CN113262793A - Novel titanium dioxide composite photocatalyst and preparation and application methods thereof - Google Patents
Novel titanium dioxide composite photocatalyst and preparation and application methods thereof Download PDFInfo
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Abstract
The invention discloses a novel titanium dioxide composite photocatalyst and preparation and application methods thereof. Wherein the preparation method comprises the following steps: adsorbing metal ions by titanium dioxide powder and/or particles with surface colonized microbial films to obtain a composite precursor; and carrying out thermochemical reaction on the composite precursor and zinc chloride or alkali metal oxide in a protective atmosphere to obtain the composite photocatalyst, wherein the catalyst has stable and efficient photocatalytic capability.
Description
Technical Field
The invention relates to the technical field of titanium dioxide micropore loading metal ion composite photocatalytic materials.
Background
In recent years, with the rapid development of petrochemical industry, coal chemical industry, printing and dyeing, pharmacy and other industries, the total amount of wastewater discharged in China is 466.62 hundred million tons in 2015, 500 hundred million tons in 2018 are broken through, and 554.65 hundred million tons in 2019 are increased by 6.4 percent on a same scale, wherein the high-concentration, difficult-degradation and high-toxicity organic wastewater accounts for 45.5 percent. Such organic wastewater is difficult to achieve the emission or recycling standard through conventional treatment, thereby causing the continuous increase of sustainable organic pollutants in the environment and the waste of water resources. The photocatalytic oxidation technology in various wastewater treatment processes has wide application prospects due to the advantages of strong oxidizability, mild reaction conditions, cleanness, high efficiency, large treatment capacity and the like. In which TiO alone2Has been widely studied as a photocatalyst, however, TiO2Low utilization rate of visible light, and TiO2Photo-generated electron-hole pairs generated by light excitation are easy to recombine, so that TiO2Has low photocatalytic efficiency, and in addition, TiO2The composite photocatalyst prepared by doping other metals can improve the utilization efficiency of titanium dioxide to visible light to a certain extent, but because of TiO2The composite catalyst is difficult to form close combination with other metals and oxides thereof, so that the composite catalyst is still difficult to stably and efficiently play a role, and the further industrialization of the composite catalyst is influenced by the factors.
Disclosure of Invention
The invention aims to provide a novel titanium dioxide composite photocatalyst, wherein a titanium dioxide carrier modified by a microorganism biofilm formation, metal particles embedded in micropores of the carrier and oxides of the metal particles are arranged in the structure of the photocatalyst, and the photocatalyst has stable and efficient photocatalytic capability.
The invention also aims to provide a preparation method and an application method of the catalyst.
The invention firstly provides the following technical scheme:
a preparation method of a novel titanium dioxide composite photocatalyst comprises the following steps:
obtaining titanium dioxide powder and/or particles with active microbial films colonized on the surfaces of the titanium dioxide powder and/or particles as basic precursors;
obtaining a composite precursor through the adsorption of the basic precursor to metal ions;
and carrying out thermochemical reaction on the composite precursor and zinc chloride or alkali metal hydroxide under a protective atmosphere to obtain the composite photocatalyst.
In the scheme, the invention utilizes the microorganisms to form the biological membrane on the surface of the titanium dioxide as the precursor material, utilizes abundant metal binding groups such as hydroxyl, carboxyl, amino and the like in the microorganisms and metabolites thereof to strengthen the adsorption of the precursor material to metal ions, and then activates pore-forming action on a composite precursor through alkali metal oxide and/or zinc chloride to finally obtain the novel method of the porous photocatalyst under the synergistic action of the carrier modified by the microorganism biofilm formation and the metal ions loaded by the carrier.
In the scheme, when the zinc chloride reacts with the composite precursor, zinc chloride molecules are soaked in carbon of the composite precursor to form a skeleton effect, high polymers of the carbon are carbonized and then deposited on the skeleton, and after impurities such as zinc chloride and the like are absorbed after the reaction, the original occupied positions of the zinc chloride molecules form pores, so that the porous structure active carbon with a huge surface is formed.
