CN108588130B - Method for preparing titanium dioxide tube-based composite material by biological method - Google Patents
Method for preparing titanium dioxide tube-based composite material by biological method Download PDFInfo
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Abstract
The invention discloses a method for preparing a titanium dioxide tube-based composite material by a biological method, which comprises the steps of LB culture medium preparation, anaerobic culture medium preparation, inoculation and culture of MR-1 strains, synthesis of titanium dioxide nanotubes (TNTs), mother liquor preparation, preparation of the titanium dioxide nanotube-based composite material and the like, wherein the microorganism Shewanella oneidensis MR-1 taken from the environment is used as a biological reducing agent and a template agent, and Ag is synthesized in situ on the wall of the TNTs2S NPs to form Ag in one step2The method is economical, effective, low-carbon and environment-friendly, avoids adding chemical reagents, does not consume any energy, and simultaneously produces the Ag based composite material2The S/TNTs nanotube-based composite material is used for catalyzing and reducing organic pollutant p-nitrophenol which is difficult to degrade in the environment and has biotoxicity, and has high catalytic efficiency.
Description
Technical Field
The invention relates to a method for preparing a titanium dioxide nanotube-based composite material, in particular to a method for preparing a titanium dioxide nanotube-based composite material by a biological method.
Technical Field
The silver sulfide nano-particles are narrow-energy-band semiconductors, have high optical performance, catalytic performance and chemical stability, and are widely applied to the fields of photocells, ion conductors, infrared detectors, catalytic degradation of pollutants and the like. However, silver sulfide nanoparticles have a large specific surface energy and are easy to agglomerate, and the silver sulfide nanoparticles are generally loaded on a certain carrier to improve the dispersibility and stability of the silver sulfide nanoparticles. One-dimensional titanium dioxide nanotubes (TiO)2nanotubes, TNTs for short) have a larger specific surface area and can provide more active sites, and the one-dimensional nanotubes are favorable for electron transfer to improve the catalytic efficiency.However, the existing methods for synthesizing silver sulfide loaded titanium dioxide based composite materials include electrochemical methods, thermal decomposition methods, continuous ion deposition methods and the like, most of the methods use toxic and harmful chemical reagents and require certain special conditions (such as high temperature and high pressure), so that the method not only causes secondary pollution to the environment, but also has harsh conditions, high processing cost and low energy utilization rate.
The biological synthesis of nano material is a technology of self-assembling bioactive molecule inside or outside cell to form nano material. Compared with the traditional physical and chemical methods, the biological method has the advantages of cleanness, no toxicity, environmental friendliness, mild and controllable reaction conditions, no need of additionally adding a reducing agent, high efficiency and the like.
The Shewanella oneidensis MR-1 (S. oneidensis MR-1 for short) is a model metal reducing bacterium, and can utilize various metal compounds, sulfides and the like as electron receptors to carry out respiratory metabolism under the anaerobic condition. S. oneidensis MR-1 is capable of transferring electrons generated in cytoplasm or intracellular membrane to an electron acceptor existing in extracellular environment, finally, through a diverse electron transfer system consisting of c-hemoglobin or reductase enzyme localized on intracellular membrane, periplasm of cell membrane and extracellular membrane. The electron acceptor includes more than 20 different electron acceptors such as organic matter, metal oxide and sulfide, so the method has wide application prospect in the aspects of environmental bioremediation and biodegradation.
Therefore, it is necessary to establish a preparation method for preparing silver-loaded titanium dioxide nanotube-based composite material based on microorganisms taken from the environment to realize Ag2The S/TNTs nano composite material has the advantages of economy, effectiveness, low carbon and environmental protection.
Disclosure of Invention
The invention aims to: the method for preparing the titanium dioxide tube-based composite material by the biological method avoids the addition of chemical reagents, does not consume any energy, and realizes the purposes of economy, effectiveness, low carbon and environmental protection.
