CN108588130B - A method for preparing titanium dioxide tube-based composite material by biological method - Google Patents

A method for preparing titanium dioxide tube-based composite material by biological method Download PDF

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CN108588130B
CN108588130B CN201810259030.2A CN201810259030A CN108588130B CN 108588130 B CN108588130 B CN 108588130B CN 201810259030 A CN201810259030 A CN 201810259030A CN 108588130 B CN108588130 B CN 108588130B
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石先阳
杨迷
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Abstract

本发明公开了一种生物法制备二氧化钛管基复合材料的方法，经LB培养基配制、厌氧培养基配制、MR‑1菌种的接种和培养、二氧化钛纳米管(TNTs)合成、母液的配制、二氧化钛纳米管基复合材料的制备等步骤，以取自环境中的微生物Shewanella oneidensis MR‑1为生物还原剂和模板剂，在TNTs管壁上原位合成Ag2S NPs，从而一步形成Ag2S/TNTs纳米管基复合材料，本方法不仅经济有效且低碳环保，避免了化学试剂的添加，而且不消耗任何能源，同时本方法生产的Ag2S/TNTs纳米管基复合材料，用于催化还原环境难降解具有生物毒性的有机污染物对硝基苯酚，催化效率高。

Figure 201810259030

The invention discloses a method for preparing a titanium dioxide tube-based composite material by a biological method. , the preparation of titanium dioxide nanotube-based composite materials and other steps, using the microorganism Shewanella oneidensis MR-1 taken from the environment as a biological reducing agent and a template agent, in-situ synthesis of Ag 2 S NPs on the TNTs tube wall, thereby forming Ag 2 in one step. S/TNTs nanotube-based composite material, the method is not only economical, effective, low-carbon and environmentally friendly, avoids the addition of chemical reagents, and does not consume any energy, and the Ag 2 S/TNTs nanotube-based composite material produced by this method is used for The catalytic reduction environment is difficult to degrade the biologically toxic organic pollutant p-nitrophenol, and the catalytic efficiency is high.

Figure 201810259030

Description

Method for preparing titanium dioxide tube-based composite material by biological method
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)

