CN115477394B - Coupling method of nano titanium dioxide and microalgae, biological system and application - Google Patents
Coupling method of nano titanium dioxide and microalgae, biological system and application Download PDFInfo
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- CN115477394B CN115477394B CN202211256057.9A CN202211256057A CN115477394B CN 115477394 B CN115477394 B CN 115477394B CN 202211256057 A CN202211256057 A CN 202211256057A CN 115477394 B CN115477394 B CN 115477394B
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000010168 coupling process Methods 0.000 title claims abstract description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000008878 coupling Effects 0.000 claims abstract description 21
- 238000005859 coupling reaction Methods 0.000 claims abstract description 21
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 claims abstract description 16
- 229930064664 L-arginine Natural products 0.000 claims abstract description 16
- 235000014852 L-arginine Nutrition 0.000 claims abstract description 16
- -1 di (2-hydroxy propionic acid) diammonium titanium hydroxide Chemical compound 0.000 claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 24
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 15
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 9
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims description 8
- 241000195648 Pseudochlorella pringsheimii Species 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 6
- 235000013878 L-cysteine Nutrition 0.000 claims description 5
- 239000004201 L-cysteine Substances 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 240000009108 Chlorella vulgaris Species 0.000 claims description 2
- 235000007089 Chlorella vulgaris Nutrition 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 25
- 230000015556 catabolic process Effects 0.000 abstract description 24
- 241000195493 Cryptophyta Species 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 8
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000013043 chemical agent Substances 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract description 2
- 230000003204 osmotic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 235000002374 tyrosine Nutrition 0.000 description 8
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 8
- 208000004350 Strabismus Diseases 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 210000003763 chloroplast Anatomy 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DTQHSUHILQWIOM-UHFFFAOYSA-J 2-hydroxypropanoate titanium(4+) dihydroxide Chemical compound O[Ti++]O.CC(O)C([O-])=O.CC(O)C([O-])=O DTQHSUHILQWIOM-UHFFFAOYSA-J 0.000 description 1
- 241000223600 Alternaria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001062954 Clinopodium Species 0.000 description 1
- 241001563035 Clinopodium polycephalum Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000001851 biosynthetic effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960004642 ferric ammonium citrate Drugs 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Biotechnology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Botany (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of microorganisms and photocatalysis, in particular to a coupling method of nano titanium dioxide and microalgae, a biological system and application. The biological system of coupling the nano titanium dioxide and the microalgae is prepared by using L-cysteine, L-arginine, di (2-hydroxy propionic acid) diammonium titanium hydroxide and the stratospheric tetra-chain algae. The nanometer titanium dioxide particles in the biological system have a synergistic effect with microalgae, and under the same degradation condition, the degradation efficiency of the biological system on phenol in solution is 1.32 times that of the biological system of nanometer titanium dioxide and inactivated microalgae, and is 2.30 times that of the biological system only containing microalgae. The invention solves the problem that microalgae are difficult to survive in high-concentration chemical agents due to high osmotic pressure, and provides a method capable of efficiently degrading phenol in solution.
Description
Technical Field
The invention relates to the technical field of microorganism and catalytic degradation, in particular to a coupling method of nano titanium dioxide and microalgae, a biological system and application.
Background
Phenol is used as an important organic chemical raw material and is widely applied to various fields such as synthetic resin, rubber, plastic, medicine, pesticide, dye, paint and the like. However, the wide use of phenol has led to a drastic increase in the amount of phenol-containing wastewater discharged, for example, the phenol concentration in industrial wastewater discharged from phenol manufacturers may reach 12000 to 15000mg/L, the phenol concentration in industrial wastewater discharged from gasification peat manufacturers may reach 1200 to 10800mg/L, the phenol concentration in industrial wastewater discharged from plastics manufacturers may reach 600 to 2000mg/L, etc. As a biotoxic organic matter, the massive emission of phenol brings toxic stimulus to the living beings in the environment.