In order to achieve the above purpose, the invention provides the following technical scheme:
a method for preparing a titanium dioxide tube-based composite material by a biological method comprises the following steps:
s1, preparing an LB culture medium: weighing a certain amount of tryptone, yeast powder and NaCl, adding into deionized water, mixing, subpackaging, sealing, sterilizing at high temperature under high pressure, cooling, and storing for later use;
s2, preparing an anaerobic culture medium: weighing a certain amount of N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, sodium lactate, sodium chloride, ammonium sulfate, magnesium sulfate heptahydrate, trace element stock solution and ultrapure water, uniformly mixing, adjusting the pH to 7.0 by using NaOH solution, fixing the volume, subpackaging in serum bottles, filling nitrogen for 5min to completely remove dissolved oxygen in the bottles, sealing by using a butyl rubber plug, covering, sterilizing at high temperature and high pressure, and storing for later use;
s3, inoculation and culture of MR-1 strain: firstly, inoculating the S.oniedensis MR-1 strain into an LB culture medium for culture, centrifuging the cultured bacterium solution for 2-8min under the condition of 5000-7000rpm, discarding the supernatant, and resuspending the thallus at the bottom by using a sterilized anaerobic culture medium for later use;
s4, synthetic titanium dioxide nanotubes (TNTs): adding a certain amount of titanium dioxide powder into a NaOH solution, magnetically stirring until the titanium dioxide powder is uniform, refluxing, diluting with distilled water, performing suction filtration, dispersing into a dilute hydrochloric acid solution, stirring overnight, washing with ultrapure water to be neutral, drying at constant temperature, calcining the solid, naturally cooling to room temperature, and grinding into powder by using an agate mortar for later use;
s5, preparation of mother liquor: dissolving a surfactant sodium dodecyl benzene sulfonate in an anaerobic culture medium to prepare a 0.5-2 wt% sodium dodecylbenzenesulfonate solution, adding a certain amount of TNTs and excessive polyvinylpyrrolidone into the solution, stirring uniformly to obtain a mixed solution A, then adding a certain amount of silver nitrate and sodium thiosulfate pentahydrate, dissolving, performing ultrasonic treatment for 5-15min, and performing magnetic stirring for 2-4h to obtain a mixed solution B;
s6, preparing a titanium dioxide nanotube-based composite material: injecting the mixed solution B into a serum bottle filled with an anaerobic culture medium by using a sterile syringe, injecting a certain amount of MR-1 bacterial solution, and thenShake culturing the serum bottle containing MR-1 bacteria liquid for 40-60h, centrifuging the reacted system to remove thallus, washing with ultrapure water and anhydrous alcohol for several times, centrifuging again to obtain reaction product, and drying to obtain silver sulfide nanoparticle-loaded titanium dioxide (Ag)2S/TNTs) nanotube-based composite material.
Preferably, in the step S2, the preparation method of the trace element stock solution is: taking 1.0-2.0g nitrilotriacetic acid, fixing the volume to 500mL by using ultrapure water, adjusting the pH value to 6.5 by using a potassium hydroxide solution, then adding 2.0-3.0g magnesium sulfate, 0.5-1.5g calcium chloride dihydrate, 0.5-1.5g sodium chloride, 0.3-0.7g manganese sulfate, 0.01-0.03g zinc sulfate heptahydrate, 0.05-0.15g ferrous sulfate heptahydrate, 0.01-0.03g cobalt sulfate heptahydrate, 0.01-0.04g nickel chloride hexahydrate, 0.01-0.03g aluminum potassium sulfate dodecahydrate, 0.005-0.015g copper sulfate pentahydrate, 0.005-0.015g boric acid, 0.005-0.015g sodium molybdate dihydrate and 0.1-0.5mg sodium selenite pentahydrate, stirring and dissolving by using the ultrapure water to 1000mL, and placing the mixture in a refrigerator with the constant volume to 4 ℃ for storage.
Preferably, in the step S1, the amounts of the prepared raw materials are 8-12g/L of tryptone and 3-7g/L, NaCl 8-12g/L of yeast powder respectively; in the step S2, the final volume of 1L is taken as a standard, and the amounts of the prepared raw materials are respectively: 4.5-5.0g of N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, 2.0-2.5g of sodium lactate, 0.4-0.5g of sodium chloride, 0.2-0.3g of ammonium sulfate, 0.01-0.04g of magnesium sulfate heptahydrate and 2-7mL of microelement stock solution; the concentration of the NaOH solution for adjusting the pH is 0.05-0.2 mol/L.
Preferably, in the step S1, the prepared raw materials respectively have the amount of tryptone 10g/L and yeast powder 5g/L, NaCl 10 g/L.
Preferably, in the step S2, the use amounts of the prepared raw materials are respectively, with the final volume of 1L as a standard: 4.766g of N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, 2.242g of sodium lactate, 0.46g of sodium chloride, 0.255g of ammonium sulfate, 0.024g of magnesium sulfate heptahydrate and 5mL of microelement stock solution; the concentration of the NaOH solution for adjusting the pH is 0.1 mol/L.
