CN108404937B - Nanocomposite MoS2/Ag/TiO2Preparation method of NTs - Google Patents

Nanocomposite MoS2/Ag/TiO2Preparation method of NTs Download PDF

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CN108404937B
CN108404937B CN201810239525.9A CN201810239525A CN108404937B CN 108404937 B CN108404937 B CN 108404937B CN 201810239525 A CN201810239525 A CN 201810239525A CN 108404937 B CN108404937 B CN 108404937B
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nts
tio
mos
titanium mesh
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李婷婷
汪柱宏
刘超超
王鑫凯
唐春明
丁攻圣
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Nanchang Hangkong University
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Abstract

Nanocomposite MoS2/Ag/TiO2The preparation method of NTs adopts the principle that a titanium mesh is taken as a substrate, and a simple photoreduction method and a hydrothermal method are utilized to prepare the NTs on TiO2In-situ growth of integrated MoS on NTs/Ti net2/Ag/TiO2NTs. Under the irradiation of visible light (lambda is more than or equal to 420nm), 4cm2MoS on titanium mesh2/Ag/TiO2The NTs catalyst can basically degrade 100mL of 10mg/L tetracycline hydrochloride solution within 2 hours. The invention has the advantages that the composite material is prepared on a titanium mesh, the problem of catalyst immobilization is solved, the composite material is convenient and quick to use, convenient to recover and recycle, the catalytic activity is not easy to lose efficacy, the composite material can be connected with an external circuit, the separation efficiency of photoproduction electrons and holes is improved by applying bias voltage, and the catalytic efficiency is further improved.

Description

Nanocomposite materialMoS2/Ag/TiO2Preparation method of NTs
Technical Field
The invention belongs to the technical field of preparation of nano composite materials, and particularly relates to an in-situ growth MoS on a titanium mesh2/Ag/TiO2NTs method and photocatalytic degradation of antibiotic pollutant tetracycline hydrochloride.
Background
TiO, a widely studied nano-semiconductor photocatalyst2Has the advantages of no toxicity, low price, easy obtainment, high physical and chemical stability, high photocatalytic activity and the like, and draws the attention of a plurality of researchers in the environmental field. Wherein, TiO grown on the titanium sheet by using an anodic oxidation method2Nanotube (TiO)2nanotubes, TiO for short2NTs) have the advantages of large specific surface area, vertical charge transfer, stability against photo-and chemical attack. However, TiO2 NTs has a forbidden band width of 3.2 eV, can only absorb ultraviolet light in sunlight, and its high photon-generated carrier recombination rate results in low photon efficiency and low catalytic oxidation activity under visible light. In addition, in the photocatalysis process, the backlight surface of the titanium plate cannot be excited by light, which is not beneficial to TiO2The absorption and reflection of light by NTs is prone to scattering and loss of photons. When TiO is present2When the length of NTs exceeds 10 micrometers, the adhesive force on the titanium sheet is weak, the titanium sheet is easy to fall off and break, the titanium sheet cannot be randomly formed, and only the flat plate state can be maintained, so that the construction of a photocatalytic reaction device is limited. Since the MoS2 nano-sheet has a narrow band gap (1.17 eV) and a proper energy band position, the MoS is prepared2Nanosheet and TiO2NTs can be compounded with TiO2The response of NTs to light extends into the visible region. In addition, the surface plasmon resonance effect generated by the noble metal nanoparticles (such as Ag, Au, Pt and the like) under the irradiation of visible light can promote the generation of photo-generated electrons. Thus, noble metal nanoparticles and MoS2Both nanosheets being co-extensive with TiO2NTs (N, N2Photocatalytic activity of NTs. Dissolved oxygen molecules can be easily captured and separated in the process of photocatalytic degradation experimentsAnd generates hydroxyl radicals and superoxide radicals. At the same time, the holes are able to react with water molecules to generate hydroxyl radicals. The free radicals and the cavities are high-activity species, have strong oxidizability, and can oxidize antibiotic pollutants into non-toxic and harmless substances.
