the effect that ideal.But consider from host material angle, charcoal large specific surface area, pore-size distribution rule, gap knot
Structure is flourishing and has stable physicochemical properties, is a kind of material of function admirable.If using charcoal as matrix, by nanometer
Zinc oxide, which is dispersed in biological carbon surface, can greatly reduce building-up effect between nano particle, and suitably reduce the half of nano zine oxide
Conductor bandwidth, so that charcoal is modified to have significant photocatalytic effect while having adsorption effect.But it will receive at present
Mode of the rice zinc oxide in conjunction with charcoal is all to carry out artificial workload by some means physically or chemically, these loads
Mode often complex steps, complicated for operation, increase the consumption of experimental material and reagent, virtually increase experimental cost.
Summary of the invention
It is a kind of using phoenix the technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide
The method of eye lotus accumulation nano zine oxide preparation photocatalysis biology carbon composite.Eichhornia crassipes in solution during the growth process to receiving
Rice zinc oxide carries out nature absorption, and nano zine oxide enters in Eichhornia crassipes plant body, combines closely with plant, be fired into charcoal
Afterwards, nano zine oxide is dispersed in biological carbon surface, and the semiconductor bandwidth of nano zine oxide is effectively reduced, and is more held
It is easily excited by ultraviolet lamp, gained biology carbon composite is placed in the lower efficient drop that can be achieved to tetracycline of low pressure ultraviolet lamp irradiation
Solution.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of method using Eichhornia crassipes accumulation nano zine oxide preparation photocatalysis biology carbon composite is provided, it is specific to walk
It is rapid as follows:
1) Eichhornia crassipes being grown in nature lake is taken, is cleaned and is placed in the culture solution containing nano zine oxide with distilled water
Culture, culture 15~45 days after take out Eichhornia crassipes clean, then drying, crush it is spare；
2) smashed Eichhornia crassipes is calcined under an inert atmosphere, cooling post-processing obtains nano zine oxide-charcoal light
Catalytic composite materials.
According to the above scheme, 20~30g of step 1) the Eichhornia crassipes single-strain fresh weight.
According to the above scheme, the Particle Size of Nanometer ZnO is 20~40nm.
According to the above scheme, the preparation method of the culture solution containing nano zine oxide described in step 1) are as follows: by nano zine oxide plus
Enter in water, ultrasonic disperse uniformly obtains nano oxidized zinc solution, and the nano oxidized zinc solution of gained is mixed with nutrient solution, adds distillation
Water dilutes to obtain the culture solution containing nano zine oxide.
According to the above scheme, nano oxidized zinc concentration is 100~400mg/L in the culture solution containing nano zine oxide.
According to the above scheme, the culture solution is Huo Gelan nutrient solution, Huo Gelan nutrient solution and the culture containing nano zine oxide
Liquid volume ratio is 1:100~200.
According to the above scheme, the step 1) drying condition are as follows: 12~36h is dried at 60~100 DEG C.
According to the above scheme, Eichhornia crassipes partial size is less than 1mm after step 1) crushes.
According to the above scheme, calcination temperature is 550~600 DEG C in step 2), and calcination time is 2~3h.
According to the above scheme, post-processing in step 2) are as follows: grinding, washing to pH value are neutrality, re-dry, sieving.
According to the above scheme, the step 2) drying condition are as follows: dry 12h at 105 DEG C.
According to the above scheme, step 2) sieving was 80 meshes.
The invention also includes the photocatalysis biology carbon composite being prepared according to the above method, nanometer in composite material
The carrying capacity of zinc oxide is 16.71~90.16mg/g.
The invention also includes application of the above-mentioned photocatalysis biology carbon composite in terms of photocatalysis degradation organic contaminant.
According to the above scheme, the organic pollutant is tetracycline.
The invention also includes the above-mentioned sides using Eichhornia crassipes accumulation nano zine oxide preparation photocatalysis biology carbon composite
Application of the method in removal water body in terms of nano material pollutant.