Preferably, in the preparation process of the trace element stock solution in the step S2, the amounts of the added raw materials are as follows: 1.5g of nitrilotriacetic acid, 3.0g of magnesium sulfate, 1.0g of calcium chloride dihydrate, 1.0g of sodium chloride, 0.5g of manganese sulfate, 0.18g of zinc sulfate heptahydrate, 0.1g of ferrous sulfate heptahydrate, 0.18g of cobalt sulfate heptahydrate, 0.025g of nickel chloride hexahydrate, 0.02g of aluminum potassium sulfate dodecahydrate, 0.01g of copper sulfate pentahydrate, 0.01g of boric acid, 0.01g of sodium molybdate dihydrate and 0.3mg of sodium selenite pentahydrate.
Preferably, in the preparation process of the mother liquor in the step S5, the amounts of the raw materials added are as follows: 25mL of anaerobic culture medium, 600mg of TNTs 400-.
Preferably, in the step S4, the method for synthesizing titanium dioxide nanotubes (TNTs) specifically comprises: adding 1-3g of titanium dioxide powder into 50-200mL of 7-12mol/L NaOH solution, magnetically stirring until the titanium dioxide powder is uniform, refluxing for 36-60h at the temperature of 110-135 ℃, diluting a reflux product with distilled water, performing suction filtration, dispersing into 0.05-0.2mol/L diluted HCl solution, stirring overnight, washing with ultrapure water to be neutral, drying at constant temperature, calcining the solid at the temperature of 400-550 ℃ for 40-80min, naturally cooling to room temperature, and grinding into powder by using an agate mortar for later use.
Preferably, the titanium dioxide powder has a specification of P25 and a purity of greater than 99%.
Preferably, in the step S6, the preparation process of the silver sulfide nanoparticle-supported titanium dioxide nanotube-based composite material specifically includes: injecting the mixed solution B into a serum bottle filled with an anaerobic culture medium by using a sterile syringe, and then injecting a certain amount of S.oniedensis MR-1 bacterial solution into the serum bottle to ensure that the concentration of the bacterial cells in the reaction system is 5 multiplied by 106-8×106CFU·mL-1Then culturing the serum bottle in a shaker at 26-35 ℃ and 180rpm under 120-180-2S/TNTs) nanotube-based composite materialAnd (5) feeding.
The invention has the beneficial effects that:
the invention relates to a method for preparing a titanium dioxide tube-based composite material by a biological method, which adopts a microorganism S.oneidensis MR-1 taken from the environment as a biological reducing agent, avoids the addition of chemical reagents, does not consume any energy, and takes the S.oneidensis MR-1 as a reducing agent and a template agent to synthesize Ag2S NPs on the wall of a TNTs tube in situ so as to form Ag in one step2The method is economical, effective, low-carbon and environment-friendly. At the same time, Ag in the method2S NPs are uniformly distributed on the outer tube wall of the TNTs and are used for catalyzing and reducing organic pollutant p-nitrophenol (4-NP) which is difficult to degrade and has biotoxicity in the environment, and the result shows that the catalytic efficiency of the composite material is far higher than that of a single material, and the catalytic efficiency is up to 98.3% within 50 min.
Drawings
FIG. 1: ag prepared by the invention2XRD patterns of S/TNTs and TNTs;
FIG. 2: ag prepared by the invention2TEM images of S/TNTs and TNTs;
FIG. 3: ag prepared by the invention2TEM image and particle size distribution histogram of S NPs;
FIG. 4: ag prepared by the invention2HEMEM plots of S/TNTs;
FIG. 5: ag prepared by the invention2EDX patterns of S/TNTs;
FIG. 6: synthesizing Ag with different Ag/Ti molar ratios in the precursor2And (3) a degradation curve diagram of catalytic degradation of 4-NP by the S/TNTs nano composite material.
Detailed Description
To facilitate understanding of those skilled in the art, the present invention will be further described with reference to specific examples.
Example 1:
a method for preparing a titanium dioxide tube-based composite material by a biological method comprises the following steps:
s1, preparing an LB culture medium: weighing a certain amount of tryptone, yeast powder and NaCl by taking 10g/L of tryptone and 5g/L, NaCl 10g/L of yeast powder as standards, adding into deionized water, uniformly mixing, subpackaging, sealing, sterilizing at high temperature and high pressure, cooling, and storing for later use.
