CN115477394A - 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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- CN115477394A CN115477394A CN202211256057.9A CN202211256057A CN115477394A CN 115477394 A CN115477394 A CN 115477394A CN 202211256057 A CN202211256057 A CN 202211256057A CN 115477394 A CN115477394 A CN 115477394A
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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 64
- 238000010168 coupling process Methods 0.000 title claims abstract description 42
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 230000008878 coupling Effects 0.000 claims abstract description 32
- 238000005859 coupling reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 26
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 15
- PCIGTTWKYUNLEP-UHFFFAOYSA-N azane;2-hydroxypropanoic acid;titanium;dihydrate Chemical compound N.N.O.O.[Ti].CC(O)C(O)=O.CC(O)C(O)=O PCIGTTWKYUNLEP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 11
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- 241000195649 Chlorella <Chlorellales> Species 0.000 claims description 5
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- 239000004201 L-cysteine Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 240000009108 Chlorella vulgaris Species 0.000 claims description 4
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- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 26
- 230000015556 catabolic process Effects 0.000 abstract description 25
- 241000195493 Cryptophyta Species 0.000 abstract description 18
- 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
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000013043 chemical agent Substances 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- AGYAOGDEHQSPNF-UHFFFAOYSA-N [Ti].[OH-].[OH-].[NH4+].[NH4+] Chemical compound [Ti].[OH-].[OH-].[NH4+].[NH4+] AGYAOGDEHQSPNF-UHFFFAOYSA-N 0.000 abstract description 2
- 244000005700 microbiome Species 0.000 abstract description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 abstract 3
- 230000003204 osmotic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 238000011282 treatment Methods 0.000 description 11
- 230000001851 biosynthetic effect Effects 0.000 description 9
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- 231100000331 toxic Toxicity 0.000 description 5
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- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 241000195652 Auxenochlorella pyrenoidosa Species 0.000 description 3
- 235000007091 Chlorella pyrenoidosa Nutrition 0.000 description 3
- 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
- 230000003197 catalytic 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
Images
Classifications
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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
- 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
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 nano titanium dioxide and microalgae is prepared by utilizing L-cysteine, L-arginine, di (2-hydracrylic acid) diammonium dihydroxide titanium and tetralin slantingly-grown algae. The nano 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 to phenol in a solution is 1.32 times that of the biological system containing nano titanium dioxide and inactivated microalgae, and is 2.30 times that of the biological system containing only microalgae. The invention not only solves the problem that the microalgae is difficult to survive in high-concentration chemical agents due to high osmotic pressure, but also provides a method for efficiently degrading phenol in a solution.
Description
Technical Field
The invention relates to the technical field of microorganisms and catalytic degradation, in particular to a coupling method of nano titanium dioxide and microalgae, a biological system and application.
Background
Phenol is an important organic chemical raw material and is widely applied to the fields of synthetic resin, rubber, plastics, medicines, pesticides, dyes, coatings and the like. However, the widespread use of phenol has led to a dramatic increase in the discharge of phenol-containing wastewater, for example, phenol concentrations in industrial wastewater from phenol production enterprises can reach 12000-15000 mg/L, phenol concentrations in industrial wastewater from gasified peat production enterprises can reach 1200-10800 mg/L, and phenol concentrations in industrial wastewater from plastic production enterprises can reach 600-2000 mg/L. As a biotoxic organic substance, the large discharge of phenol causes toxic irritation to organisms in the environment.
The current treatment method for phenol-containing wastewater comprises the following steps: physical treatment methods such as adsorption treatment and solvent extraction, chemical treatment methods such as advanced oxidation, wet oxidation and electrochemical catalytic oxidation, and biological treatment methods such as activated sludge. Different treatment methods have respective application ranges and limitations, for example, physical treatment methods have the defects of difficult regeneration of adsorbents and difficult recovery of extraction solvents, which results in high treatment cost and poor economy; a large amount of chemical reagents are needed in the treatment process of the chemical treatment method, toxic byproducts are easily generated, secondary pollution is brought to the environment, and the low-carbon and environment-friendly requirements are not met; the biological treatment method has the problems of poor adaptive capacity of activated sludge, excessive generated sludge and the like, and the microalgae has low phenol degradation efficiency when treating phenol-containing wastewater without generating sludge, and phenol has toxicity to the microalgae, so that the normal growth of the microalgae can be inhibited, and the biological degradation efficiency is influenced.