The current treatment method for phenol-containing wastewater comprises the following steps: physical treatment methods such as adsorption treatment method and solvent extraction method, chemical treatment methods such as advanced oxidation method, wet oxidation method, electrochemical catalytic oxidation method, and biological treatment methods such as activated sludge method. Different treatment methods have respective application ranges and limitations, such as difficult regeneration of the adsorbent, difficult recovery of the extraction solvent and the like, which result in high treatment cost and poor economical efficiency; a large amount of chemical reagents are needed in the treatment process of the chemical treatment method, toxic byproducts are easy to generate, secondary pollution is caused to the environment, and the requirements of low carbon and environmental protection are not met; the biological treatment method has the problems of poor adaptability of activated sludge, excessive sludge and the like, and the microalgae treatment of phenol-containing wastewater does not produce sludge, but the degradation efficiency of the microalgae on phenol is low, and the phenol has toxicity on the microalgae, so that the normal growth of the microalgae can be inhibited, and the biodegradation efficiency is influenced.
Disclosure of Invention
The invention aims to provide a method for coupling nano titanium dioxide with microalgae, a biological system and application thereof, wherein nano titanium dioxide is biosynthesized in microalgae liquid, and the formed coupling system accelerates the degradation of phenol by the microalgae under the catalysis of nano titanium dioxide, so that the toxicity of phenol to the microalgae is reduced.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
a coupling method of nano titanium dioxide and microalgae comprises the following steps:
s1, taking microalgae culture solution, dissolving L-cysteine in the microalgae culture solution, and stirring and uniformly mixing to obtain microalgae solution;
s2, adding L-arginine into the microalgae solution, regulating the pH value to 6.3-8.5, and slowly adding titanium dioxide precursor di (2-hydroxy propionic acid) diammonium titanium hydroxide while stirring to obtain a biological system of coupling nano titanium dioxide with microalgae.
According to the nano titanium dioxide and microalgae coupling method provided by the embodiment of the invention, L-cysteine with better biocompatibility is added into microalgae culture solution, and L-arginine or tyrosine and di (2-hydroxy propionic acid) diammonium titanium hydroxide are adopted for biochemical reaction to obtain the biological synthesis nano titanium dioxide nano particles. By adopting the method, the synthesized titanium dioxide can be connected with amino acid, has better biocompatibility on biological systems, and the dispersed microalgae is used as a carrier, so that the problem that nano titanium dioxide is easy to agglomerate is well overcome, a biological system of coupling nano titanium dioxide with microalgae is formed, phenol is degraded cooperatively with the microalgae under the photocatalysis of the nano titanium dioxide, the degradation efficiency of the phenol is improved, the toxicity of the phenol on the microalgae is reduced, the growth of the microalgae is promoted, and the virtuous circle capable of continuously degrading phenol wastewater is formed.
With reference to the first aspect, the microalgae in the microalgae culture solution comprises at least one or more of Alternaria obliqua, chlorella vulgaris, chlorella ellipsoidea or Chlorella albuminosa, preferably, it is Tetrastigmata obliqua.
In combination with the first aspect, in step S2, the reaction temperature is 20 to 30 ℃, and the reaction condition is normal pressure. The reaction temperature is close to room temperature, the reaction condition is mild, and the normal growth and propagation of microalgae are facilitated.
With reference to the first aspect, in step S1, the amount of the L-cysteine added is: 2.5mmol/L to 5.0mmol/L.
With reference to the first aspect, in step S2, the amount of L-arginine or tyrosine added is: 0.55-2.30 mmol/L, wherein the mol ratio of the di (2-hydroxy propionic acid) diammonium titanium hydroxide to the L-arginine or the tyrosine is 2-9: 1.
preferably, the addition amount of the di (2-hydroxy propionic acid) diammonium titanium hydroxide is 5mmol/L, and the addition amount of the L-arginine or the tyrosine is 1.52mmol/L.
The concentration of each component in the step S1 and the step S2 is below 10mmol/L, so that the toxic influence of chemical reagents on microalgae in a biological system of coupling nano titanium dioxide and the microalgae is reduced, and the degradation efficiency of the microalgae is improved.
In combination with the first aspect, the molar ratio of the di (2-hydroxy propionic acid) diammonium titanium hydroxide to the L-arginine or the tyrosine is 3-5: 1.
with reference to the first aspect, the stirring mode is magnetic stirring, and the stirring speed is 1000-1200 rpm, preferably 1100 rpm.
The second aspect of the embodiment of the invention provides a biological system coupling nano titanium dioxide with microalgae, which is prepared by the method. The biological system of coupling the nano titanium dioxide and the microalgae not only maintains the strong oxidation-reduction property of the titanium dioxide to organic pollutants, but also reduces the toxic damage of the organic pollutants to the microalgae due to the existence of the biological synthesized nano titanium dioxide.
