CN108579737B - Preparation method of titanium dioxide-carbon nanotube composite photocatalyst modified by nanogold - Google Patents
Preparation method of titanium dioxide-carbon nanotube composite photocatalyst modified by nanogold Download PDFInfo
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- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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Abstract
The invention provides a nanometerThe preparation method of the titanium dioxide-carbon nanotube composite photocatalyst modified by gold comprises the following steps: taking an aqueous solution of alcohol and stable gas as media, and processing by using a micro-nano bubble generator to obtain micro-nano bubble water; mixing and dispersing the micro-nano bubble water, the carbon nano tube and the titanium salt to obtain a dispersion liquid; mixing the dispersion liquid with an ammonia water solution, and hydrolyzing to obtain a hydrolysate; d) mixing the hydrolysate with gold salt and micro-nano bubble water, and then sequentially carrying out illumination reduction and heating reaction to obtain a reaction product; carrying out heat treatment on the reaction product to obtain Au-TiO2-CNTs composite photocatalyst. The preparation method provided by the invention is simple and feasible, and the preparation process is greatly simplified; the prepared composite photocatalyst is stable in combination and has an effective and excellent catalytic degradation effect; meanwhile, toxic organic solvents and templates are not needed in the preparation process, so that the cost and the harm to the environment are greatly reduced.
Description
Technical Field
The invention belongs to the technical field of air purification, and particularly relates to a preparation method of a titanium dioxide-carbon nanotube composite photocatalyst modified by nanogold.
Background
Currently, many of the air pollutants represented by typical Volatile Organic Compounds (VOCs) have carcinogenic and teratogenic effects, and a series of chronic diseases can be generated after the human body is in contact with the pollutants for a long time. Therefore, effective control and elimination of typical VOCs become one of the hotspots of current research, especially the research and development of a continuous, efficient and stable air purification technology, and have important significance for energy conservation and emission reduction, reduction of generation of toxic and harmful particulate matters, and practical improvement of living environment.
The photocatalyst oxidation technology can directly utilize visible light or sunlight to catalyze and degrade VOCs under the action of a photocatalyst, has the characteristics of environmental friendliness, low equipment requirement, mild reaction conditions, no secondary pollution and the like, and becomes a mainstream technology in the field of air purification. At present, Au-TiO is used as a visible light catalyst2the-CNTs (namely gold-titanium dioxide-carbon nano tubes) have excellent visible light catalytic performance and high-efficiency adsorption capacity on VOCs (volatile organic compounds), and have great value in the field of air purificationHair tension potential.
In the prior art, Au-TiO2The preparation process of the-CNTs composite photocatalyst is complex, the combination of the three components is difficult to control, the photocatalytic effect is easy to influence, and a large amount of toxic organic solvents and templates (such as J.Li, S.B.Tang, L.Lu, et al.J.Am.chem.Soc.2007,129, 9401; Y.X.Zhang, B.Gao, G.L.Puma, et al.Sci.Adv.Mater.2010,2,503) are consumed in the preparation process, so that the cost is increased, and secondary harm is generated to the ecological environment. Therefore, the development of a simple, efficient and harmless preparation method has become an urgent problem to be solved in the art.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a titanium dioxide-carbon nanotube composite photocatalyst modified by nanogold, the preparation method provided by the present invention can greatly simplify the preparation process, the prepared composite photocatalyst is stable in combination and has excellent catalytic degradation effect, and no toxic organic solvent or template agent is used in the preparation process, so that the cost and the harm to the environment are greatly reduced.
The invention provides a preparation method of a titanium dioxide-carbon nanotube composite photocatalyst modified by nanogold, which comprises the following steps:
a) taking an aqueous solution of alcohol and stable gas as media, and processing by using a micro-nano bubble generator to obtain micro-nano bubble water;
b) mixing and dispersing the micro-nano bubble water, the carbon nano tube and the titanium salt to obtain a dispersion liquid;
c) mixing the dispersion liquid with an ammonia water solution, and hydrolyzing to obtain a hydrolysate;
d) mixing the hydrolysate with gold salt and micro-nano bubble water, and then sequentially carrying out illumination reduction and heating reaction to obtain a reaction product;
e) carrying out heat treatment on the reaction product to obtain Au-TiO2-CNTs composite photocatalyst.
Preferably, in the step a), the working pressure of the micro-nano bubble generator is 0.25-0.65 MPa, the air inflow of the steady-state gas is 1.5-4.5L/min, and the water solution of the alcohol is 5-10L.
Preferably, in the step a), the alcohol in the alcohol aqueous solution comprises one or more of ethanol and glycerol;
the mass concentration of the alcohol aqueous solution is 1-50%;
the steady state gas comprises air and N2、O2、CO2And H2One or more of them.