Disclosure of Invention
The invention aims to provide a MoS taking a titanium mesh as a substrate2/Ag/TiO2Preparation method of NTs for further enhancing TiO2The visible light absorption capacity and the electronic transmission capacity of the NTs widen the absorption range of the NTs in a visible light area, improve the photoelectric conversion efficiency of the NTs, and further provide a new material for photocatalytic degradation of antibiotic pollutants. The material is prepared by a photo-reduction method and a hydrothermal method, is simple to operate, low in cost, high in yield, good in degradation effect and good in repeatability, is prepared on a titanium net, solves the problem of catalyst immobilization, is convenient and quick to use, is not easy to lose, is convenient to recover, can be connected with an external circuit, and improves the separation efficiency of photo-generated electrons and holes by applying bias voltage.
The invention is realized by that the nano composite material of the invention is made of MoS2Nanosheet, Ag nanoparticle and TiO2The ternary heterojunction formed by NTs is 4cm under the irradiation of visible light (lambda is more than or equal to 420nm)2MoS on titanium mesh2/ Ag/TiO2The NTs catalyst can completely degrade 100mL of 10mg/L tetracycline hydrochloride within 2 hours.
The MoS taking the titanium mesh as the substrate2/Ag/TiO2The preparation method of NTs is characterized by comprising the following steps:
(1) pretreatment of a titanium mesh: cutting a commercially available titanium mesh (grid is 3mm multiplied by 1mm, thickness is 0.5 mm) into a size of 3cm multiplied by 2cm, then ultrasonically cleaning for 30min by sequentially using acetone, ethanol and deionized water, putting into an oven, drying for 12h at 80 ℃, and taking out for later use;
（2）TiO2preparation of NTs/Ti network: dissolving 0.5-2 wt% of hydrofluoric acid into 40mL of dimethyl sulfoxide to prepare an electrolyte. Under the direct current voltage of 20-40V, a platinum sheet (1 cm multiplied by 3 cm) is taken as a cathode, and a titanium net (2 cm multiplied by 3 cm)Is used as an anode and is electrolyzed in the electrolyte for 8-10 h. Then, calcining for 2-4 hours at 450-550 ℃ under an aerobic condition, and crystallizing to convert the crystal into anatase and rutile TiO2NTs；
(3) Preparation of Ag/TiO by photo-reduction method2NTs networks. Adding TiO into the mixture2The NTs/Ti net (effective area 2cm is multiplied by 2 cm) is immersed in 0.002-0.014 mol/L AgNO3In the solution, carrying out ultrasonic treatment at 40kHz for 30min, then washing the solution clean by deionized water, immersing the solution in 0.1-0.5 mol/L methanol solution, illuminating for 10-30 min, then washing the solution clean by deionized water, and drying;
(4) MoS preparation by hydrothermal method2/Ag/TiO2NTs. Sodium molybdate and thioacetamide are selected as molybdenum source and sulfur source. Ultrasonically dissolving 10-20 mg of sodium molybdate and 20-40 mg of thioacetamide into 35mL of deionized water, adding the solution into a 50mL hydrothermal kettle, and putting the hydrothermal kettle into the Ag/TiO prepared in the step (3)2NTs net, hydrothermal reaction for 24h, and temperature controlled at 220 ℃. And (3) taking out the titanium mesh after the reaction is finished, washing the titanium mesh clean by using deionized water, placing the titanium mesh in a drying oven, and drying the titanium mesh for 12 hours at the temperature of 80 ℃. And putting the obtained material into a tubular furnace, introducing nitrogen for calcination, calcining at 450 ℃ for 2h, and raising and lowering the temperature at the rate of 2 ℃ per min.
The MoS taking the titanium mesh as the substrate2/Ag/TiO2Nano composite material MoS prepared by preparation method of NTs2/Ag/TiO2NTs can be subjected to photocatalytic degradation under the irradiation of visible light (lambda is more than or equal to 420nm) to treat tetracycline hydrochloride which is a typical antibiotic pollutant.