A third aspect of embodiments of the present invention provides an application of a biological system coupled with nano-titania and microalgae in photocatalytic degradation of phenol wastewater.
The biological system of coupling nano titanium dioxide and microalgae prepared by the invention can be used for degrading phenol in wastewater. The biosynthesis nanometer titanium dioxide in the biological system can reduce the toxicity inhibition of phenol to microalgae cells through photocatalysis, weaken the stress reaction of microalgae, promote the propagation of microalgae cells, thereby indirectly improving the photosynthesis efficiency of the microalgae and the chloroplast content in the microalgae and enhancing the activity of the biological system; and chloroplasts in the microalgae can block the recombination process of photoelectrons and hole pairs in the biosynthesis of the titanium dioxide, reduce the electron transfer resistance in the photocatalytic process of the titanium dioxide photodegradation, and are beneficial to electron transfer in the degradation reaction. By means of the synergistic effect of the biological system, the degradation capability of the biological system to phenol is obviously improved compared with that of a biological system without the synergistic effect.
With reference to the third aspect, the volume ratio of the biological system inoculated to the phenol wastewater is 0.5-5: the higher the phenol concentration, the greater the amount of biological system that needs to be inoculated.
In combination with the third aspect, the temperature of the photocatalytic degradation is 20-35 ℃, preferably 30 ℃, and the temperature is too high or too low, which is not beneficial to the normal growth and propagation of microalgae.
With reference to the third aspect, the illumination intensity of the photocatalytic degradation is 4000-5000 LX.
The biological system of coupling nano titanium dioxide and microalgae is obtained by reacting low-concentration L-cysteine, L-arginine or tyrosine and di (2-hydroxy propionic acid) diammonium titanium hydroxide with microalgae liquid at room temperature. The biological system solves the problem that microalgae are difficult to survive in a high-concentration chemical reagent, can combine the photocatalytic degradation effect of titanium dioxide on organic pollutants with the decomposition effect of microalgae on pollutants, realizes the synergistic effect between the biosynthesis of nano titanium dioxide particles and the microalgae, and can efficiently degrade phenol in a solution.
Drawings
FIG. 1 is an SEM spectrum of a biological system of nano-titania coupled with microalgae at a magnification of 10000 times;
FIG. 2 is an XRD spectrum of a biological system in which nano-titania is coupled with microalgae;
FIGS. 3-6 are XPS spectra of a biological system in which nano-titania is coupled with microalgae;
FIG. 7 is a graph showing photocatalytic degradation efficiency of three different systems of example 1, comparative example 1 and comparative example 2 for phenol solutions having a concentration of 100 mg/L.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the embodiment of the invention, the oblique-growing four-chain algae are purchased from a fresh water algae seed library of China academy of sciences, and are dominant algae seeds for degrading phenol obtained through screening together with common chlorella, protein chlorella and chlorella ellipsoidea. Screening: four kinds of algae including chlorella, chlorella ellipsoidea, chlorella albuminosa and tetracos-clinopodium are first cultured in BG11 culture medium to obtain concentrated microalgae liquid (algae OD) 680 =1.0). Concentrating according to microalgae respectivelyThe volume ratio of the solution to phenol solutions with different concentrations of 1:100 is inoculated into a 100ml sterile triangular flask, and the concentrations of the degraded phenol solutions are 50mg/L, 100mg/L and 200mg/L respectively. The culture was carried out in a light incubator having an illumination intensity of 4500LX and a temperature of 30 ℃, and the illumination condition was set to (light/dark cycle=16/8 hours). The results show that: the degradation rate of the chlorella and the chlorella ellipsoidea on phenol is slowest, and the degradation rate of the chlorella albuminosa and the tetrachaia clinopodii on phenol is fastest. In the experiment, the four-chain alga of the clinopodium polycephalum is selected for carrying out the phenol degradation experiment.
The components and concentrations of the components of the BG11 medium were as follows: naNO 3 1.5g/L，K 2 HPO 4 0.004g/L，MgSO 4 ·7H 2 O 0.075g/L，CaCl 2 ·2H 2 O0.036 g/L, citric acid 0.006g/L, ferric ammonium citrate 0.006g/L,2Na-EDTA 0.001g/L, na 2 CO 3 0.02g/L，H 3 BO 3 2.86g/L，MnCl 2 ·4H 2 O 1.86g/L，ZnSO 4 ·7H 2 O 0.22g/L，Na 2 MoO 4 ·2H 2 O 0.39g/L，CuSO 4 ·5H 2 O0.08 g/L and Co (NO) 3 ) 2 ·6H 2 O0.05 g/L. The pH was adjusted to 7.1 with 1M NaOH solution or HCl solution.