When the alkali metal hydroxide reacts with the composite precursor, the alkali metal hydroxide can burn part of carbon, and an activated carbon pore structure is formed through intercalation of generated simple substance metal in the graphite layer sheet.
According to some preferred embodiments of the present invention, the microorganism is selected from one or more of escherichia coli, yeast, and bacillus subtilis.
According to some preferred embodiments of the present invention, the metal ions are selected from one or more of iron, cobalt, nickel, cerium, copper, manganese, aluminum ions.
According to some preferred embodiments of the invention, the alkali metal hydroxide is selected from KOH and/or NaOH.
According to some preferred embodiments of the invention, the base precursor is obtained by co-culturing the titanium dioxide powder and/or granules with the microorganism after addition to the culture medium.
According to some preferred embodiments of the invention, the medium is neutral LB medium and/or YPD medium.
More preferably, the LB medium is composed of tryptone, yeast extract and sodium chloride, and the YPD medium is composed of yeast extract, peptone and glucose.
According to some preferred embodiments of the invention, the active microorganism is a microorganism cultured to log phase.
According to some preferred embodiments of the present invention, the temperature of the cultivation is 15 to 45 ℃ and the cultivation time is 12 to 72 hours.
According to some preferred embodiments of the present invention, the adsorption is performed by adding the basic precursor to a metal ion solution, wherein the concentration of the metal ion in the solution is 1 to 10000 mg/L.
According to some preferred embodiments of the present invention, the temperature of the adsorption is 15 to 55 ℃, and the adsorption time is 0.5 to 24 hours.
According to some preferred embodiments of the present invention, the composite precursor and zinc chloride or alkali metal oxide are mixed and ground, and then the thermochemical reaction is performed by the obtained ground product.
More preferably, the particle size of the ground material is 0.1 to 3 mm.
According to some preferred embodiments of the present invention, the thermochemical reaction temperature is 300 to 1700 ℃.
According to some preferred embodiments of the present invention, the thermochemical reaction time is 0.5 to 5 hours.
According to some preferred embodiments of the present invention, the temperature rise rate of the thermochemical reaction is 5 to 30 ℃/min.
According to some preferred embodiments of the present invention, the concentration of the metal ions in the metal ion solution is 950-.
According to some preferred embodiments of the invention, the preparation method comprises the steps of:
(1) adding titanium dioxide powder into a culture medium containing the microorganisms for co-culture so that the microorganisms are attached and colonized on the surface of the titanium dioxide to form a biofilm formation material;
(2) adding the film forming material into the solution of the metal ions for adsorption, and centrifuging after adsorption is finished to obtain a metal ion-film forming material composite precursor;
(3) and (2) carrying out vacuum freeze drying on the composite precursor to prepare a dry powder composite, uniformly mixing the dry powder composite with zinc chloride or alkali metal oxide, grinding, carrying out thermochemical reaction in a protective atmosphere, washing the product with deionized water, and drying at low temperature to obtain the catalyst.
According to some preferred embodiments of the present invention, in the step (2), the centrifugation is performed at a rotation speed of 3000 to 20000rpm and/or for a centrifugation time of 1 to 60 min.
According to some preferred embodiments of the present invention, in the step (3), the vacuum freeze-drying time is 0.5 to 24 hours.
According to some preferred embodiments of the invention, the protective atmosphere in step (3) is provided by one or more of nitrogen, hydrogen, argon.
The invention further provides a catalyst prepared by the preparation method, and the specific surface area of the catalyst can reach 170m on average2And the metal particles are embedded into the catalyst pore channels, and the shape of the metal particles is a rod-shaped structure.
The invention further provides an application method of the catalyst prepared by the preparation method, which is used for photocatalytic degradation of organic wastewater.