Disclosure of Invention
The invention aims to provide a method for coupling nano titanium dioxide and microalgae, a biological system and application, wherein the nano titanium dioxide is biosynthesized in microalgae liquid, and the formed coupling system enables the microalgae to accelerate the degradation of phenol under the catalytic action of the nano titanium dioxide and reduce the toxicity of the phenol to the microalgae.
In order to achieve the purpose of the invention, 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 a microalgae culture solution, dissolving L-cysteine in the microalgae culture solution, and stirring and uniformly mixing to obtain a microalgae solution;
s2, adding L-arginine into the microalgae liquid, adjusting the pH value to 6.3-8.5, slowly adding a titanium dioxide precursor di (2-hydroxypropionic acid) diammonium dihydroxide titanium and stirring while adding to obtain a biological system coupling the nano titanium dioxide and the microalgae.
According to the method for coupling the nano titanium dioxide and the microalgae, provided by the embodiment of the invention, L-cysteine with good biocompatibility is added into a microalgae culture solution, and L-arginine or tyrosine and di (2-hydroxypropionic acid) diammonium dihydroxide titanium are adopted to carry out biochemical reaction to obtain the biosynthetic nano titanium dioxide nanoparticles. By adopting the method, the synthesized titanium dioxide can be possibly connected with amino acid, has better biocompatibility to a biological system, and the dispersed microalgae is used as a carrier, so that the problem that the nano titanium dioxide is easy to agglomerate is well solved, the biological system coupling the nano titanium dioxide and the microalgae is formed, and the nano titanium dioxide and the microalgae can cooperatively degrade phenol under the photocatalysis of the nano titanium dioxide, so that the degradation efficiency of the phenol is improved, the toxicity of the phenol to the microalgae is reduced, the growth of the microalgae is promoted, and a virtuous cycle 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 oblique-living tetrachain algae, chlorella vulgaris, chlorella ellipsoidea or chlorella pyrenoidosa, and preferably oblique-living tetrachain algae.
With reference to the first aspect, in step S2, the reaction temperature is 20 to 30 ℃, and the reaction conditions are normal pressure. The reaction temperature is close to room temperature, the reaction condition is mild, and the normal growth and propagation of the microalgae are facilitated.
In combination with the first aspect, in step S1, the amount of the L-cysteine added is: 2.5mmol/L to 5.0mmol/L.
In combination with the first aspect, in step S2, the L-arginine or tyrosine is added in an amount of: 0.55mmol/L to 2.30mmol/L, wherein the molar ratio of the bis (2-hydroxypropionic acid) diammonium dihydroxide titanium to the L-arginine or the tyrosine is 2 to 9:1.
preferably, the addition amount of the di (2-hydroxypropionic acid) diammonium dihydroxide titanium is 5mmol/L, and the addition amount of the L-arginine or 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 in a biological system coupling the nano titanium dioxide and the microalgae on the microalgae is reduced, and the degradation efficiency of the microalgae is improved.
In combination with the first aspect, the molar ratio of titanium bis (2-hydroxypropionate) diammonium dihydroxide to L-arginine or tyrosine is 3 to 5:1.
in combination with the first aspect, the stirring manner is magnetic stirring, and the stirring speed is 1000 to 1200 rpm, preferably 1100 rpm.
The second aspect of the embodiment of the invention provides a biological system coupling nano titanium dioxide and microalgae, and the biological system is prepared by adopting the method. The biological system coupling the nano titanium dioxide and the microalgae not only keeps the strong oxidation and reduction 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 biosynthetic nano titanium dioxide.
The third aspect of the embodiment of the invention provides an application of a biological system coupling nano titanium dioxide and microalgae in photocatalytic degradation of phenol wastewater.
The biological system of the nano titanium dioxide and the microalgae coupled prepared by the invention can be used for degrading phenol in wastewater. The biosynthetic nano titanium dioxide in the biological system degrades phenol through photocatalysis, can reduce the toxicity inhibition of phenol on microalgae cells, weaken the stress reaction of microalgae, and promote the propagation of the microalgae cells, thereby indirectly improving the efficiency of the photosynthesis of the microalgae and the content of chloroplast in the microalgae and enhancing the activity of the biological system; the chloroplasts in the microalgae can obstruct the process of compounding photoelectrons and hole pairs in the biosynthesis of titanium dioxide, reduce the electron transfer resistance in the process of photodegradation and catalysis of the titanium dioxide and facilitate the electron transfer in the degradation reaction. By virtue of the synergistic effect of the biological system, the degradation capability of the biological system to phenol is obviously improved compared with that of the biological system without the synergistic effect.