L-cysteine, L-arginine, tyrosine and titanium bis (2-hydroxypropionate) dihydroxide are all analytically pure reagents.
Example 1
The embodiment provides a coupling method of nano titanium dioxide and microalgae, which comprises the following preparation steps:
(1) Weighing 0.0100g L-cysteine, dissolving in 20mL of the culture solution of the strabismus tetrandrus, and stirring and uniformly mixing to obtain the strabismus tetrandrus liquid;
(2) Weighing 0.0053g L-arginine, dissolving in the above algae liquid, adjusting pH to about 6.8 with nitric acid, and magnetically stirring for 15min. Then 0.2mL of titanium dioxide precursor di (2-hydroxy propionic acid) diammonium hydroxide titanium is added into the algae liquid at room temperature (about 25 ℃), stirring is carried out while adding, stirring is continued for 20min after adding, and stirring speed is 1000 rpm. And (3) adsorbing nano titanium dioxide particles formed by hydrolysis in the stirring process on the surface of the stratospheric algae to obtain a biological system of coupling the nano titanium dioxide with the microalgae.
Example 2
The embodiment provides a coupling method of nano titanium dioxide and microalgae, which comprises the following preparation steps:
(1) Weighing 0.0100g L-cysteine, dissolving in 20mL of the culture solution of the strabismus tetrandrus, and stirring and uniformly mixing to obtain the strabismus tetrandrus liquid;
(2) 0.0053g of tyrosine is weighed and dissolved in the algae liquid, the pH value is regulated to about 8.3 by using concentrated nitric acid, the magnetic stirring is carried out for 15min, then 0.2mL of titanium dioxide precursor di (2-hydroxy propionic acid) diammonium hydroxide titanium is added at room temperature (about 25 ℃), stirring is carried out while adding, stirring is continued for 20min after adding, and the stirring speed is 1100 r/min. And (3) adsorbing nano titanium dioxide particles formed by hydrolysis in the stirring process on the surface of the stratospheric algae to obtain a biological system of coupling the nano titanium dioxide with the microalgae.
Example 3
The embodiment provides a coupling method of nano titanium dioxide and microalgae, which comprises the following preparation steps:
(1) Weighing 0.0100g L-cysteine, dissolving in 20mL of chlorella ellipsoidea culture solution, stirring and mixing uniformly to obtain chlorella ellipsoidea solution;
(2) 0.0053g L-arginine is weighed and dissolved in the algae liquid, the pH value is regulated to about 7.0 by concentrated nitric acid, the magnetic stirring is carried out for 15min, then 0.2mL of titanium dioxide precursor di (2-hydroxy propionic acid) diammonium hydroxide titanium is added at room temperature (about 25 ℃), stirring is carried out while adding, stirring is continued for 20min after adding, and the stirring speed is 1100 r/min. And (3) adsorbing nano titanium dioxide particles formed by hydrolysis on the surface of the chlorella ellipsoidea in the stirring process to obtain a biological system of coupling the nano titanium dioxide with the microalgae.
Comparative example 1
The comparative example provides a biological system of coupling nano titanium dioxide with microalgae, and the microalgae in the obtained biological system is inactivated, and the preparation steps are as follows:
the biological system of coupling nano titanium dioxide and microalgae is obtained according to the reaction step of the embodiment 1, and then the biological system is heated in a hot water bath at 60 ℃ for 20min, so as to inactivate the strabismus tetradacis in the biological system.
Comparative example 2
The comparative example provides a pure microalgae biological system, wherein the microalgae is selected from the group consisting of Tetrastigmata obliquus.
Comparative example 3
The comparative example provides a biological system of coupling nano titanium dioxide with microalgae, which comprises the following preparation steps:
the mass of the L-arginine weighed in the example 1 and the volume of the titanium dioxide precursor di (2-hydroxy propionic acid) diammonium titanium hydroxide added are respectively changed into 0.0400g and 1.44mL, and the rest steps are completely the same as the example 1, so that a biological system of coupling nano titanium dioxide with higher chemical agent concentration with microalgae is obtained.