1.一种生物法制备二氧化钛管基复合材料的方法，其特征在于，包括如下步骤：1. a method for preparing titanium dioxide tube-based composite material by biological method, is characterized in that, comprises the steps: S1、配制LB培养基：称取一定量的胰蛋白胨、酵母粉、NaCl，加入去离子水中，混匀，分装密封，高温高压灭菌冷却后保存，备用；S1. Preparation of LB medium: Weigh a certain amount of tryptone, yeast powder, and NaCl, add it into deionized water, mix well, package and seal, sterilize under high temperature and autoclave, and store it for later use; S2、配制厌氧培养基：称取一定量的N-（2-羟乙基）哌嗪-N'-2-乙烷磺酸、乳酸钠、氯化钠、硫酸铵、七水合硫酸镁、微量元素储备液、纯水，混匀，并用NaOH溶液调节pH至7.0，定容并分装于血清瓶中，充氮气5 min以排尽瓶内溶解氧，用丁基橡胶塞密封，加盖，高温高压灭菌后保存备用；所述微量元素储备液配制方法为：取1.0-2.0 g次氮基三乙酸，用超纯水定容至500 mL，再用氢氧化钾溶液调节pH值至6.5，然后加入硫酸镁2.0-3.0 g、二水氯化钙0.5-1.5 g、氯化钠0.5-1.5 g、硫酸锰0.3-0.7 g、七水硫酸锌0.01-0.03g、七水硫酸亚铁0.05-0.15 g、七水硫酸钴0.01-0.03 g、六水氯化镍0.01-0.04 g、十二水合硫酸铝钾0.01-0.03 g、五水硫酸铜0.005-0.015 g、硼酸0.005-0.015 g、二水钼酸钠0.005-0.015 g、五水亚硒酸钠0.1-0.5 mg，搅拌溶解后用超纯水定容至1000 mL，放置在4℃冰箱中保存；S2. Preparation of anaerobic medium: Weigh 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, mix well, adjust the pH to 7.0 with NaOH solution, dilute to volume and dispense into serum bottles, fill with nitrogen for 5 min to drain the dissolved oxygen in the bottle, seal with butyl rubber stopper, and cap, After high temperature and high pressure sterilization, save it for later use; the preparation method of the trace element stock solution is as follows: take 1.0-2.0 g of nitrilotriacetic acid, dilute the volume to 500 mL with ultrapure water, and then adjust the pH value to 6.5 with potassium hydroxide solution , then add magnesium sulfate 2.0-3.0 g, calcium chloride dihydrate 0.5-1.5 g, sodium chloride 0.5-1.5 g, manganese sulfate 0.3-0.7 g, zinc sulfate heptahydrate 0.01-0.03 g, ferrous sulfate heptahydrate 0.05 g -0.15 g, cobalt sulfate heptahydrate 0.01-0.03 g, nickel chloride hexahydrate 0.01-0.04 g, aluminum potassium sulfate dodecahydrate 0.01-0.03 g, copper sulfate pentahydrate 0.005-0.015 g, boric acid 0.005-0.015 g, Sodium hydromolybdate 0.005-0.015 g, sodium selenite pentahydrate 0.1-0.5 mg, stir and dissolve, dilute to 1000 mL with ultrapure water, and store in a refrigerator at 4°C; S3、MR-1菌种的接种和培养：先将S.oniedensis MR-1菌株接种到LB培养基中培养，将培养后的菌液5000-7000 rpm条件下离心2-8 min，弃去上清液，并用灭菌后的厌氧培养基将底部的菌体重悬，备用；S3. Inoculation and culture of MR-1 strains: First inoculate S. oniedensis MR-1 strains into LB medium for culture, centrifuge the cultured strains at 5000-7000 rpm for 2-8 min, discard the clear liquid, and resuspend the bacteria at the bottom with the sterilized anaerobic medium for later use; S4、合成二氧化钛纳米管（TNTs）：取一定量的二氧化钛粉末加入到NaOH溶液中，磁力搅拌至均匀，经回流后，用蒸馏水稀释后抽滤，然后分散到稀盐酸溶液中搅拌过夜，再用超纯水洗涤至中性，恒温烘干处理后，将固体煅烧后自然冷却至室温，用玛瑙研钵成粉末，备用；S4. Synthesis of titanium dioxide nanotubes (TNTs): add a certain amount of titanium dioxide powder to NaOH solution, stir magnetically until uniform, after reflux, dilute with distilled water, filter with suction, then disperse into dilute hydrochloric acid solution and stir overnight, and then use Wash with ultrapure water to neutrality, dry at constant temperature, calcine the solid, cool it to room temperature naturally, and use an agate mortar to form powder for use; S5、母液的配制：将表面活性剂十二烷基苯磺酸钠溶解于厌氧培养基中，配制成0.5-2wt%的十二氨基苯磺酸钠溶液，向溶液中加入一定量的TNTs、和过量的聚乙烯吡咯烷酮，搅拌至均匀得到混合液A，然后加入一定量的硝酸银和五水合硫代硫酸钠，溶解后先超声5-15min后磁力搅拌2-4 h得到混合液B；S5. Preparation of mother liquor: Dissolve the surfactant sodium dodecylbenzenesulfonate in the anaerobic medium, prepare a 0.5-2wt% sodium dodecylbenzenesulfonate solution, and add a certain amount of TNTs to the solution , and excess polyvinylpyrrolidone, stir until uniform to obtain mixed solution A, then add a certain amount of silver nitrate and sodium thiosulfate pentahydrate, after dissolving, ultrasonically sonicate for 5-15 min and then magnetically stir for 2-4 h to obtain mixed solution B; S6、二氧化钛纳米管基复合材料的制备：将混合液B用无菌注射器注入到装有厌氧培养基的血清瓶中，并注入一定量的MR-1菌液，然后将含MR-1菌液的血清瓶进行摇床培养一段时间，再将反应后的体系初步离心去除溶液中的菌体，然后分别用超纯水和无水乙醇清洗数次，并再次离心获得反应产物，最后将反应产物干燥可得到硫化银纳米颗粒负载二氧化钛（Ag2S/TNTs）纳米管基复合材料。