Preferably, in the step b), the ratio of the mass of the carbon nano tube to the molar weight of the titanium salt is (12-119) mg to (2-10) mmol;
the mass ratio of the volume of the micro-nano bubble water to the carbon nano tube is (40-120) mL to (12-119) mg.
Preferably, in the step c), the mass concentration of the ammonia water solution is 1-5%;
and controlling the addition amount of the ammonia water solution until the mixed solution is in a sol state.
Preferably, in the step c), the hydrolysis time is 8-24 h.
Preferably, in the step d), the ratio of the volume of the micro-nano bubble water to the molar quantity of the gold salt is 10mL to (0.004-0.032) mmol;
the molar ratio of the gold salt to the titanium salt in the step b) is (0.004-0.032) to (2-10).
Preferably, in the step d), the power of the illumination is 10-300W, and the time of the illumination reduction is 5-15 min;
the heating reaction temperature is 25-90 ℃, and the time is 4-20 h.
Preferably, in the step e), the temperature of the heat treatment is 200-450 ℃ and the time is 1.5-3 h.
Preferably, the carbon nanotubes are multi-walled carbon nanotubes; the pipe diameter of the multi-walled carbon nanotube is 8-60 nm;
the titanium salt is selected from TiCl4And TiOSO4One or more of the above;
the gold salt is selected from AuCl3And HAuCl4One or more of them.
Hair brushThe invention provides a preparation method of a titanium dioxide-carbon nano tube composite photocatalyst modified by nano gold, which comprises the following steps: a) taking an aqueous solution of alcohol and stable gas as media, and processing by using a micro-nano bubble generator to obtain micro-nano bubble water; b) mixing and dispersing the micro-nano bubble water, the carbon nano tube and the titanium salt to obtain a dispersion liquid; c) mixing the dispersion liquid with an ammonia water solution, and hydrolyzing to obtain a hydrolysate; d) mixing the hydrolysate with gold salt and micro-nano bubble water, and then sequentially carrying out illumination reduction and heating reaction to obtain a reaction product; e) carrying out heat treatment on the reaction product to obtain Au-TiO2-CNTs composite photocatalyst. Compared with the prior art, the preparation method provided by the invention is simple and feasible, and the preparation process is greatly simplified; the prepared composite photocatalyst is stable in combination and has an effective and excellent catalytic degradation effect; meanwhile, toxic organic solvents and templates are not needed in the preparation process, so that the cost and the harm to the environment are greatly reduced. Test results show that the Au-TiO prepared by the invention2After 2h of ultrasonic treatment of the-CNTs composite photocatalyst, nano Au and TiO2The particles are not peeled off from the carbon nanotubes due to ultrasonic dispersion, and have a close interface relationship; under simulated illumination, the obtained Au-TiO2The CNTs composite photocatalyst has excellent adsorption rate, degradation rate and mineralization rate on styrene, and generates excellent catalytic degradation effect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows Au-TiO prepared in example 12-scanning electron microscopy of MWCNTs composite photocatalyst;
FIG. 2 is a transmission electron micrograph of a sample after the ultrasonic dispersion treatment of example 1;
FIG. 3 is TiO2、Au-TiO2And Au-TiO obtained in example 12-raman spectra contrast of MWCNTs;
FIG. 4 shows Au-TiO prepared in example 22A catalytic degradation curve diagram of the MWCNTs composite photocatalyst for styrene.
Detailed Description
The invention provides a preparation method of a titanium dioxide-carbon nanotube composite photocatalyst modified by nanogold, which comprises the following steps:
a) taking an aqueous solution of alcohol and stable gas as media, and processing by using a micro-nano bubble generator to obtain micro-nano bubble water;
b) mixing and dispersing the micro-nano bubble water, the carbon nano tube and the titanium salt to obtain a dispersion liquid;
c) mixing the dispersion liquid with an ammonia water solution, and hydrolyzing to obtain a hydrolysate;
d) mixing the hydrolysate with gold salt and micro-nano bubble water, and then sequentially carrying out illumination reduction and heating reaction to obtain a reaction product;
e) carrying out heat treatment on the reaction product to obtain Au-TiO2-CNTs composite photocatalyst.
The method takes micro-nano bubble water as a soft template, combines the specific treatment process, and obtains Au-TiO by carrying out micro-nano bubble interface charge-induced synthesis technology, in-situ self-assembly and photoreduction on titanium salt, gold salt raw materials and a carbon nano tube carrier2CNTs composite photocatalyst, the preparation process is simple and easy to implement, and the obtained Au-TiO2The CNTs composite photocatalyst has a stable interface structure, shows high visible light activity and catalytic degradation, and simultaneously, toxic organic solvents and templates are not needed in the preparation process, so that the cost and the harm to the environment are greatly reduced.