S2, preparing an anaerobic culture medium: weighing 4.766g of N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, 2.242g of sodium lactate, 0.46g of sodium chloride, 0.255g of ammonium sulfate, 0.024g of magnesium sulfate heptahydrate, 5mL of trace element stock solution and 950mL of ultrapure water, uniformly mixing, adjusting the pH to 7.0 by using 0.1mol/L NaOH solution, fixing the volume to 1L, subpackaging in serum bottles, filling nitrogen for 5min to completely discharge dissolved oxygen in the bottles, sealing by using a butyl rubber plug, covering, sterilizing at high temperature and high pressure, and storing for later use;
the preparation method of the microelement stock solution comprises the following steps: taking 1.5g nitrilotriacetic acid, using ultrapure water to fix the volume to 500mL, then using potassium hydroxide solution to adjust the pH value to 6.5, then adding 3.0g magnesium sulfate, 1.0g calcium chloride dihydrate, 1.0g sodium chloride, 0.5g manganese sulfate, 0.18g zinc sulfate heptahydrate, 0.1g ferrous sulfate heptahydrate, 0.18g cobalt sulfate heptahydrate, 0.025g nickel chloride hexahydrate, 0.02g aluminum potassium sulfate dodecahydrate, 0.01g copper sulfate pentahydrate, 0.01g boric acid, 0.01g sodium molybdate dihydrate and 0.3mg sodium selenite pentahydrate, stirring and dissolving, using ultrapure water to fix the volume to 1000mL, and placing in a refrigerator at 4 ℃ for storage.
S3, inoculation and culture of MR-1 strain: the S.oniedensis MR-1 strain is firstly inoculated into an LB culture medium for culture, the cultured bacterium liquid is centrifuged for 5min under the condition of 6000rpm, the supernatant fluid is discarded, and the thallus at the bottom is resuspended by using a sterilized anaerobic culture medium for later use.
S4, synthetic titanium dioxide nanotubes (TNTs): adding 2g of titanium dioxide powder (specification is P25, the purity is more than 99%) into 100mL of 10mol/L NaOH solution, magnetically stirring until the titanium dioxide powder is uniform, refluxing for 48h at 120 ℃, diluting a reflux product with distilled water, performing suction filtration, dispersing into 0.1mol/L diluted HCl solution, stirring overnight, washing with ultrapure water until the solution is neutral, drying at constant temperature, calcining the solid at 450 ℃ for 60min, naturally cooling to room temperature, and grinding into powder with an agate mortar for later use.
S5, preparation of mother liquor: dissolving a surfactant sodium dodecyl benzene sulfonate in 25mL of anaerobic culture medium to prepare a1 wt% sodium dodecyl benzene sulfonate solution, adding 500mg of TNTs and 300mg of polyvinylpyrrolidone into the solution, stirring uniformly to obtain a mixed solution A, then adding 106mg of silver nitrate and 155mg of sodium thiosulfate pentahydrate, dissolving, performing ultrasonic treatment for 10min, and performing magnetic stirring for 3h to obtain a mixed solution B.
S6, preparing a silver sulfide nanoparticle-loaded titanium dioxide nanotube-based composite material: injecting the mixed solution B into a serum bottle filled with an anaerobic culture medium by using a sterile syringe, and then injecting a certain amount of S.oniedensis MR-1 bacterial solution into the serum bottle to ensure that the concentration of the bacterial cells in the reaction system is 6.5 multiplied by 106CFU·mL-1Then culturing the serum bottle in a shaker at 30 ℃ and 150rpm for 48h, centrifuging the reacted system for 20min under the condition of 5000rpm to remove thalli in the solution, discarding the upper layer liquid, respectively adding a proper amount of ultrapure water and absolute ethyl alcohol, shaking uniformly, centrifuging at 10000rpm for 20min, repeatedly washing for several times to obtain a reaction product, and finally drying the reaction product at 60 ℃ for 12h to obtain the silver sulfide nanoparticle-loaded titanium dioxide (Ag)2S/TNTs) nanotube-based composite material.
Example 2:
the preparation method of the titanium dioxide tube-based composite material by the biological method is the same as the step of the embodiment 1, and the difference is that:
in the step S1, the amounts of the prepared raw materials are 8g/L tryptone and 7g/L, NaCl 8g/L yeast powder.