According to some preferred embodiments of the present invention, the wastewater comprises one or more of landfill leachate, coking wastewater, printing wastewater.
According to some preferred embodiments of the present invention, the COD concentration of the wastewater is 1000 to 20000 mg/L.
According to some preferred embodiments of the present invention, the amount of the catalyst used in the photocatalytic degradation is 0.1 to 20 g/L.
According to some preferred embodiments of the present invention, the photocatalyst has one or more of a xenon lamp, a mercury lamp, a metal halide lamp, and an ultraviolet lamp as a light source.
The invention provides a novel method for preparing a titanium dioxide-multi-metal photocatalyst by utilizing microorganisms to form a biological film on the surface of titanium dioxide as a precursor material, utilizing abundant metal binding groups such as hydroxyl, carboxyl, amino and the like in the microorganisms and metabolites thereof to strengthen the adsorption of the precursor material on multi-metal ions and utilizing a thermochemical treatment means.
Compared with the prior art, the preparation method has the advantages of simple preparation process, low cost, good photocatalytic performance and huge market application potential.
The catalyst of the invention has the advantages of close combination of different components, obvious synergistic effect, high catalytic efficiency and strong catalytic capability.
Drawings
FIG. 1 is a transmission electron micrograph of Escherichia coli colonized on the titanium dioxide surface in example 1.
FIG. 2 is a transmission electron micrograph of a metal embedded in the micropores of titanium dioxide in example 1.
FIG. 3 is a graph showing the effect of photocatalytic degradation of waste leachate by copper, iron, cerium and oxides thereof embedded in micropores of titanium dioxide in example 1 in comparison with other commercial photocatalysts.
FIG. 4 is a graph comparing the photocatalytic effect of copper, iron, cerium and their oxides embedded in the micropores of titanium dioxide of example 2 with that of other commercial photocatalysts for catalytically degrading landfill leachate.
FIG. 5 is a graph comparing the photocatalytic effect of copper, iron, cerium and their oxides embedded in the micropores of titanium dioxide in example 3 with that of other commercial photocatalysts for catalytically degrading landfill leachate.
FIG. 6 is a graph comparing the effect of photocatalytic degradation of coking wastewater by manganese, cobalt and oxides thereof embedded in micropores of titanium dioxide in example 4 with other commercial photocatalysts.
FIG. 7 is a graph comparing the effect of photocatalytic degradation of printing and dyeing wastewater by iron, cobalt, cerium and oxides thereof embedded in the micropores of titanium dioxide in example 5 with other commercial photocatalysts.
Detailed Description
The present invention is described in detail below with reference to the following embodiments and the attached drawings, but it should be understood that the embodiments and the attached drawings are only used for the illustrative description of the present invention and do not limit the protection scope of the present invention in any way. All reasonable variations and combinations that fall within the spirit of the invention are intended to be within the scope of the invention.
The first embodiment is as follows:
the photocatalyst prepared by combining the microorganism biofilm formation modification carrier and the adsorption of multi-element metal ions is prepared by the following steps:
(1) adding sterilized titanium dioxide powder and Escherichia coli (Escherichia coli) into 1L LB culture medium composed of tryptone 10g/L, yeast extract 5g/L and sodium chloride 10g/L under aseptic condition, adjusting pH to about 7.0 with NaOH, shake culturing at 25 deg.C for 24h, suction filtering with suction filter to obtain a layer of dense Escherichia coli colonized on titanium dioxide surface, i.e. a microbial material with a membrane coated on titanium dioxide surface, wherein transmission electron microscope image is shown in figure 1, and can show that the surface with titanium dioxide as core is adhered with dense Escherichia coli.