In combination with the third aspect, the biological system is inoculated to the phenol wastewater in a volume ratio of 0.5-5: 100, 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 normal growth and propagation of the microalgae are not facilitated when the temperature is too high or too low.
With reference to the third aspect, the light intensity of the photocatalytic degradation is 4000 to 5000LX.
Reacting low-concentration L-cysteine, L-arginine or tyrosine and di (2-hydracrylic acid) diammonium dihydroxide titanium with microalgae liquid at room temperature to obtain a biological system coupling nano titanium dioxide and microalgae. The biological system solves the problem that microalgae is 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 the pollutants, realizes the synergistic effect between the biosynthetic nano titanium dioxide particles and the microalgae, and can efficiently degrade phenol in a solution.
Drawings
FIG. 1 is an SEM spectrogram of a biological system coupling nano titanium dioxide and microalgae, wherein the SEM magnification is 10000 times;
FIG. 2 is an XRD spectrum of a biological system coupling nano titanium dioxide and microalgae;
FIGS. 3 to 6 are XPS spectra of coupled biological systems of nano-titania and microalgae;
FIG. 7 is a graph showing the photocatalytic degradation efficiency of three different systems of example 1, comparative example 1 and comparative example 2 for a phenol solution having a concentration of 100 mg/L.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the embodiment of the invention, the oblique four-chain algae is purchased from a freshwater algae seed bank of Chinese academy of sciences, and is a dominant algae seed for degrading phenol, which is obtained by screening the oblique four-chain algae together with chlorella vulgaris, chlorella pyrenoidosa and chlorella ellipsoidea. And (3) screening: selecting four kinds of Chlorella, chlorella ellipsoidea, chlorella vulgaris and Chlorella heterotropoides, and performing amplification culture in BG11 culture medium to obtain microalgae concentrate (algae OD) 680 = 1.0). Inoculating the microalgae concentrated solution into a 100ml sterile triangular flask according to the volume ratio of the microalgae concentrated solution to a phenol solution 1 with different concentrations, wherein 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 at a light intensity of 4500LX and a temperature of 30 ℃, with the light conditions set (light/dark cycle =16/8 hours). The results show that: the degradation rate of the chlorella and the chlorella ellipsoidea to phenol is the slowest, and the degradation rate of the chlorella pyrenoidosa and the chlorella inclinogenes to phenol is the fastest. In the experiment, the slant four chain algae is selected for phenol degradation experiment.
The components of the BG11 medium and the concentrations of the components 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 0.036g/L of O, 0.006g/L of citric acid, 0.006g/L of ferric ammonium citrate, 0.001g/L of 2Na-EDTA, and 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 O is 0.05g/L. The pH was adjusted to 7.1 with 1M NaOH solution or HCl solution.
L-cysteine, L-arginine, tyrosine and bis (2-hydroxypropionic acid) diammonium dihydroxide titanium are 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 slant four-chain algae culture solution, and stirring and mixing to obtain slant four-chain algae solution;
(2) Weighing 0.0053g L-arginine, dissolving in the above algae solution, adjusting pH to about 6.8 with nitric acid, and magnetically stirring for 15min. Then, at room temperature (about 25 ℃), 0.2mL of titanium dioxide precursor bis (2-hydroxypropionic acid) diammonium dihydroxide titanium is added into the algae liquid, stirring is carried out while adding, and stirring is continued for 20min after adding, wherein the stirring speed is 1000 revolutions per minute. And (3) adsorbing nano titanium dioxide particles formed by hydrolysis in the stirring process to the surface of the clodinium clinopodii to obtain a biological system coupling the nano titanium dioxide and 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 slant four-chain algae culture solution, and stirring and mixing to obtain slant four-chain algae solution;
(2) Weighing 0.0053g of tyrosine, dissolving in the algae solution, adjusting the pH value to about 8.3 with concentrated nitric acid, magnetically stirring for 15min, adding 0.2mL of titanium dioxide precursor bis (2-hydroxypropionic acid) diammonium dihydroxide titanium at room temperature (about 25 ℃), stirring while adding, and continuing to stir for 20min after adding, wherein the stirring speed is 1100 r/min. And (3) adsorbing nano titanium dioxide particles formed by hydrolysis in the stirring process to the surface of the clodinium clinopodii to obtain a biological system coupling the nano titanium dioxide and 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, and stirring and mixing to obtain Chlorella ellipsoidea solution;
(2) Weighing 0.0053g L-arginine, dissolving in the algae solution, adjusting pH to about 7.0 with concentrated nitric acid, magnetically stirring for 15min, adding 0.2mL of titanium dioxide precursor bis (2-hydroxypropionic acid) diammonium dihydroxide titanium at room temperature (about 25 ℃), stirring while adding, and continuing to stir for 20min at the stirring speed of 1100 r/min. And adsorbing the nano titanium dioxide particles formed by hydrolysis in the stirring process to the surface of the chlorella ellipsoidea to obtain a biological system coupling the nano titanium dioxide and the microalgae.