The invention has the technical effects that: 1. in the invention, Ag nano particles and MoS are subjected to photo-reduction and hydrothermal methods2Nanosheet deposited TiO2Formation of MoS on NTs/Ti nets2/Ag/TiO2NTs nanocomposites. Under irradiation of visible light, TiO2And MoS2Can be excited to generate electron-hole pairs. Due to TiO2The position of the conduction band is higher than MoS2And Ag, TiO2The photo-generated electrons on the conduction band can be transferred to the MoS through the action of the heterojunction2On the conduction band of (1), and then MoS2The electrons on the surface are transferred to Ag or directly toAttached Ag nano particle surface. Meanwhile, the surface plasma effect generated by the Ag nano particles under the irradiation of visible light can promote the generation of photo-generated electrons, which is beneficial to improving the photocatalytic efficiency. MoS2/Ag/TiO2Heterojunction and schottky barrier in NTs can effectively separate photo-generated electron-hole pairs and reduce their recombination probability, and both synergistically promote enhanced photocatalytic activity.
2. The invention adopts a photo-reduction method and a hydrothermal method to prepare Ag nano particles and MoS2The nanosheets being uniformly deposited on the TiO2The nozzles, inner and outer walls of the NTs. The method is simple and low in cost, and the prepared MoS2/Ag/ TiO2NTs can be directly used for photocatalytic degradation treatment of antibiotic (tetracycline hydrochloride) wastewater. Modified Ag nanoparticles and MoS2Nanosheet of TiO2NTs compared to unmodified TiO2NTs, the former has 1.5 times higher photocatalytic degradation efficiency to tetracycline hydrochloride than the latter. In addition, titanium mesh based MoS2/Ag/TiO2NTs is convenient to recycle, high in repeated utilization rate and good in photocatalytic activity and stability.
3. The invention takes a commercially available titanium mesh as a substrate, and obtains three-dimensional TiO after anodic oxidation2The NTs/Ti net can be used for constructing various configurations such as flat plate, cylinder, Z-shaped and other functional electrodes according to actual needs by virtue of flexibility and plasticity. The structure is beneficial to prolonging the contact time of tetracycline hydrochloride molecules and the surface of the electrode, thereby increasing the probability of participating in the reaction. In addition, incident light can be reflected and refracted on the surface of the three-dimensional grid for multiple times, so that the photon absorption rate is increased. TiO22The conductivity and the solidity of the NTs/Ti net are convenient for the NTs/Ti net to be connected with an external circuit, so that a practical photoelectrocatalysis system is constructed.
Drawings
FIG. 1 shows TiO of the present invention2NTs、MoS2/Ag/TiO2Scanning Electron microscopy of NTs (A is unmodified TiO)2NTs; b is MoS2And Ag modified TiO2NTs）。
FIG. 2 shows TiO of the present invention2NTs、MoS2/Ag/TiO2X-ray of NTsLine diffraction pattern.
FIG. 3 shows TiO of the present invention2NTs、MoS2/Ag/TiO2Ultraviolet-visible diffuse reflectance spectra of NTs.
FIG. 4 shows TiO of the present invention2NTs、MoS2/Ag/TiO2Graph of photocurrent response of NTs.
FIG. 5 is a MoS of the present invention2/Ag/TiO2Graph comparing the effect of degrading tetracycline hydrochloride by photo (electro) catalysis under the irradiation of visible light by NTs and other samples.