(2) Preparing mixed metal ion solutions with the concentrations of copper chloride, ferric chloride and cerium chloride being 1000mg/L respectively, adding wet bacteria loaded on the surface of titanium dioxide into the prepared copper, iron and cerium ion solutions, and stirring and adsorbing for 10 hours at 25 ℃; then centrifuging for 10min under the condition of 10000rpm to obtain a mixture of titanium dioxide film-forming supported iron, copper and cerium;
(3) washing the mixture with deionized water for three times, centrifugally collecting, performing vacuum freeze drying for 12h to prepare dry powder, then adding potassium hydroxide for uniform mixing, performing thermochemical treatment at the temperature rise rate of 10 ℃/min and the temperature of 1000 ℃ for 2.5h under the protection atmosphere of argon, cooling to obtain the titanium dioxide-embedded copper, iron and cerium metal photocatalyst, wherein a transmission electron microscope picture of the titanium dioxide-embedded copper, iron and cerium metal photocatalyst is shown in a figure of figure 2, and after thermochemical carbonization of escherichia coli, copper, iron and cerium metal particles are embedded into a pore channel of a titanium dioxide carrier to obtain the rod-shaped photocatalyst.
The transmission electron microscope picture is shown as the attached figure 2, and the metal particles are embedded into the rod-shaped photocatalyst in the pore canal of the titanium dioxide carrier.
The photocatalyst obtained in this example was tested for its catalytic performance by the following procedure:
weighing 1g of the photocatalytic material obtained in the embodiment, adding the photocatalytic material into 500mL of waste leachate, wherein COD in the waste water is 3563.16mg/L, irradiating the waste water by using an ultraviolet lamp with a wavelength of 256nm, carrying out photocatalytic oxidation for 60min, sampling every 10min to measure COD in the waste water, calculating the removal rate of the COD, wherein the removal rate of the COD reaches 85.49% in 60min, and comparing the catalytic oxidation effects of three market catalysts, namely a catalyst A (a carbon nitride type photocatalyst), a catalyst B (a titanium dioxide photocatalyst) and a catalyst C (a nano zinc oxide photocatalyst), under the same condition, the comparison shows that the three market catalysts are catalytically oxidized for 60min under the same condition, and the removal rates of the COD are 48.39%, 50.18% and 54.36% respectively, as shown in the attached drawing 3. The result shows that the catalyst material can efficiently catalyze and oxidize organic matters in the waste leachate, and the performance of the catalyst material is more excellent than that of a catalyst in the market.
Example two:
the photocatalyst prepared by combining the microorganism biofilm formation modification carrier and the adsorption of multi-element metal ions is prepared by the following steps:
(1) adding sterilized titanium dioxide powder and Escherichia coli (Escherichia coli) into 1L LB culture medium composed of tryptone 10g/L, yeast extract 5g/L and sodium chloride 10g/L under aseptic condition, adjusting pH to about 7.0 with NaOH, shake culturing at 25 deg.C for 24h, and suction filtering with suction filter to obtain a layer of compact Escherichia coli colonized on the surface of titanium dioxide, i.e. the microbial material with membrane coated titanium dioxide surface.
(2) Preparing mixed metal ion solutions with the concentrations of copper chloride, ferric chloride and cerium chloride of 800mg/L respectively, adding wet bacteria loaded on the surface of titanium dioxide into the prepared copper, iron and cerium ion solutions, and stirring and adsorbing for 8 hours at 25 ℃; then centrifuging for 10min under the condition of 10000rpm to obtain a mixture of titanium dioxide film-forming supported iron, copper and cerium;
(3) washing the mixture with deionized water for three times, centrifugally collecting, preparing dry powder by vacuum freeze drying for 12h, then adding zinc chloride for uniform mixing, carrying out thermochemical treatment at the temperature rise rate of 15 ℃/min and the temperature of 1200 ℃ for 2.5h under the protection atmosphere of argon, and cooling to obtain the rod-shaped photocatalyst with copper, iron and cerium metal particles embedded in the pore channels of the titanium dioxide carrier.