Comparative example 1
The comparative example provides a biological system coupling nano titanium dioxide and microalgae, and the microalgae in the obtained biological system is inactivated, and the preparation steps are as follows:
and (2) obtaining a biological system coupling the nano titanium dioxide and the microalgae according to the reaction steps in the example 1, and heating the biological system in a hot water bath at 60 ℃ for 20min to inactivate the clodinium elegans in the biological system.
Comparative example 2
The present comparative example provides a pure microalgae biosystem wherein the microalgae is selected from the group consisting of slant-grown tetradactylodes.
Comparative example 3
The comparative example provides a biological system coupling nano titanium dioxide and microalgae, and the preparation steps are as follows:
the mass of L-arginine weighed in the example 1 and the volume of the added titanium dioxide precursor bis (2-hydroxypropionic acid) diammonium dihydroxide titanium are respectively changed into 0.0400g and 1.44mL, and the rest steps are completely the same as the example 1, so that the biological system of the nano titanium dioxide and the microalgae coupled with higher chemical agent concentration is obtained.
Characterization of
The microstructure of the nano titanium dioxide and microalgae coupling system obtained in examples 1 to 3 was characterized by a Scanning Electron Microscope (SEM), an X-ray diffraction technique (XRD) and an X-ray photoelectron spectroscopy (XPS). Among them, SEM results, XRD results, and XPS results of the biosystem prepared in example 1 are shown in fig. 1, fig. 2, and fig. 3 to fig. 6, respectively.
Fig. 1 is an SEM image of a biological system in which nano titanium dioxide is coupled with microalgae, and it can be seen that the biosynthetic nano titanium dioxide particles are aggregated and attached to the surface of the fusiform microalgae having a large middle and small ends. The XRD spectrogram of fig. 2 shows anatase characteristic peaks at 2 θ angles of 25.3 °, 37.8 ° and 25.8 °, further proving that the biosynthetic nano titania is successfully prepared, and diffraction peaks of the biosynthetic nano titania are similar to those of the anatase nano titania, indicating that the crystal form of the biosynthetic nano titania is anatase.
To further study the elemental composition and valence state of the resulting biological system, XPS testing was 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 titanium oxide lattice O-Ti-O-Ti, the two peaks at 531.4eV and 531.5eV are the photoelectron peaks corresponding to O1s in the hydroxyl OTi-O-H on the lattice surface, respectively, and Ti 2p 3/2 、Ti 2p 1/2 The appearance of the peak corresponding to O1s further proves the successful synthesis of the biological nano titanium dioxide. The peaks at 284.4eV, 285.1eV and 288.0eV in fig. 5 correspond to the photoelectron peak at C1s in the C-C bond, C = O bond and O-C = O bond, respectively, and the photoelectron peak at 400.4eV in fig. 6 appears at N1s, corresponding to the Ti-N bond. The appearance of the C1s peak in fig. 5 and the N1s peak in fig. 6 illustrates the coupling of the biosynthesized nano-titania to the microalgae in the biosystem.
Testing
The biological systems prepared in examples 1 to 3, comparative example 1 and comparative example 2 were subjected to photocatalytic degradation tests on solutions with a phenol concentration of 100mg/L, and the biological systems and the phenol solutions were mixed in a volume ratio of 1.
And detecting the phenol concentration in the photocatalytic degradation process by adopting a high performance liquid chromatography for different degradation times, and drawing a curve by taking the degradation time as a horizontal coordinate and the detected phenol solution concentration as a vertical coordinate to obtain a trend graph of the phenol concentration changing along with time in the photocatalytic degradation process of each biological system. The detection operations are carried out after the following pre-treatments: a small amount of the phenol solution to be tested was centrifuged at 6000 rpm for 5 minutes, after which 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 solution with concentration of 100mg/L is shown in FIG. 7.