S6. Preparation of titanium dioxide nanotube-based composite material: inject the mixture B into the serum bottle containing anaerobic medium with a sterile syringe, and inject a certain amount of MR-1 bacterial solution, and then inject the mixture containing MR-1 bacteria The serum bottle of the solution was shaken for a period of time, and then the reaction system was initially centrifuged to remove the bacteria in the solution, then washed several times with ultrapure water and absolute ethanol, and centrifuged again to obtain the reaction product. The product was dried to obtain silver sulfide nanoparticle-supported titanium dioxide (Ag 2 S/TNTs) nanotube-based composites. 2.根据权利要求 1 所述的一种生物法制备二氧化钛管基复合材料的方法，其特征在于，2. The method for preparing a titanium dioxide tube-based composite material by a biological method according to claim 1, wherein, 所述S1步骤中，配制的各原料的量分别为胰蛋白胨8-12 g/L、酵母粉3-7 g/L、NaCl 8-12 g/L；In the step S1, the amount of each raw material prepared is 8-12 g/L of tryptone, 3-7 g/L of yeast powder, and 8-12 g/L of NaCl; 所述S2步骤中，以最后定容1L为标准，配制的各原料用量分别为：N-（2-羟乙基）哌嗪-N'-2-乙烷磺酸4.5-5.0 g、乳酸钠2.0-2.5 g、氯化钠0.4-0.5 g、硫酸铵0.2-0.3 g、七水合硫酸镁0.01-0.04 g、微量元素储备液2-7 mL、纯水950 mL；所述调节pH用的NaOH溶液浓度为0.05-0.2 mol/L。In the step S2, taking the final volume of 1L as the standard, the dosages of the prepared raw materials are: N-(2-hydroxyethyl)piperazine-N'-2-ethanesulfonic acid 4.5-5.0 g, sodium lactate 2.0 g -2.5 g, sodium chloride 0.4-0.5 g, ammonium sulfate 0.2-0.3 g, magnesium sulfate heptahydrate 0.01-0.04 g, trace element stock solution 2-7 mL, pure water 950 mL; the NaOH solution for pH adjustment The concentration is 0.05-0.2 mol/L. 3.根据权利要求 1或2所述的一种生物法制备二氧化钛管基复合材料的方法，其特征在于，所述S1步骤中，配制的各原料量分别为胰蛋白胨10 g/L、酵母粉5 g/L、NaCl 10 g/L。3. the method for preparing titanium dioxide tube-based composite material by a kind of biological method according to claim 1 and 2, is characterized in that, in described S1 step, each raw material amount of preparation is respectively tryptone 10 g/L, yeast powder 5 g/L, NaCl 10 g/L. 4.根据权利要求 1或2所述的一种生物法制备二氧化钛管基复合材料的方法，其特征在于，所述S2步骤中，以最后定容1L为标准，配制的各原料用量分别为：N-（2-羟乙基）哌嗪-N'-2-乙烷磺酸4.766 g、乳酸钠2.242 g、氯化钠0.46 g、硫酸铵0.255 g、七水合硫酸镁0.024 g、微量元素储备液5 mL；所述调节pH用的NaOH溶液浓度为0.1 mol/L。4. the method for preparing titanium dioxide tube-based composite material by a kind of biological method according to claim 1 and 2, is characterized in that, in described S2 step, take final constant volume 1L as the standard, the consumption of each raw material prepared is respectively: N-(2-hydroxyethyl)piperazine-N'-2-ethanesulfonic acid 4.766 g, sodium lactate 2.242 g, sodium chloride 0.46 g, ammonium sulfate 0.255 g, magnesium sulfate heptahydrate 0.024 g, trace element stock solution 5 mL; the concentration of the NaOH solution used for pH adjustment is 0.1 mol/L. 5.根据权利要求 1所述的一种生物法制备二氧化钛管基复合材料的方法，其特征在于，所述S2步骤的微量元素储备液配制过程中，加入的各原料的量分别为：次氮基三乙酸1.5 g、硫酸镁3.0 g、二水氯化钙1.0 g、氯化钠1.0 g、硫酸锰0.5 g、七水硫酸锌0.18 g、七水硫酸亚铁0.1 g、七水硫酸钴0.18 g、六水氯化镍0.025 g、十二水合硫酸铝钾0.02 g、五水硫酸铜0.01 g、硼酸0.01 g、二水钼酸钠0.01 g、五水亚硒酸钠0.3 mg。5. The method for preparing a titanium dioxide tube-based composite material by a biological method according to claim 1, wherein in the preparation process of the trace element reserve solution in the step S2, the amount of each raw material added is respectively: nitrous oxide 1.5 g of triacetic acid, 3.0 g of magnesium sulfate, 1.0 g of calcium chloride dihydrate, 1.0 g of sodium chloride, 0.5 g of manganese sulfate, 0.18 g of zinc sulfate heptahydrate, 0.1 g of ferrous sulfate heptahydrate, 0.18 g of cobalt sulfate heptahydrate g, 0.025 g of nickel chloride hexahydrate, 0.02 g of potassium aluminum sulfate dodecahydrate, 0.01 g of copper sulfate pentahydrate, 0.01 g of boric acid, 0.01 g of sodium molybdate dihydrate, and 0.3 mg of sodium selenite pentahydrate. 