In the step S2, with the final volume of 1L as a standard, the amounts of the prepared raw materials are: 4.5g of N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, 2.5g of sodium lactate, 0.4g of sodium chloride, 0.3g of ammonium sulfate, 0.04g of magnesium sulfate heptahydrate, 2mL of trace element stock solution and 950mL of ultrapure water; wherein the concentration of NaOH solution for adjusting pH is 0.05 mol/L; when the microelement stock solution is prepared, the dosage of each added raw material is as follows: 1.0g of nitrilotriacetic acid, 2.0g of magnesium sulfate, 0.5g of calcium chloride dihydrate, 1.5g of sodium chloride, 0.3g of manganese sulfate, 0.01g of zinc sulfate heptahydrate, 0.15g of ferrous sulfate heptahydrate, 0.03g of cobalt sulfate heptahydrate, 0.01g of nickel chloride hexahydrate, 0.03g of aluminum potassium sulfate dodecahydrate, 0.005g of copper sulfate pentahydrate, 0.005g of boric acid, 0.015g of sodium molybdate dihydrate and 0.1mg of sodium selenite pentahydrate.
In step S3, centrifugation was performed at 5000rpm for 8min during centrifugation of the bacterial suspension.
In step S4, 1g of titanium dioxide powder is added into 200mL of 7mol/L NaOH solution, refluxed for 36h at 135 ℃, dispersed into 0.2mol/L diluted HCl solution, stirred overnight, and calcined at 550 ℃ for 40 min.
In the step S5, dissolving a surfactant sodium dodecyl benzene sulfonate in 25mL of anaerobic culture medium to prepare a 0.5 wt% sodium dodecylbenzenesulfonate solution, adding 400mg of TNTs and 350mg of polyvinylpyrrolidone into the solution, stirring uniformly to obtain a mixed solution A, then adding 120mg of silver nitrate and 170mg of sodium thiosulfate pentahydrate, performing ultrasonic treatment for 5min after dissolution, and performing magnetic stirring for 4h to obtain a mixed solution B.
In step S6, the MR-1 bacterial suspension was injected into the serum bottle so that the concentration of the bacterial cells in the reaction system was 5X 106CFU·mL-1Culturing in shaking table at 26 deg.C and 180rpm for 60h, centrifuging at 4200rpm for 25min to remove thallus, centrifuging at 12000rpm for 15min to obtain reaction product, and drying at 50 deg.C for 15h to obtain titanium dioxide (Ag) loaded on silver sulfide nanoparticles2S/TNTs) nanotube-based composite material.
Example 3:
a method for preparing a titanium dioxide tube-based composite material by a biological method, which comprises the same steps as example 1, except that:
in the step S1, the amounts of the prepared raw materials are tryptone 12g/L and yeast powder 3g/L, NaCl 12g/L, respectively.
In the step S2, with the final volume of 1L as a standard, the amounts of the prepared raw materials are: 5.0g of N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, 2.0g of sodium lactate, 0.5g of sodium chloride, 0.2g of ammonium sulfate, 0.01g of magnesium sulfate heptahydrate, 7mL of trace element stock solution and 950mL of ultrapure water; wherein the concentration of NaOH solution for adjusting pH is 0.2 mol/L; when the microelement stock solution is prepared, the dosage of each added raw material is as follows: 2.0g of nitrilotriacetic acid, 3.0g of magnesium sulfate, 1.5g of calcium chloride dihydrate, 0.5g of sodium chloride, 0.7g of manganese sulfate, 0.03g of zinc sulfate heptahydrate, 0.05g of ferrous sulfate heptahydrate, 0.01g of cobalt sulfate heptahydrate, 0.04g of nickel chloride hexahydrate, 0.01g of aluminum potassium sulfate dodecahydrate, 0.015g of copper sulfate pentahydrate, 0.015g of boric acid, 0.005g of sodium molybdate dihydrate and 0.5mg of sodium selenite pentahydrate.
In step S3, centrifugation was performed at 7000rpm for 2min during centrifugation of the bacterial suspension.
In step S4, 3g of titanium dioxide powder was added to 50mL of 12mol/L NaOH solution, refluxed at 110 ℃ for 60 hours, dispersed in 0.05mol/L diluted HCl solution, stirred overnight, and calcined at 400 ℃ for 80 min.
In the step S5, dissolving a surfactant sodium dodecyl benzene sulfonate in 25mL of anaerobic culture medium to prepare a2 wt% sodium dodecyl benzene sulfonate solution, adding 600mg of TNTs and 400mg of polyvinylpyrrolidone into the solution, stirring uniformly to obtain a mixed solution A, then adding 90mg of silver nitrate and 140mg of sodium thiosulfate pentahydrate, performing ultrasonic treatment for 15min after dissolution, and performing magnetic stirring for 2h to obtain a mixed solution B.
In step S6, the MR-1 bacterial suspension was injected into the serum bottle so that the concentration of the bacterial cells in the reaction system was 8X 106CFU·mL-1Culturing in a shaker at 35 deg.C and 120rpm for 40h, centrifuging at 5800rpm for 15min to remove thallus, centrifuging at 8000rpm for 30min to obtain reaction product, and drying at 70 deg.C for 8h to obtain titanium dioxide (Ag) loaded on silver sulfide nanoparticles2S/TNTs) nanotube-based composite material.