The beneficial effects of the present invention are:
1) present invention is using Eichhornia crassipes as charcoal source, and Eichhornia crassipes is as alien species in recent years in many eutrophic waters
Domain is overflowed, and the present invention is to turn waste into wealth, and realizes the resource utilization of Eichhornia crassipes；
2) present invention eliminates complicated artificial workload side using the nano zine oxide in Eichhornia crassipes nature adsorption aqueous solution
Formula, nano zine oxide can be effectively disperseed after entering in plant body in Eichhornia crassipes body, and with the cell wall of plant, cell
Liquid, vacuole etc. combine, and in conjunction with the compact internal structures such as nano zine oxide and plant cell wall, bast, xylem, can also be with
Carbohydrate, protein in plant combine, and realize nano zine oxide in the intracorporal effective attachment of Eichhornia crassipes plant, avoid oxygen
Change zinc and calcine reunion deactivation prob, finally under high temperature limited oxygen condition, the Eichhornia crassipes Plant Transformation for having adsorbed nano zine oxide is
Have a biological carbon composite of photocatalytic effect, nano zine oxide in conjunction with the charcoal matrix more closely, and nano oxygen
Change zinc granule diameter to be maintained, and uniform in charcoal Dispersion on surface；
3) the method for the present invention can suitably reduce the forbidden bandwidth of nano zine oxide semiconductor, so that material is more easily purple
Outer lamp excitation, improves its photocatalytic effect；
4) life can be fired into after nano material pollutant in biological carbon composite of the invention progress Adsorption water body
Object Carbon Materials continue to recycle, and reduce the harmfulness that nano material generates water body environment.
Detailed description of the invention
Fig. 1 is that the SEM of 3 gained photocatalysis biology carbon composite of the embodiment of the present invention schemes；
Fig. 2 is that Eichhornia crassipes is grown 15 days in 4 culture solution of 3 culture solution of embodiment, 3 culture solution of comparative example and comparative example respectively
Photo afterwards；
Fig. 3 is the semiconductor forbidden bandwidth figure of photocatalysis biology carbon composite and nano zine oxide obtained by embodiment 1-3；
Fig. 4 is biological carbon materials prepared by photocatalysis biology carbon composite obtained by embodiment 1-4 and comparative example 4 to four
The degradation rate curve graph of ring element.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing to the present invention make into
One step detailed description.
The partial size of nano zine oxide used in the embodiment of the present invention is 20-40nm.
Embodiment 1
A method of photocatalysis biology carbon composite being prepared using Eichhornia crassipes accumulation nano zine oxide, specific steps are such as
Under:
(1) taking and being grown in fresh weight in nature lake is 20~30g and the consistent Eichhornia crassipes of growing way, cleans standby with distilled water
With preparation Huo Gelan nutrient solution and nano oxidized zinc solution (using ultrasonication crusher machine 1h), by 5mL nutrient solution and ultrasonication
Nano oxidized zinc solution mixing after 1h adds distilled water to be made into 1L culture solution (wherein nano oxidized zinc concentration is 100mg/L), will
Eichhornia crassipes is placed in culture solution and cultivates in laboratory conditions, and laboratory condition is daylight 12h, and intensity of illumination is
12000Lux, is placed in 12h at dark at night, and diurnal temperature is respectively 24 DEG C and 22 DEG C；
(2) Eichhornia crassipes is taken out after Eichhornia crassipes culture 15 days to clean, dry 12h at a temperature of 105 DEG C, be crushed to partial size and be less than
1mm is spare；
(3) smashed Eichhornia crassipes is placed under condition of nitrogen gas, is warming up to 600 DEG C with the rate of 12 DEG C/min, keeps the temperature 2h
After be cooled to room temperature, take out and fire obtained Eichhornia crassipes charcoal and ground；
(4) washing the charcoal after grinding to pH value is neutrality, dry, must accumulate nano zine oxide after crossing 80 meshes
Photocatalysis biology carbon composite.
Comparative example 1
Photocatalysis biology carbon composite is prepared using method similar to Example 1, the difference is that, with etc. quality
Zinc chloride substitution nano zine oxide prepare culture solution, zinc oxide concentration is 100mg/L in culture solution.