Detailed Description
Example 1
Nanocomposite MoS of the present example2/Ag/TiO2The preparation method of NTs is as follows:
(1) pretreatment of a titanium mesh: ultrasonically cleaning a titanium mesh with acetone, ethanol and deionized water in sequence for later use; (2) preparing an organic electrolyte: 40mL of dimethyl sulfoxide solution containing 2wt% of hydrofluoric acid; (3) anodic oxidation of titanium mesh: electrolyzing for 8h in an electrolyte under a direct current voltage of 40V by taking a platinum sheet (L multiplied by W =3 multiplied by 1 cm) as a cathode and a titanium mesh (L multiplied by W =3 multiplied by 2 cm) as an anode to prepare titanium oxide nanotubes; (4) crystallization of titanium oxide nanotubes: calcining the titanium oxide nanotubes prepared in the step for 2-4 hours at 450-550 ℃ under aerobic condition to crystallize the titanium oxide nanotubes into TiO2NTs。（5）Ag/TiO2Preparation of NTs net: adding TiO into the mixture2The NTs/Ti net (effective area 2cm x 2 cm) is immersed in 0.06mol/L AgNO3In the solution, ultrasonic treatment is carried out for 30min at 40kHz, then the solution is washed clean by deionized water, and then the solution is immersed in 0.1 mol/L methanol solution, and the solution is irradiated by a xenon lamp for 30min, then the solution is washed clean by the deionized water and dried. (6) MoS2/Ag/TiO2Preparation of NTs: 10mg of sodium molybdate and 20 mg of thioacetamide are dissolved in 35ml of deionized water, firstly ultrasonic treatment is carried out for 5min, and then magnetic stirring is carried out for 10min, so as to obtain a solution. Pouring the solution into a 50mL hydrothermal kettle lining, vertically placing the material prepared in the previous step into the hydrothermal kettle lining, and sealing. And (3) putting the hydrothermal kettle into an oven, and reacting for 24 hours at 220 ℃. And taking out the material after the reaction is finished, washing the material with deionized water, and drying the material at 80 ℃ for 12 hours. Calcining at 450 ℃ for 2h under the nitrogen atmosphere, and crystallizing.
By using TiO2NTs and MoS2/Ag/TiO2NTs respectively carry out light (electric) catalytic degradation on 100mL of 10mg/L tetracycline hydrochloride wastewater:
the implementation steps are as follows:
(1) in the photocatalytic degradation process, MoS with the effective area of 2cm multiplied by 2cm is added2/Ag/TiO2NTs (titanium net) was immersed in 100mL of 10mg/L tetracycline hydrochloride wastewater, and stirred in the dark for 1 hour to attain adsorption-desorption equilibrium of tetracycline hydrochloride on the catalyst surface. Then the sample was put into a 300W xenon lamp equipped with a 420nm filter (illumination intensity of 100 mw/cm)2) Under the action of (1) to irradiate light. After sampling at regular time, monitoring the concentration change of tetracycline hydrochloride in the solution by using an ultraviolet-visible spectrophotometer;
(2) in the process of photoelectrocatalysis degradation, a double-electrode system, MoS, is adopted2/Ag/TiO2NTs (titanium mesh) as a working electrode is connected with a cathode, a platinum sheet as a counter electrode is connected with an anode, 100mL of 10mg/L tetracycline hydrochloride wastewater is added into a quartz reactor, a power supply is a direct current stabilized voltage power supply, and the voltage is set to be 0.1V. The light source adopts a 300W xenon lamp (the illumination intensity is 100 mw/cm)2) And the uv light was filtered using a 420nm filter. After sampling at regular time, monitoring the concentration change of tetracycline hydrochloride in the solution by using an ultraviolet-visible spectrophotometer;
(3) control experiment for photocatalytic degradation of tetracycline hydrochloride in unmodified TiO2NTs (titanium mesh) is carried out, and the steps are the same as (1) and (2);
as can be seen from the electron micrograph of FIG. 1, TiO2NTs directional growth, vertical arrangement, uniform size, and thin layer MoS2The nano sheets are tightly connected together and uniformly covered on the TiO2And the NTs surface forms a stable three-dimensional network structure, which is beneficial to the transmission of electrons on the surface of the material. MoS as shown in the X-ray diffraction diagram of FIG. 22/Ag/TiO2TiO in NTs2Is composed of anatase phase, MoS2Consists of a hexagonal crystal phase. FIG. 3 is a UV-visible diffuse reflectance spectrum showing that Ag nanoparticles and MoS are deposited2Nanosheet of TiO2NTs，The absorption in the ultraviolet and visible regions is significantly enhanced, with the absorption sidebands