The method for preparing the titanium dioxide tube-based composite material by the biological method of the invention is explained with reference to fig. 1-6.
FIG. 1 shows Ag prepared by the present invention2XRD patterns of S/TNTs and TNTs. As can be seen from fig. 1, the diffraction peaks at 2 θ of 25.2 °, 37.8 °, 48.0 °, 53.8 °, 55.0 °, 62.6 °, and 75.0 ° correspond to anatase phase TiO, respectively2The (101), (004), (200), (105), (211), (204), (215) crystal face (PDF #21-1272) of (1), and no other impurity peaks, which indicates that the purity of the TNTs is higher; in Ag2The XRD pattern of the S/TNTs composite material does not obviously show Ag2The diffraction peak of S, which is probably a small (< 8nm) particle of silver sulfide without a signal to induce XRD,however, careful observation can notice that the peak after recombination is closer to 37.8 degrees than TiO2Slightly higher, which corresponds to Ag2The (-103) crystal plane of S, which is mainly associated with TiO2(004) Resulting from the overlap of crystal planes.
FIG. 2 shows Ag prepared by the present invention2Transmission Electron Microscopy (TEM) images of the S/TNTs and the TNTs clearly show that the tube diameter of the TNTs is about 10nm (FIG. A1); ag prepared by adopting the biological method of the invention2The S NPs were more uniformly dispersed on the surface of TNTs and no significant aggregation was observed (FIG. A2). Anionic surfactant sodium dodecyl benzene sulfonate, Ag+S initially adsorbed on the surface of TNTs and free in solution2O3 2-Ions are gradually reduced to S in the periplasm of S.oneidensis MR-12-Then slowly released and attached to Ag on the tube wall+Reaction to form Ag2And (S) NPs. This slow release process is useful for biosynthesis of Ag2The process of S NPs has a regulating effect.
FIG. 3 shows Ag prepared by the present invention2TEM image and particle size distribution histogram of S NPs. As can be seen from the figure, biologically synthesized Ag2The S NPs are uniformly dispersed, and the particle size distribution range is narrow (figure B1); by analyzing the particle size, the particle size distribution range is 3-8nm, mainly 4-6nm, which shows that the synthesis method is uniform, stable and uniform in size.
FIG. 4 shows Ag prepared by the present invention2HEMEM images of S/TNTs. As can be seen from the figure, the crystal lattice stripes of the anatase TNTs (101) and the 024 crystal plane (d is 0.34nm) and the Ag marked on the figure are clearly seen from the figure, which shows that the composite material has better crystallinity, and the crystal lattices marked on the figure correspond to the crystal planes of the anatase TNTs (101) (d is 0.14nm), the anatase TNTs (024) (d is 0.34nm) and the Ag respectively2The S (-103) crystal plane (d ═ 0.21 nm). Ag of uniform size2S NPs are loaded on the surface of TNTs to form a better heterojunction, and a good interface is favorable for electron transfer, so that the catalytic activity of the composite material is promoted.
FIG. 5 shows Ag prepared according to the present invention2Elemental analysis results for S/TNTs (EDX chart). As can be seen from the figure, Ti, O, Ag, and Cu are contained in the composite material,S and Cu, wherein Ti and O are from TNTs, and Ag and S are biologically synthesized Ag2And (3) S nanoparticles. The peak of the Cu element is caused by a copper net for placing a sample, and no other impurity peak indicates that the synthesized composite material has higher purity.
As shown in FIG. 6, Ag is synthesized by different Ag/Ti molar ratios in the precursor2And (3) a degradation curve diagram of catalytic degradation of 4-NP by the S/TNTs nano composite material. As can be seen from the figure, the reaction conditions: [4-NP]＝0.12mmol/L，[NaBH4](5 mmol/L) [ catalyst]0.4 g/L. The reaction is carried out under the anaerobic condition, and the result shows that when the molar ratio of Ag to Ti in the precursor is 1:10, the catalytic efficiency of the composite material is the highest, and within 50min, the degradation efficiency of the composite material on 4-NP is 98.3%. Under the same reaction conditions, Ag2Both increases and decreases in S loading reduce the catalytic performance of the composite for 4-NP.