The photocatalyst obtained in this example was tested for its catalytic performance by the following procedure:
weighing 1g of the photocatalytic material obtained in the embodiment, adding the photocatalytic material into 500mL of waste leachate, wherein COD in the waste water is 3563.16mg/L, irradiating the waste water by using an ultraviolet lamp with a wavelength of 256nm, carrying out photocatalytic oxidation for 60min, sampling every 10min to measure COD in the waste water, calculating the removal rate of the COD, wherein the removal rate of the COD reaches 74.41% in 60min, and comparing the catalytic oxidation effects of three market catalysts, namely a catalyst A (a carbon nitride type photocatalyst), a catalyst B (a titanium dioxide photocatalyst) and a catalyst C (a nano zinc oxide photocatalyst), under the same condition, the results are shown in figure 4, and the comparison shows that the three market catalysts are catalytically oxidized for 60min under the same condition, and the removal rates of the COD are 48.39%, 50.18% and 54.36% respectively. The result shows that the catalyst material can effectively catalyze and oxidize organic matters in the waste leachate, and the performance of the catalyst material is more excellent than that of a catalyst in the market.
Example three:
the photocatalyst prepared by combining the microorganism biofilm formation modification carrier and the adsorption of multi-element metal ions is prepared by the following steps:
(1) adding sterilized titanium dioxide powder and Escherichia coli (Escherichia coli) into 1L LB culture medium composed of tryptone 10g/L, yeast extract 5g/L and sodium chloride 10g/L under aseptic condition, adjusting pH to about 7.0 with NaOH, shake culturing at 25 deg.C for 24h, and suction filtering with suction filter to obtain a layer of compact Escherichia coli colonized on the surface of titanium dioxide, i.e. the microbial material with membrane coated titanium dioxide surface.
(2) Preparing mixed metal ion solutions with the concentrations of copper chloride, ferric chloride and cerium chloride of 500mg/L respectively, adding wet bacteria loaded on the surface of titanium dioxide into the prepared copper, iron and cerium ion solutions, and stirring and adsorbing for 5 hours at 25 ℃; then centrifuging for 10min under the condition of 10000rpm to obtain a mixture of titanium dioxide film-forming supported iron, copper and cerium;
(3) washing the mixture with deionized water for three times, centrifugally collecting, preparing dry powder by vacuum freeze drying for 12h, then adding zinc chloride for uniform mixing, carrying out thermochemical treatment at the temperature rise rate of 15 ℃/min and the temperature of 800 ℃ for 2h under the protective atmosphere of argon, and cooling to obtain the rod-shaped photocatalyst with copper, iron and cerium metal particles embedded in the pore channels of the titanium dioxide carrier.
The photocatalyst obtained in this example was tested for its catalytic performance by the following procedure:
weighing 1g of the photocatalytic material obtained in the embodiment, adding the photocatalytic material into 500mL of waste leachate, wherein COD in the waste water is 3563.16mg/L, irradiating the waste water by using an ultraviolet lamp with a wavelength of 256nm, carrying out photocatalytic oxidation for 60min, sampling every 10min to measure COD in the waste water, calculating the removal rate of the COD, wherein the removal rate of the COD reaches 61.49% in 60min, and comparing the catalytic oxidation effects of three market catalysts, namely a catalyst A (a carbon nitride type photocatalyst), a catalyst B (a titanium dioxide photocatalyst) and a catalyst C (a nano zinc oxide photocatalyst), under the same condition, the results are shown in figure 5, and the comparison shows that the three market catalysts are catalytically oxidized for 60min under the same condition, and the removal rates of the COD are 48.39%, 50.18% and 54.36% respectively. The result shows that the catalyst material can effectively catalyze and oxidize organic matters in the waste leachate, and the performance of the catalyst material is more excellent than that of a catalyst in the market.