Characterization of
The microstructure of the nano titania and microalgae coupling system obtained in examples 1 to 3 was characterized by using a Scanning Electron Microscope (SEM), an X-ray diffraction technique (XRD) and an X-ray photoelectron spectroscopy technique (XPS). The SEM results, XRD results and XPS results of the biosystems prepared in example 1 are shown in fig. 1, 2, and 3 to 6, respectively.
Fig. 1 is an SEM image of a biological system in which nano-titania is coupled to microalgae, and it can be seen that the biosynthetic nano-titania particles aggregate and adhere to the surface of the spindle-shaped microalgae with large middle and small ends. The XRD spectrum of FIG. 2 shows anatase characteristic peaks at 2 theta angles of 25.3 degrees, 37.8 degrees and 25.8 degrees, further proves that the biosynthesis nano titanium dioxide is successfully prepared, and the diffraction peak of the biosynthesis nano titanium dioxide is similar to that of the anatase nano titanium dioxide, and shows that the crystal form of the biosynthesis nano titanium dioxide is the anatase.
To further investigate the elemental composition and elemental valence state in the resulting biological system, XPS tests were performed. It can be seen from FIG. 3 that Ti 2p appears at 458.0eV and 463.8eV, respectively 3/2 And Ti 2p 1/2 The corresponding photoelectron peak indicates that positive tetravalent titanium exists in the biological system; the peak at 530.1eV in FIG. 4 is the photoelectron peak corresponding to O1s in the titanyl lattice O-Ti-O-Ti, and is two places of 531.4eV and 531.5eVRespectively is the photoelectron peak corresponding to O1s in hydroxyl OTi-O-H on the surface of the crystal lattice, ti 2p 3/2 、Ti 2p 1/2 And the occurrence of the corresponding peak of O1s further demonstrates the successful synthesis of the biological nano-titania. Peaks at 284.4eV, 285.1eV and 288.0eV in fig. 5 correspond to photoelectron peaks of C1s in C-C bond, c=o bond and O-c=o bond, respectively, and photoelectron peaks of N1s appear at 400.4eV in fig. 6, corresponding to Ti-N bond. The occurrence of the C1s peak in fig. 5 and the N1s peak in fig. 6 illustrates that the biosynthesized nano-titania is coupled to microalgae in a biological system.
Testing
The biological systems prepared in examples 1-3, comparative example 1 and comparative example 2 were subjected to photocatalytic degradation test on solutions with phenol concentration of 100mg/L, respectively, and the biological systems were mixed with phenol solutions in a volume ratio of 1:100, and were uniformly disturbed, and the degradation temperature was set to 30℃and the illumination intensity was 4500LX.
And detecting the phenol concentration in the photocatalytic degradation process for different degradation times by adopting a high performance liquid chromatography, and drawing a curve by taking the degradation time as an abscissa and the detected phenol solution concentration as an ordinate to obtain a trend chart of the phenol concentration in the photocatalytic degradation process of each biological system along with the time. The detection operations are all carried out after the following pretreatment: a small amount of the phenol solution to be examined was centrifuged at 6000 rpm for 5 minutes, and then the supernatant was filtered using a 0.45 μm organic phase filter.
Wherein, the photocatalytic degradation efficiency data of examples 1 to 3, comparative example 1 and comparative example 2 are shown in Table 1; the photocatalytic degradation efficiency of three different biological systems of example 1, comparative example 1 and comparative example 2 on phenol solutions having a concentration of 100mg/L is shown in FIG. 7.