6.根据权利要求 1 所述的一种生物法制备二氧化钛管基复合材料的方法，其特征在于，所述S5步骤母液的配制过程中，加入的各原料的量分别为：厌氧培养基25 mL、TNTs400-600 mg、聚乙烯吡咯烷酮不少于300 mg、硝酸银90-120mg、五水合硫代硫酸钠140-170mg。6. The method for preparing a titanium dioxide tube-based composite material by a biological method according to claim 1, wherein, in the preparation process of the mother liquor in the step S5, the amount of each raw material added is respectively: anaerobic medium 25 mL, TNTs 400-600 mg, polyvinylpyrrolidone not less than 300 mg, silver nitrate 90-120 mg, and sodium thiosulfate pentahydrate 140-170 mg. 7.根据权利要求 1 所述的一种生物法制备二氧化钛管基复合材料的方法，其特征在于，所述S4步骤中，二氧化钛纳米管（TNTs）合成方法具体为：取二氧化钛粉末1-3 g加入到50-200 mL、7-12 mol/L的NaOH溶液中，磁力搅拌至均匀，在110-135℃条件下回流36-60 h后，回流产物用蒸馏水稀释后抽滤，然后分散到0.05-0.2 mol/L的稀HCl溶液中搅拌过夜，再用超纯水洗涤至中性，恒温烘干处理后，将固体在400-550℃条件下煅烧40-80 min后自然冷却至室温，用玛瑙研钵成粉末，备用。7 . The method for preparing a titanium dioxide tube-based composite material by a biological method according to claim 1 , wherein in the step S4 , the method for synthesizing titanium dioxide nanotubes (TNTs) is as follows: 1-3 g of titanium dioxide powder is taken. 8 . Add it to 50-200 mL, 7-12 mol/L NaOH solution, stir magnetically until uniform, reflux at 110-135 °C for 36-60 h, dilute the reflux product with distilled water, filter with suction, and then disperse to 0.05 -0.2 mol/L dilute HCl solution was stirred overnight, then washed with ultrapure water until neutral, dried at constant temperature, calcined at 400-550 °C for 40-80 min, and cooled to room temperature naturally. Agate mortar into powder, set aside. 8.根据权利要求 1或6 所述的一种生物法制备二氧化钛管基复合材料的方法，其特征在于，所述二氧化钛粉末规格为P25，其纯度大于99%。8. The method for preparing a titanium dioxide tube-based composite material by a biological method according to claim 1 or 6, wherein the titanium dioxide powder specification is P25, and its purity is greater than 99%. 9.根据权利要求 1所述的一种生物法制备二氧化钛管基复合材料的方法，其特征在于，所述S6步骤中，硫化银纳米颗粒负载二氧化钛纳米管基复合材料的制备过程，具体为：将混合液B用无菌注射器注入到装有厌氧培养基的血清瓶中，然后向上述血清瓶中注入一定量S.oniedensis MR-1菌液，使菌体在反应体系中的浓度为5×106-8×106CFU·mL-1，然后将上述血清瓶在26-35℃、120-180 rpm的摇床中培养40-60 h，将反应后的体系先在4200-5800 rpm条件下离心15-25 min去除溶液中的菌体，然后分别用超纯水和无水乙醇清洗数次，并于8000-12000 rpm下离心15-30 min以获得反应产物，最后将反应产物在50-70℃下干燥8-15 h，可得到硫化银纳米颗粒负载二氧化钛（Ag2S/TNTs）纳米管基复合材料。9. The method for preparing a titanium dioxide tube-based composite material by a biological method according to claim 1, wherein in the step S6, the preparation process of the silver sulfide nanoparticle-loaded titanium dioxide nanotube-based composite material is specifically: The mixed solution B was injected into the serum bottle containing the anaerobic medium with a sterile syringe, and then a certain amount of S. oniedensis MR-1 bacterial solution was injected into the above-mentioned serum bottle, so that the concentration of the bacterial cells in the reaction system was 5 ×10 6 -8×10 6 CFU·mL -1 , then the above serum bottle was incubated at 26-35°C and 120-180 rpm in a shaker for 40-60 h, and the reaction system was first incubated at 4200-5800 rpm Centrifuge for 15-25 min under conditions to remove the bacteria in the solution, then wash with ultrapure water and absolute ethanol for several times, and centrifuge at 8000-12000 rpm for 15-30 min to obtain the reaction product, and finally put the reaction product in After drying at 50-70 °C for 8-15 h, silver sulfide nanoparticle-supported titanium dioxide (Ag 2 S/TNTs) nanotube-based composites can be obtained.
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