As can be seen from the comparison of the first to third embodiments, the overall processing conditions of the first embodiment have the best technical effect, and on this basis, the same processing conditions as those of the first embodiment are selected for the following fourth and fifth embodiments as follows:
example four:
the photocatalyst prepared by combining the microorganism biofilm formation modification carrier and the adsorption of multi-element metal ions is prepared by the following steps:
(1) adding titanium dioxide powder and yeast (saccharomyces) into 1L YPD culture medium under aseptic condition, performing shake culture at 25 ℃ for 48h to logarithmic phase, and performing suction filtration by using a suction filter to obtain wet bacteria loaded on titanium dioxide, wherein the YPD culture medium has the following formula: 1% yeast extract, 2% peptone, 2% glucose;
(2) preparing mixed metal ion solutions with the concentrations of manganese chloride and cobalt chloride being 1000mg/L respectively, adding the microbial material with the film-forming surface of the titanium dioxide into the mixed metal ion solutions, and stirring and adsorbing for 10 hours at 25 ℃; centrifuging for 10min at 10000rpm to obtain a titanium dioxide biofilm and a microorganism mixture loaded with manganese and cobalt ions;
(3) washing the mixture for three times by using deionized water, centrifugally collecting, performing vacuum freeze drying for 12 hours to prepare dry powder, then adding potassium hydroxide, uniformly mixing, performing thermochemical treatment at the temperature rise rate of 10 ℃/min and the temperature of 1000 ℃ for 2.5 hours under the protection atmosphere of argon, cooling to obtain the titanium dioxide-embedded manganese and cobalt metal photocatalyst, and testing the catalytic performance of the photocatalyst obtained in the embodiment by the following process:
weighing 1g of the composite photocatalytic material obtained in the embodiment, adding the composite photocatalytic material into 500mL of coking wastewater, the COD of the wastewater is 2845.15mg/L, ultraviolet lamp irradiation with the wavelength of 256nm is utilized to carry out photocatalytic oxidation for 60min, sampling is carried out every 10min to measure the COD in the wastewater, the COD removal rate is calculated, the COD removal rate reaches 62.49 percent at 60min, the catalytic oxidation effects of three market catalysts, namely a catalyst A (carbon nitride type photocatalyst), a catalyst B (titanium dioxide photocatalyst) and a catalyst C (nano zinc oxide photocatalyst), are compared under the same condition, the results are shown in figure 6, and the comparison shows that after 60min, the removal rates of COD of the three market catalysts are 48.91%, 50.83% and 56.69%, respectively, and the results show that the catalyst provided by the invention has photocatalytic performance, can effectively catalyze and oxidize organic matters in coking wastewater, and the catalytic performance is more excellent than that of the market catalysts.
Example five:
the photocatalyst prepared by combining the microorganism biofilm formation modification carrier and the adsorption of multi-element metal ions is prepared by the following steps:
(1) titanium dioxide powder and Bacillus subtilis are added into 1L of LB culture medium under the aseptic condition, and after shaking culture is carried out for 24 hours at 25 ℃ to reach logarithmic phase, wet bacteria loaded on titanium dioxide are obtained by suction filtration through a suction filtration machine. The formulation of LB medium was as follows: 10g/L of tryptone, 5g/L of yeast extract and 10g/L of sodium chloride, and adjusting the pH of the culture medium to be about 7.0 by using NaOH;
(2) preparing mixed metal ion solutions with the concentrations of ferric chloride, cobalt chloride and cerium chloride being 1000mg/L respectively, adding wet thalli loaded on the surface of titanium dioxide into the prepared iron, cobalt and cerium metal ion solutions, and stirring and adsorbing for 10 hours at the temperature of 25 ℃; then centrifuging for 10min under the condition of 10000rpm to obtain a mixture of titanium dioxide film-forming supported iron, cobalt and cerium;