also being slightly red-shifted toward the long wavelength band. As can be seen from the photocurrent response graph of FIG. 4, MoS2/Ag/TiO2The intensity of photocurrent generated by NTs is far higher than that of unmodified TiO2NTs, indicating modification of Ag nanoparticles and MoS2The composite material catalyst of the nanosheet can better promote the separation of photo-generated electrons and holes, and has stronger photocatalytic degradation performance. Curve 1 in FIG. 5 shows the MoS under dark conditions2/Ag/TiO2The NTs hardly degraded tetracycline hydrochloride. Curve 2 shows that, when no catalyst is added, the degradation rate of tetracycline hydrochloride is only 27% after 120 min of irradiation with visible light (lambda is more than or equal to 420 nm). Curves 3 and 4 show that pure TiO is present during photocatalytic degradation2NTs can only degrade 60% tetracycline hydrochloride, whereas MoS2/Ag/TiO2The degradation activity of NTs is as high as 93%. Curves 5, 6 show that during the photoelectrocatalytic degradation process, the MoS2/Ag/TiO2The degradation effect of NTs on tetracycline hydrochloride is better than that of pure TiO2NTs. Thus, under the irradiation of visible light, MoS is adopted2/Ag/ TiO2NTs is used as a catalyst, so that the high-efficiency and rapid decomposition of tetracycline hydrochloride wastewater is realized, and the MoS prepared by the method is proved2/Ag/ TiO2NTs is a high-efficiency nano composite material for treating antibiotic wastewater.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (3)

1. Nanocomposite MoS2/Ag/TiO2The preparation method of NTs is characterized in that: the method comprises the following steps:
(1) to be provided withPreparing TiO by anodic oxidation method with commercially available titanium mesh as substrate2NTs/Ti mesh;
(2) TiO obtained in the step (1)2The NTs/Ti net is immersed in AgNO3Ultrasonic treating in the solution, washing with deionized water, and immersing in methanol solution with illumination intensity of 100 mW/cm2Preparing Ag/TiO by photo-reduction method under the action of 300W xenon lamp2A network of NTs;
(3) the Ag/TiO obtained in the step (2)2The NTs net is immersed in 35mL of aqueous solution containing sodium molybdate and thioacetamide, and the MoS is prepared by a hydrothermal method2/Ag/TiO2NTs；
(4) MoS obtained in the step (3) and grown on a titanium mesh in situ2/Ag/TiO2NTs is calcined and crystallized in nitrogen atmosphere;
the specific operating conditions of the photo-reduction method in the step (2) are as follows: the ultrasonic frequency is 40kHz, the ultrasonic time is 30min, and the illumination intensity is 100 mW/cm2Under the action of a 300W xenon lamp, illuminating for 10-30 min; the hydrothermal method of the step (3) has the following specific operating conditions: the hydrothermal reaction temperature is 220 ℃ and the time is 24 hours; the calcining temperature in the nitrogen atmosphere in the step (4) is 450 ℃, the constant temperature time is 2h, and the heating and cooling rates are 2 ℃/min.
2. Nanocomposite MoS according to claim 12/Ag/TiO2The preparation method of NTs is characterized in that: TiO in the step (1)2The preparation method of the NTs/Ti net comprises the following steps:
a, titanium mesh pretreatment: cutting a titanium mesh into a size of 2cm multiplied by 3cm, then ultrasonically cleaning the titanium mesh for 30min by using acetone, ethanol and deionized water in sequence, then drying the titanium mesh in an oven, and taking the titanium mesh out for later use;
b, preparing organic electrolyte: the electrolyte consists of a dimethyl sulfoxide solution of hydrofluoric acid with the mass fraction of 0.5-2%;
c . TiO2preparation of NTs/Ti network: under the direct current voltage of 20-40V, a titanium mesh is used as an anode, a platinum sheet is used as a cathode, and the electrolysis is carried out in an organic electrolyte for 8-10 h to prepare TiO2NTs；
C, under the aerobic condition of 450-550 ℃, carrying out the TiO prepared in the step c2And (4) calcining NTs for 2-4 h to crystallize the NTs.
3. Nanocomposite MoS according to claim 12/Ag/TiO2The preparation method of NTs is characterized in that: AgNO in the step (2)3The concentration of the methanol is 0.002-0.014 mol/L, and the concentration of the methanol is 0.1-0.5 mol/L; in the step (3), the dosage of the sodium molybdate is 10-20 mg, and the dosage of the thioacetamide is 20-40 mg.
CN201810239525.9A 2018-03-22 2018-03-22 Nanocomposite MoS2/Ag/TiO2Preparation method of NTs Expired - Fee Related CN108404937B (en)

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