Embodiment 2
A method of photocatalysis biology carbon composite being prepared using Eichhornia crassipes accumulation nano zine oxide, specific steps are such as
Under:
(1) taking and being grown in fresh weight in nature lake is 20~30g and the consistent Eichhornia crassipes of growing way, cleans standby with distilled water
With preparation Huo Gelan nutrient solution and nano oxidized zinc solution (using ultrasonication crusher machine 1h), by 5mL nutrient solution and ultrasonication
Nano oxidized zinc solution mixing after 1h adds distilled water to be made into 1L culture solution (wherein nano oxidized zinc concentration is 200mg/L), will
Eichhornia crassipes is placed in culture solution and cultivates in laboratory conditions, and laboratory condition is daylight 12h, and intensity of illumination is
12000Lux, is placed in 12h at dark at night, and diurnal temperature is respectively 24 DEG C and 22 DEG C；
(2) Eichhornia crassipes is taken out after Eichhornia crassipes culture 15 days to clean, dry 12h at a temperature of 105 DEG C, be crushed to partial size and be less than
1mm is spare；
(3) smashed Eichhornia crassipes is placed under condition of nitrogen gas, is warming up to 600 DEG C with the rate of 12 DEG C/min, keeps the temperature 2h
After be cooled to room temperature, take out and fire obtained Eichhornia crassipes charcoal and ground；
(4) washing the charcoal after grinding to pH value is neutrality, dry, must accumulate nano zine oxide after crossing 80 meshes
Photocatalysis biology carbon composite.
Comparative example 2
Photocatalysis biology carbon composite is prepared using method similar to Example 2, the difference is that, with etc. quality
Zinc chloride substitution nano zine oxide prepare culture solution, zinc oxide concentration is 200mg/L in culture solution.
Embodiment 3
A method of photocatalysis biology carbon composite being prepared using Eichhornia crassipes accumulation nano zine oxide, specific steps are such as
Under:
(1) taking and being grown in fresh weight in nature lake is 20~30g and the consistent Eichhornia crassipes of growing way, cleans standby with distilled water
With preparation Huo Gelan nutrient solution and nano oxidized zinc solution (using ultrasonication crusher machine 1h), by 5mL nutrient solution and ultrasonication
Nano oxidized zinc solution mixing after 1h adds distilled water to be made into 1L culture solution (wherein nano oxidized zinc concentration is 400mg/L), will
Eichhornia crassipes is placed in culture solution and cultivates in laboratory conditions, and laboratory condition is daylight 12h, and intensity of illumination is
12000Lux, is placed in 12h at dark at night, and diurnal temperature is respectively 24 DEG C and 22 DEG C；
(2) Eichhornia crassipes is taken out after Eichhornia crassipes culture 15 days to clean, dry 12h at a temperature of 105 DEG C, be crushed to partial size and be less than
1mm is spare；
(3) smashed Eichhornia crassipes is placed under condition of nitrogen gas, is warming up to 600 DEG C with the rate of 12 DEG C/min, keeps the temperature 2h
After be cooled to room temperature, take out and fire obtained Eichhornia crassipes charcoal and ground；
(4) washing the charcoal after grinding to pH value is neutrality, dry, must accumulate nano zine oxide after crossing 80 meshes
Photocatalysis biology carbon composite.
Electronic Speculum is scanned to photocatalysis biology carbon composite obtained by the present embodiment as shown in Figure 1 to observe to obtain
SEM figure, amplification factor 5000, it is evenly dispersed on biological carbon materials surface to can be observed nano zine oxide, soilless sticking phenomenon.
Comparative example 3
Photocatalysis biology carbon composite is prepared using method similar to Example 3, the difference is that, with etc. quality
Zinc chloride substitution nano zine oxide prepare culture solution, zinc oxide concentration is 400mg/L in culture solution.
Comparative example 4
A method of photocatalysis biological carbon materials are prepared using Eichhornia crassipes, comprising the following steps:
(1) taking and being grown in fresh weight in nature lake is 20~30g and the consistent Eichhornia crassipes of growing way, cleans standby with distilled water
With 5mL nutrient solution and distilled water are made into 1L solution, Eichhornia crassipes are placed in the solution containing nutrient solution by configuration Huo Gelan nutrient solution
In and cultivate in laboratory conditions, laboratory condition is daylight 12h, intensity of illumination 12000Lux, dark 12h, daytime
Night temperature is respectively 24 DEG C and 22 DEG C；
It is cleaned after taking out the Eichhornia crassipes that culture is completed after (2) 15 days, dries 12h at a temperature of 105 DEG C, be crushed to partial size and be less than
1mm, it is spare；
(3) smashed Eichhornia crassipes is placed under condition of nitrogen gas, is kept after being warming up to 600 DEG C with the rate of 12 DEG C/min
2h is cooled to room temperature, and is taken out the Eichhornia crassipes charcoal fired and completed and is ground；
(4) washing the charcoal after grinding to pH value is neutrality, dry, obtains Eichhornia crassipes biology raw material of wood-charcoal after crossing 80 meshes
Material.