According to the invention, firstly, the aqueous solution of alcohol and stable gas are used as media, and the micro-nano bubble water is obtained by utilizing the micro-nano bubble generator for processing.
The invention utilizes a micro-nano generator to carry out micro-nano treatment on a gas-liquid medium to form micro-nano bubble water. Wherein, the alcohol in the alcohol aqueous solution preferably comprises one or more of ethanol and glycerol. The mass concentration of the aqueous alcohol solution is preferably 1% to 50%. The usage amount of the alcohol aqueous solution is preferably 5-10L.
The steady state gas preferably comprises air, N2、O2、CO2And H2One or more of them. The intake amount of the steady-state gas is preferably 1.5-4.5L/min.
When the micro-nano generator is used for carrying out micro-nano treatment on a gas-liquid medium, the working pressure of the micro-nano generator is preferably 0.25-0.65 MPa. The gas-liquid medium is utilized to be processed under the working pressure, the size and the space of bubbles are ideal, the micro-nano bubble water suitable for serving as the template agent is obtained, the unique micro-nano bubble water serves as a soft template, special interface negative charge characteristics and affinity to a solid phase interface can be generated in a preparation system of the invention, and high-valence positive ions such as Ti in raw materials can be effectively promoted by combining the specific processing process of the invention4+And Au3+Pre-adsorbing and self-assembling on the surface of the carbon nano tube, and accurately regulating and controlling nano Au on TiO2The space of the CNTs is modified, and then the visible light catalytic material with selective adsorption and degradation effects on typical indoor VOCs is obtained.
According to the invention, after micro-nano bubble water is obtained, the micro-nano bubble water, the carbon nano tube and the titanium salt are mixed and dispersed to obtain the dispersion liquid.
In the present invention, the carbon nanotubes are preferably multi-walled carbon nanotubes (i.e., MWCNTs). The preferred pipe diameter of the multi-wall carbon nano-tube is 8-60 nm. The purity of the multi-walled carbon nanotube is preferably more than or equal to 90%.
In the present invention, the titanium salt is preferably TiCl4And TiOSO4One or more of them.
In the present invention, the ratio of the mass of the carbon nanotube to the molar amount of the titanium salt is preferably (12 to 119) mg to (2 to 10) mmol, and the carbon nanotube and TiO are mixed together2The mass ratio of (A) is 4-37%.
In the invention, the mass ratio of the volume of the micro-nano bubble water to the carbon nano tubes is preferably (40-120) mL to (12-119) mg.
In the invention, the mode of mixing and dispersing the micro-nano bubble water, the carbon nano tube and the titanium salt is preferably ultrasonic dispersion. In the invention, the mixing and dispersing time is preferably 15-40 min. The temperature of the mixing and dispersing is not particularly limited, and the mixing and dispersing can be carried out at room temperature, such as at 25-30 ℃. After the mixing and dispersing, a dispersion liquid is obtained.
According to the invention, after the dispersion is obtained, the dispersion is mixed with an aqueous ammonia solution and hydrolyzed to obtain a hydrolysate.
In the present invention, the mass concentration of the aqueous ammonia solution is preferably 1% to 5%. When the dispersion liquid is mixed with the aqueous ammonia solution, the amount of the aqueous ammonia solution to be added is preferably controlled so that the mixed liquid becomes a sol. In some embodiments, the amount of the ammonia solution added is controlled to be 8% to 40% of the dispersion, and the mixed solution is subjected to sol at the amount. The invention preferably adopts a mode of dripping the ammonia water solution into the dispersion liquid to mix the dispersion liquid and the ammonia water solution, the dripping is stopped when the ammonia water solution is dripped to a sol state, and the dispersion liquid and the dripped ammonia water solution continue to carry out hydrolysis reaction. In the invention, the hydrolysis time is preferably 8-24 h. The temperature of the mixing and the hydrolysis is not particularly limited, and the mixing and the hydrolysis can be carried out at room temperature, for example, at the room temperature of 25-30 ℃, and a hydrolysate is obtained after the hydrolysis.
According to the invention, after obtaining the hydrolysate, the hydrolysate is mixed with gold salt and micro-nano bubble water, and then illumination reduction and heating reaction are sequentially carried out, so as to obtain the reaction product.
In the present invention, the gold salt is preferably AuCl3And HAuCl4One or more of them. The molar ratio of the gold salt to the titanium salt in the step is preferably (0.004-0.032): (2-10).
In the present invention, the micro-nano bubble water is the same as that in the above technical scheme, and is not described herein again. The ratio of the volume of the micronano bubble water to the molar quantity of the gold salt is preferably 10mL to (0.004-0.032) mmol.