The invention relates to a method for preparing a titanium dioxide tube-based composite material by a biological method, which adopts a microorganism S.oneidensis MR-1 taken from the environment as a biological reducing agent, avoids the addition of chemical reagents, does not consume any energy, and takes the S.oneidensis MR-1 as a reducing agent and a template agent to synthesize Ag in situ on the wall of a TNTs tube2S NPs to form Ag in one step2The method is economical, effective, low-carbon and environment-friendly. Also, Ag in the method of the present invention2S NPs are uniformly distributed on the outer tube wall of the TNTs and are used for catalyzing and reducing organic pollutant p-nitrophenol (4-NP) which is difficult to degrade and has biotoxicity in the environment, and the result shows that the catalytic efficiency of the composite material is far higher than that of a single material, and the catalytic efficiency is up to 98.3% within 50 min.
The invention has been described above with reference to the accompanying drawings, it is obvious that the invention is not limited to the specific implementation in the above-described manner, and it is within the scope of the invention to adopt such insubstantial modifications of the inventive concept and solution, or to apply the inventive concept and solution directly to other applications without such modifications.
Claims (9)
1. A method for preparing a titanium dioxide tube-based composite material by a biological method is characterized by comprising the following steps:
s1, preparing an LB culture medium: weighing a certain amount of tryptone, yeast powder and NaCl, adding into deionized water, mixing, subpackaging, sealing, sterilizing at high temperature under high pressure, cooling, and storing for later use;
s2, preparing an anaerobic culture medium: weighing a certain amount of N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, sodium lactate, sodium chloride, ammonium sulfate, magnesium sulfate heptahydrate, trace element stock solution and pure water, mixing uniformly, adjusting pH to 7.0 with NaOH solution, fixing volume, subpackaging in serum bottles, charging nitrogen for 5min to completely remove dissolved oxygen in the bottles, sealing with butyl rubber plugs, capping, sterilizing at high temperature and high pressure, and storing for later use; the preparation method of the microelement stock solution comprises the following steps: taking 1.0-2.0g of nitrilotriacetic acid, fixing the volume to 500mL by using ultrapure water, adjusting the pH value to 6.5 by using a potassium hydroxide solution, then adding 2.0-3.0g of magnesium sulfate, 0.5-1.5g of calcium chloride dihydrate, 0.5-1.5g of sodium chloride, 0.3-0.7g of manganese sulfate, 0.01-0.03g of zinc sulfate heptahydrate, 0.05-0.15g of ferrous sulfate heptahydrate, 0.01-0.03g of cobalt sulfate heptahydrate, 0.01-0.04g of nickel chloride hexahydrate, 0.01-0.03g of aluminum potassium sulfate dodecahydrate, 0.005-0.015g of copper sulfate pentahydrate, 0.005-0.015g of boric acid, 0.005-0.015g of sodium molybdate dihydrate, and 0.1-0.5mg of sodium selenite pentahydrate, stirring and dissolving by using the ultrapure water to 1000mL, and placing the mixture in a refrigerator with the constant volume to be preserved at 4 ℃;
s3, inoculation and culture of MR-1 strain: firstly, the method is carried outS.oniedensisInoculating the MR-1 strain into an LB culture medium for culture, centrifuging the cultured bacterial liquid at 5000-7000rpm for 2-8min, discarding the supernatant, and resuspending the bottom thallus with a sterilized anaerobic culture medium for later use;
s4, synthetic titanium dioxide nanotubes (TNTs): adding a certain amount of titanium dioxide powder into a NaOH solution, magnetically stirring until the titanium dioxide powder is uniform, refluxing, diluting with distilled water, performing suction filtration, dispersing into a dilute hydrochloric acid solution, stirring overnight, washing with ultrapure water to be neutral, drying at constant temperature, calcining the solid, naturally cooling to room temperature, and grinding into powder by using an agate mortar for later use;
s5, preparation of mother liquor: dissolving a surfactant sodium dodecyl benzene sulfonate in an anaerobic culture medium to prepare a 0.5-2 wt% sodium dodecylbenzenesulfonate solution, adding a certain amount of TNTs and excessive polyvinylpyrrolidone into the solution, stirring uniformly to obtain a mixed solution A, then adding a certain amount of silver nitrate and sodium thiosulfate pentahydrate, dissolving, performing ultrasonic treatment for 5-15min, and performing magnetic stirring for 2-4h to obtain a mixed solution B;
s6, preparing a titanium dioxide nanotube-based composite material: injecting the mixed solution B into a serum bottle filled with an anaerobic culture medium by using a sterile injector, injecting a certain amount of MR-1 bacterial solution, then carrying out shake culture on the serum bottle containing the MR-1 bacterial solution for a period of time, preliminarily centrifuging the reacted system to remove thalli in the solution, then respectively washing the system for a plurality of times by using ultrapure water and absolute ethyl alcohol, centrifuging the system again to obtain a reaction product, and finally drying the reaction product to obtain the silver sulfide nanoparticle-loaded titanium dioxide (Ag)2S/TNTs) nanotube-based composite material.