The Eichhornia crassipes of identical growing way is cultivated respectively in 3 (400Zn of embodiment 3 (400NPs) and comparative example2+) culture solution
In, and to cultivate in comparative example 4 without the Eichhornia crassipes in zinc oxide or zinc ion, the solution for containing only nutrient solution as blank control
(0), the photo after growing 15 days is as shown in Figure 2, it can be seen that after Eichhornia crassipes is grown 15 days in 3 culture solution of embodiment, blade
There is yellow leaf phenomenon, and Eichhornia crassipes plant is all withered and yellow after growing 15 days in the culture solution of comparative example 3, it is completely dead.
It, will be prepared by embodiment 1-3 since directly quantitative test can not be carried out to nano zine oxide in gained charcoal
It accumulates Eichhornia crassipes biological carbon materials obtained by nano zine oxide Eichhornia crassipes biology carbon composite and comparative example 1-4 and carries out ICP-OES
Test, the content of wherein nano zine oxide is substantially indicated with this, the results are shown in Table 1.
Zn content in 1 gained biological carbon materials of 1 embodiment 1-3 of table and comparative example
As can be seen from Table 1, it is cultivated using the nano zine oxide of same concentrations with liquor zinci chloridi, gained biology raw material of wood-charcoal
Zn content difference is larger in material.All in all Eichhornia crassipes plant is more preferable to nano zine oxide assimilation effect, gained biological carbon materials
Zn content is also higher, and reason may be bigger than the toxicity that nano zine oxide generates plant for zinc ion, especially to plant
Root, this toxic action are unfavorable for absorption of the plant root to zinc ion, are also unfavorable for zinc ion in the intracorporal transfer of plant
With transport.
It is urged intuitively to investigate the light of the accumulation nano zine oxide Eichhornia crassipes biology carbon composite of preparation of the embodiment of the present invention
Change performance, UV-vis DRS is carried out to photocatalysis biology carbon composite obtained by embodiment 1-3 and nano zinc oxide material
Test, is handled the data obtained using Tauc plot method, gained semiconductor forbidden bandwidth figure is as shown in Figure 3.It can from Fig. 3
Know, the forbidden band that can effectively reduce nano zine oxide by the method that Eichhornia crassipes calcines nano zine oxide progress nature absorption again is wide
It spends, the forbidden bandwidth of nano zine oxide is distinguished by original 3.17eV in photocatalysis biology carbon composite obtained by embodiment 1-3
3.15,3.02,3.08eV are reduced to, and minimum by the forbidden bandwidth of 2 gained nano-zinc oxide composite material of embodiment.Forbidden band
Width reduction is conducive to catalysis material and is excited, and plays its photocatalytic effect.In conjunction with 1 acquired results of table, using 200mg/L's
Nano zine oxide carries out plant culture and is more advantageous to the absorption of plant pair nano zine oxide and improves nano zinc oxide material
Photocatalytic effect.
Embodiment 4
Eichhornia crassipes is placed in 2 culture solution of embodiment and is persistently cultivated, when incubation time is 45 days, the stem of Eichhornia crassipes plant
It is all in yellow black with leaf, plant necrosis can not carry out the absorption of nano zine oxide, the biological carbon materials being prepared at this time again
The relative amount of nano zine oxide is 90.16mg/g.