TABLE 1 phenol degradation efficiency data for biosystems obtained in examples 1-3 and comparative examples 1-3
It can be seen from table 1 and fig. 7 that, under the same degradation time and degradation conditions, the biological system coupling the nano titanium dioxide and the slant chain algae has the highest degradation efficiency on phenol, wherein the phenol degradation efficiency of the biological system corresponding to example 1 is 1.32 times and 2.30 times that of comparative example 1 and comparative example 2, respectively, and the phenol degradation efficiency of the biological system coupling the nano titanium dioxide and the microalgae inactivated by the microalgae (comparative example 1) is 1.75 times that of the pure microalgae system (comparative example 2), which indicates that the coupling of the nano titanium dioxide and the biosynthetic nano titanium dioxide improves the photocatalytic degradation efficiency on phenol, and even if the inactivation operation is performed on the microalgae in the biological system coupling the nano titanium dioxide and the microalgae, the phenol degradation efficiency of the biological system is still higher than that of the pure microalgae system, which indicates that the inactivated microalgae still has an adsorption effect on phenol, and is helpful for the degradation of the nano titanium dioxide particles on phenol. The degradation efficiency of the biological system prepared in the embodiment 1 on phenol is 1.32 times that of the biological system prepared in the comparative example 1, which shows that the synergistic effect exists in the biological system coupled by the nano titanium dioxide and the microalgae, the nano titanium dioxide can promote the microalgae cells to secrete extracellular polymers, the peroxidation damage of the microalgae cells is effectively avoided, the growth and the propagation of the microalgae are accelerated, the activity of the biological system is enhanced, and the photocatalysis rate of the microalgae on phenol is accelerated; after the microalgae grows and breeds better, more chloroplasts are generated inside the microalgae to intercept the composition of photo-generated electrons and holes in nano titanium dioxide particles, so that the electron exchange density and capacitance in a biological system are increased, the electron transfer is easier, and the photocatalytic degradation of the nano titanium dioxide to phenol is accelerated. From the phenol degradation efficiency of example 1 and comparative example 3, it can be seen that when the concentration of the chemical agent in the biological system exceeds the concentration range defined in the present invention, the chemical agent will produce toxic effect on the microalgae in the biological system and even cause death of the microalgae, thereby reducing the degradation efficiency of the biological system.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A coupling method of nano titanium dioxide and microalgae is characterized by comprising the following steps:
s1, taking a microalgae culture solution, dissolving L-cysteine in the microalgae culture solution, and stirring and uniformly mixing to obtain a microalgae solution;
s2, adding L-arginine into the microalgae liquid, adjusting the pH value to 6.3-8.5, slowly adding a titanium dioxide precursor di (2-hydroxypropionic acid) diammonium dihydroxide titanium and stirring while adding to obtain a biological system coupling the nano titanium dioxide and the microalgae.
2. The method for coupling nanometer titanium dioxide with microalgae according to claim 1, wherein the microalgae in the microalgae culture solution comprises at least one or more of TetraCHACHUANZA JIAODAN, chlorella vulgaris, chlorella ellipsoidea or Chlorella proteolifera.
3. The method for coupling nano titanium dioxide and microalgae according to claim 1, wherein the reaction temperature in step S2 is 20-30 ℃ and the reaction condition is normal pressure.
4. The method for coupling nano titanium dioxide with microalgae according to claim 1, wherein the amount of L-cysteine added in step S1 is: 2.5 mmol/L-5.0 mmol/L.
5. The method for coupling nano titanium dioxide and microalgae according to claim 1, wherein in step S2, the amount of L-arginine or tyrosine added is: 0.55mmol/L to 2.30mmol/L, wherein the molar ratio of the bis (2-hydroxypropionic acid) diammonium dihydroxide titanium to the L-arginine or the tyrosine is 2 to 9:1.
6. the method for coupling nano titanium dioxide and microalgae as claimed in claim 5, wherein the molar ratio of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium to L-arginine or tyrosine is 3-5: 1.
7. the coupling method of nano titanium dioxide and microalgae according to claim 1, wherein the stirring manner is magnetic stirring, and the stirring speed is 1000-1200 rpm.
8. A biological system coupling nano titanium dioxide and microalgae, which is characterized by being prepared by the method of any one of claims 1 to 7.
9. Use of the biological system of claim 8 in photocatalytic degradation of phenol wastewater.
10. The use according to claim 9, wherein the biological system is inoculated into the phenol wastewater in a volume ratio of 0.5 to 5:100, respectively; 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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