2. The method of claim 1, wherein the titanium dioxide tube-based composite material is prepared by a biological method,
in the step S1, the prepared raw materials respectively account for 8-12g/L of tryptone and 3-7g/L, NaCl 8-12g/L of yeast powder;
in the step S2, the final volume of 1L is taken as a standard, and the amounts of the prepared raw materials are respectively: 4.5-5.0g of N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, 2.0-2.5g of sodium lactate, 0.4-0.5g of sodium chloride, 0.2-0.3g of ammonium sulfate, 0.01-0.04g of magnesium sulfate heptahydrate, 2-7mL of microelement stock solution and 950mL of pure water; the concentration of the NaOH solution for adjusting the pH is 0.05-0.2 mol/L.
3. The method for biologically preparing the titanium dioxide tube-based composite material according to claim 1 or 2, wherein the raw materials prepared in the step S1 are tryptone 10g/L and yeast powder 5g/L, NaCl 10 g/L.
4. The method for preparing the titanium dioxide tube-based composite material according to the claim 1 or 2, wherein in the step S2, the final volume of 1L is taken as a standard, and the amounts of the prepared raw materials are respectively as follows: 4.766g of N- (2-hydroxyethyl) piperazine-N' -2-ethanesulfonic acid, 2.242g of sodium lactate, 0.46g of sodium chloride, 0.255g of ammonium sulfate, 0.024g of magnesium sulfate heptahydrate and 5mL of microelement stock solution; the concentration of the NaOH solution for adjusting the pH is 0.1 mol/L.
5. The method for preparing the titanium dioxide tube-based composite material according to the claim 1, wherein the amounts of the raw materials added in the preparation process of the trace element stock solution in the step S2 are respectively as follows: 1.5g of nitrilotriacetic acid, 3.0g of magnesium sulfate, 1.0g of calcium chloride dihydrate, 1.0g of sodium chloride, 0.5g of manganese sulfate, 0.18g of zinc sulfate heptahydrate, 0.1g of ferrous sulfate heptahydrate, 0.18g of cobalt sulfate heptahydrate, 0.025g of nickel chloride hexahydrate, 0.02g of aluminum potassium sulfate dodecahydrate, 0.01g of copper sulfate pentahydrate, 0.01g of boric acid, 0.01g of sodium molybdate dihydrate and 0.3mg of sodium selenite pentahydrate.
6. The method for preparing the titanium dioxide tube-based composite material according to the claim 1, wherein the amount of each raw material added in the preparation process of the mother liquor in the step S5 is as follows: 25mL of anaerobic culture medium, 600mg of TNTs 400-.
7. The method for preparing the titanium dioxide tube-based composite material according to the claim 1, wherein in the step of S4, the method for synthesizing the titanium dioxide nanotubes (TNTs) is specifically as follows: adding 1-3g of titanium dioxide powder into 50-200mL of 7-12mol/L NaOH solution, magnetically stirring until the titanium dioxide powder is uniform, refluxing for 36-60h at the temperature of 110-135 ℃, diluting a reflux product with distilled water, performing suction filtration, dispersing into 0.05-0.2mol/L diluted HCl solution, stirring overnight, washing with ultrapure water to be neutral, drying at constant temperature, calcining the solid at the temperature of 400-550 ℃ for 40-80min, naturally cooling to room temperature, and grinding into powder by using an agate mortar for later use.
8. The method of claim 1 or 6, wherein the titanium dioxide powder has a specification of P25 and a purity of greater than 99%.
9. The method for preparing the titanium dioxide tube-based composite material according to the claim 1, wherein in the step S6, the preparation process of the titanium dioxide tube-based composite material loaded with the silver sulfide nanoparticles comprises: injecting the mixed solution B into a serum bottle filled with an anaerobic culture medium by using a sterile syringe, and then injecting a certain amount of the mixed solution B into the serum bottleS.oniedensisMR-1 bacterial liquid with the concentration of the bacterial cells in the reaction system of 5X 106-8×106CFU·mL-1Then culturing the serum bottle in a shaker at 26-35 ℃ and 180rpm under 120-180-2S/TNTs) nanotube-based composite material.
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