(3) washing the mixture for three times by using deionized water, centrifugally collecting, preparing dry powder by vacuum freeze drying for 12h, then adding potassium hydroxide for uniform mixing, carrying out thermochemical treatment at the temperature rise rate of 10 ℃/min and the temperature of 1000 ℃ for 2.5h under the protection atmosphere of argon, cooling to obtain the photocatalyst with iron, cobalt and cerium metal particles embedded into the pore channels of the titanium dioxide carrier
The photocatalyst obtained in this example was tested for its catalytic ability by the following procedure:
weighing 1g of the photocatalytic material obtained in the embodiment, adding the photocatalytic material into 500mL of printing and dyeing wastewater, wherein the COD of the wastewater is 1513.45mg/L, irradiating the wastewater by using an ultraviolet lamp with a wavelength of 256nm, carrying out photocatalytic oxidation for 60min, sampling every 10min to measure the COD in the wastewater, calculating the removal rate of the COD, wherein the removal rate of the COD reaches 72.09% in 60min, comparing the catalytic oxidation effects of three market catalysts, namely a catalyst A (carbon nitride type photocatalyst), a catalyst B (titanium dioxide photocatalyst) and a catalyst C (nano zinc oxide photocatalyst) under the same condition, and finding that the three market catalysts are catalytically oxidized for 60min under the same condition, the removal rates of the COD are 53.13%, 48.39% and 66.36% respectively, wherein the results show that the catalyst material provided by the invention has photocatalytic performance and can effectively catalyze and oxidize organic matters in the printing and dyeing wastewater, the performance is more excellent than that of the catalyst in the market.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A preparation method of a novel titanium dioxide composite photocatalyst is characterized by comprising the following steps: it includes:
obtaining titanium dioxide powder and/or particles with active microbial films colonized on the surfaces of the titanium dioxide powder and/or particles as basic precursors;
obtaining a composite precursor through the adsorption of the basic precursor to metal ions;
and carrying out thermochemical reaction on the composite precursor and zinc chloride or alkali metal hydroxide under a protective atmosphere to obtain the composite photocatalyst.
2. The method of claim 1, wherein: the microorganism is selected from one or more of escherichia coli, yeast and bacillus subtilis, and/or the metal ion is selected from one or more of iron, cobalt, nickel, cerium, copper, manganese and aluminum ion; and/or the alkali metal hydroxide is selected from KOH and/or NaOH.
3. The method of claim 1, wherein: the basic precursor is obtained by co-culturing the titanium dioxide powder and/or particles and the microorganisms after being added into a culture medium; preferably, the medium is selected from neutral LB medium and/or YPD medium.
4. The production method according to claim 3, characterized in that: the temperature of the active microorganism is 15-45 ℃ from the culture to the logarithmic phase, and the culture time is 12-72 h.
5. The method of claim 1, wherein: the adsorption is realized by adding the basic precursor into a metal ion solution, and the concentration of metal ions in the solution is 1-10000 mg/L.
6. The method of claim 1, wherein: the adsorption temperature is 15-55 ℃, and the adsorption time is 0.5-24 h.
7. The method of claim 1, wherein: and mixing and grinding the composite precursor and zinc chloride or alkali metal hydroxide, and carrying out thermochemical reaction on the obtained ground product, wherein the particle size of the ground product is 0.1-3 mm.
8. The method of claim 1, wherein: the temperature of the thermochemical reaction is 300-1700 ℃, and/or the time of the thermochemical reaction is 0.5-5 h, and/or the temperature rise rate of the thermochemical reaction is 5-30 ℃/min; preferably, the concentration of the metal ions in the metal ion solution is 950-1000mg/L, the adsorption temperature is 20-30 ℃, the adsorption time is 9.5-10.5h, the thermochemical reaction temperature is 950-1050 ℃, and the temperature rise rate of the thermochemical reaction is 9.5-10.5 ℃/min.
9. The catalyst produced by the production method according to any one of claims 1 to 8.
10. Use of the catalyst prepared by the preparation method according to any one of claims 1 to 8 in photocatalytic degradation of organic wastewater.
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