TABLE 1 phenol degradation efficiency data of biological systems obtained in examples 1 to 3 and comparative examples 1 to 3
It can be seen from table 1 and fig. 7 that under the same degradation time and degradation conditions, the degradation efficiency of the biological system in which the nano titanium dioxide is coupled with the clinopodium is highest, wherein the degradation efficiency of the phenol of the biological system corresponding to example 1 is 1.32 times and 2.30 times that of the biological system in which the nano titanium dioxide is coupled with the microalgae (comparative example 1) is 1.75 times that of the biological system in which the nano titanium dioxide is coupled with the microalgae (comparative example 2), which indicates that the coupling of the microalgae with the biological synthetic nano titanium dioxide improves the photocatalytic degradation efficiency of the phenol, and even if the microalgae in the biological system in which the nano titanium dioxide is coupled with the microalgae is inactivated, the degradation efficiency of the microalgae on the phenol is still higher than that of the biological system in which the pure microalgae is, which indicates that the inactivated microalgae has adsorption effect on the phenol, and is beneficial to the degradation of the phenol by the nano titanium dioxide particles. The degradation efficiency of the biological system prepared in the embodiment 1 to phenol is 1.32 times of that of the biological system obtained in the comparative example 1, which shows that the inside of the biological system coupled by nano titanium dioxide and microalgae has a synergistic effect, the nano titanium dioxide can promote the microalgae cells to secrete extracellular polymers, effectively avoid peroxidation damage of the microalgae cells, accelerate growth and propagation of the microalgae, enhance the activity of the biological system and accelerate the photocatalysis rate of the microalgae to phenol; after microalgae grow and propagate better, more chloroplasts are generated in the microalgae to intercept the recombination of photogenerated electrons and holes in nano titanium dioxide particles, so that the electron exchange density and capacitance in a biological system are increased, and electron transfer is easier, thereby accelerating the photocatalytic degradation of the nano titanium dioxide on phenol. From the degradation efficiency of phenol in example 1 and comparative example 3, it is known that when the concentration of the chemical agent in the biological system exceeds the concentration range defined in the present invention, toxic effects are generated on microalgae in the biological system and even death thereof is caused, thereby degrading the degradation efficiency of the biological system.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. The application of a biological system coupling nano titanium dioxide and microalgae in photocatalytic degradation of phenol wastewater is characterized in that the method for preparing the biological system comprises the following steps:
s1, taking microalgae culture solution, dissolving L-cysteine in the microalgae culture solution, and stirring and uniformly mixing to obtain microalgae solution;
s2, adding L-arginine into the microalgae solution, regulating the pH value to 6.3-8.5, and slowly adding titanium dioxide precursor di (2-hydroxy propionic acid) diammonium titanium hydroxide while stirring to obtain a biological system of coupling nano titanium dioxide with microalgae.
2. The use according to claim 1, wherein the microalgae in the microalgae culture liquid comprises at least one or more of a group consisting of a four-chain alga, a chlorella vulgaris, a chlorella ellipsoidea and a chlorella albuminosa.
3. The use according to claim 1, wherein in step S2, the reaction temperature is 20 to 30 ℃ and the reaction condition is normal pressure.
4. The use according to claim 1, wherein in step S1, the L-cysteine is added in an amount of: 2.5mmol/L to 5.0mmol/L.
5. The use according to claim 1, wherein in step S2, the L-arginine is added in an amount of: 0.55-2.30 mmol/L, wherein the molar ratio of the titanium di (2-hydroxy propionic acid) di-ammonium hydroxide to the L-arginine is 2-9: 1.
6. the use according to claim 5, wherein the molar ratio of titanium bis (2-hydroxypropionate) diammonium hydroxide to L-arginine is 3-5: 1.
7. the use according to claim 1, wherein the stirring means is magnetic stirring at a stirring speed of 1000 to 1200 rpm.
8. The use according to claim 1, wherein the volume ratio of the biological system inoculated to the phenol wastewater is 0.5-5: 100; and/or
The temperature of the photocatalytic degradation is 20-35 ℃; and/or
The illumination intensity of the photocatalytic degradation is 4000-5000 LX.
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| CN103240084A (en) * | 2013-05-10 | 2013-08-14 | 天津大学 | Titanium dioxide-silver nano-composite material and synthetic method thereof |
| CN108439603A (en) * | 2018-04-04 | 2018-08-24 | 中国科学院城市环境研究所 | A method of strengthening microalgae using nano-titanium dioxide and arsenic is removed |
| AU2020103345A4 (en) * | 2020-11-10 | 2021-01-21 | Northeast Normal University | Method for treating phosphorus-containing wastewater with microalgae |
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| CN103240084A (en) * | 2013-05-10 | 2013-08-14 | 天津大学 | Titanium dioxide-silver nano-composite material and synthetic method thereof |
| CN108439603A (en) * | 2018-04-04 | 2018-08-24 | 中国科学院城市环境研究所 | A method of strengthening microalgae using nano-titanium dioxide and arsenic is removed |
| AU2020103345A4 (en) * | 2020-11-10 | 2021-01-21 | Northeast Normal University | Method for treating phosphorus-containing wastewater with microalgae |
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