To investigate the accumulation nano zine oxide Eichhornia crassipes biology carbon composite of preparation of the embodiment of the present invention to pollutant
Degradation effect has carried out tetracycline Degrading experiment, and concrete operations are as follows: 0.2g embodiment 1-4 and comparative example 4 being taken to prepare respectively
Biological carbon materials are put into the tetracycline that 1L concentration is 50mg/L, adjust pH value=7 with 0.1mol/L sodium hydroxide, then put
Enter magnetic stirring apparatus, holding revolving speed is 200rpm, and 4.5h is irradiated under 30W ultraviolet lamp after adsorbing 30min under the conditions of being protected from light, right
The degradation effect of tetracycline is as shown in Figure 4.As shown in Figure 4, when the nano zine oxide solution concentration of preparation culture solution is by 100mg/L
When increasing to 200mg/L, the degradation rate of tetracycline is consequently increased.The biological raw material of wood-charcoal of embodiment 2 after irradiation 4.5h under 30W ultraviolet lamp
Expect that catalysis degradation modulus increases to 400mg/ up to 65.79% (when nano oxidized zinc solution 200mg/L), but when nano oxidized zinc concentration
When L, gained photocatalysis biology carbon composite declines the degradation rate of tetracycline instead.4 biological carbon materials of embodiment are to Fourth Ring
The degradation effect of element is best, and the degradation rate of 5h is 85.13%.
Detailed description above is carried out to the present invention and specific embodiment, but without departing from spirit of the invention
On the basis of modification and improvement, the protection for belonging to of the invention encloses.
Claims (10)
1. a kind of method using Eichhornia crassipes accumulation nano zine oxide preparation photocatalysis biology carbon composite, which is characterized in that
Specific step is as follows:
1) Eichhornia crassipes being grown in nature lake is taken, cleans to be placed in the culture solution containing nano zine oxide with distilled water and train
Support, culture 15~45 days after take out Eichhornia crassipes clean, then drying, crush it is spare；
2) smashed Eichhornia crassipes is calcined under an inert atmosphere, cooling post-processing obtains nano zine oxide-charcoal photocatalysis
Composite material.
2. the side according to claim 1 using Eichhornia crassipes accumulation nano zine oxide preparation photocatalysis biology carbon composite
Method, which is characterized in that 20~30g of step 1) the Eichhornia crassipes single-strain fresh weight.
3. the side according to claim 1 using Eichhornia crassipes accumulation nano zine oxide preparation photocatalysis biology carbon composite
Method, which is characterized in that the preparation method of the culture solution containing nano zine oxide described in step 1) are as follows: water is added in nano zine oxide
In, ultrasonic disperse uniformly obtains nano oxidized zinc solution, and the nano oxidized zinc solution of gained is mixed with nutrient solution, adds distilled water dilute
It releases to obtain the culture solution containing nano zine oxide；The Particle Size of Nanometer ZnO is 20~40nm.
4. the side according to claim 3 using Eichhornia crassipes accumulation nano zine oxide preparation photocatalysis biology carbon composite
Method, which is characterized in that nano oxidized zinc concentration is 100~400mg/L in the culture solution containing nano zine oxide；The training
Nutrient solution is Huo Gelan nutrient solution, and Huo Gelan nutrient solution and the nutrient solution volume ratio containing nano zine oxide are 1:100~200.
5. the side according to claim 1 using Eichhornia crassipes accumulation nano zine oxide preparation photocatalysis biology carbon composite
Method, which is characterized in that calcination temperature is 550~600 DEG C in step 2), and calcination time is 2~3h.
6. the side according to claim 1 using Eichhornia crassipes accumulation nano zine oxide preparation photocatalysis biology carbon composite
Method, which is characterized in that post-processing in step 2) are as follows: grinding, washing to pH value are neutrality, re-dry, sieving；Step 2) is described dry
Dry condition are as follows: dry 12h at 105 DEG C；Step 2) sieving was 80 meshes.
7. a kind of photocatalysis biology carbon composite that -6 any the methods are prepared according to claim 1, feature exist
In the carrying capacity of nano zine oxide is 16.71~90.16mg/g in composite material.
8. a kind of photocatalysis biology carbon composite answering in terms of photocatalysis degradation organic contaminant as claimed in claim 7
With.
9. photocatalysis biology carbon composite answering in terms of photocatalysis degradation organic contaminant according to claim 8
With, which is characterized in that the organic pollutant is tetracycline.
10. preparing photocatalysis biology carbon composite using Eichhornia crassipes accumulation nano zine oxide described in a kind of claim 1-6
Application of the method in removal water body in terms of nano material pollutant.
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