The method has no special limitation on the mixing mode of the hydrolysate, the gold salt and the micro-nano bubble water, and the three can be uniformly mixed. In the invention, the order of mixing the hydrolysate with the gold salt and the micro-nano bubble water is preferably to mix the gold salt with the micro-nano bubble water to obtain the micro-nano bubble water solution containing the gold salt, and then mix the micro-nano bubble water solution with the hydrolysate.
Mixing the three materials, and performing light reduction. In the present invention, the light reduction is preferably performed under visible light or ultraviolet light, and the light source may be provided by light source irradiation. In the invention, the power of the illumination is preferably 10-300W. The time for the light reduction is preferably 5-15 min.
After the reduction by light irradiation, a heating reaction is also carried out. In the invention, the heating reaction temperature is preferably 25-90 ℃. The heating reaction time is preferably 4-20 h. The manner of heating is not particularly limited, and in one embodiment, oil bath heating is employed. After the heating reaction, a reaction product is obtained.
The method takes micro-nano bubble water as a soft template, and can effectively promote TiO by sequentially carrying out titanium salt hydrolysis and gold salt reduction2The nano particles and the Au nano particles are self-assembled and crystallized and nucleated on the surface of the carbon nano tube, and meanwhile, the spatial modification sites of the nano Au can be accurately regulated and controlled.
According to the invention, after the reaction product is obtained, the reaction product is subjected to heat treatment to obtain Au-TiO2-CNTs composite photocatalyst.
In the present invention, it is preferable to further perform freeze-drying before the heat treatment of the reaction product. The conditions for the freeze-drying are not particularly limited and may be those conventionally used in the art. After the freeze-drying, a heat treatment is performed.
In the invention, the temperature of the heat treatment is preferably 200-450 ℃. The time of the heat treatment is preferably 1.5-3 h. The reaction product obtained in the treatment step is further subjected to heat treatment, so that Au-TiO with stable interface combination and firm structure can be obtained2-CNTs composite photocatalyst.
The invention provides a preparation method of a titanium dioxide-carbon nano tube composite photocatalyst modified by nano-gold, compared with the prior art, the preparation method provided by the invention is simple and easy to implement,the preparation process is greatly simplified; the prepared composite photocatalyst is stable in combination and has an effective and excellent catalytic degradation effect; meanwhile, toxic organic solvents and templates are not needed in the preparation process, so that the cost and the harm to the environment are greatly reduced. Test results show that the Au-TiO prepared by the invention2After 2h of ultrasonic treatment of the-CNTs composite photocatalyst, nano Au and TiO2The particles are not peeled off from the carbon nanotubes due to ultrasonic dispersion, and have a close interface relationship; under simulated illumination, the obtained Au-TiO2The CNTs composite photocatalyst has excellent adsorption rate, degradation rate and mineralization rate on styrene, and generates excellent catalytic degradation effect.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. The raw materials used in the following examples are commercially available, wherein the tube diameter of the multi-walled carbon nanotube is 8-60 nm, and the purity is not less than 90%.
Example 1
1.1 preparation of samples
8L of 11% ethanol water solution and air are used as media, a micro-nano bubble generator provided with a high-pressure micro-nano nozzle is used for processing, the working pressure is 0.40MPa, the air inflow is 1.5L/min, and micro-nano bubble water is obtained after processing. Placing 80mL of micro-nano bubble water in a 250mL conical flask, and mixing the obtained product according to the mass ratio of MWCNTs: TiO22Adding 83.2mg of MWCNTs and 4mmol of TiCl into the micro-nano bubble water in turn (26 percent)4And placing the conical flask in an ultrasonic instrument for ultrasonic treatment for 15min to obtain uniform dispersion liquid. Gradually dropwise adding 2.6% diluted ammonia water solution into the dispersion liquid until sol state appears, and then continuing hydrolysis reaction at room temperature of 30 ℃ for 13h to obtain hydrolysate. To the resulting hydrolyzate was added HAuCl in an amount of 0.018mmol4Irradiating the micro-nano bubble aqueous solution by 10mL under a 300W xenon lamp light source for 12min, and then placing the micro-nano bubble aqueous solution in an oil bath to react for 12h at 70 ℃ to obtain a dark gray reaction product. The obtained dark gray reaction product is calcined and insulated for 2 hours at the temperature of 420 ℃ after being frozen and dried,to obtain Au-TiO2-MWCNTs composite photocatalyst.
1.2 characterization and Performance testing of the samples
For the obtained Au-TiO2The micro-morphology of the MWCNTs composite photocatalyst is characterized, and the result is shown in FIG. 1, wherein FIG. 1 shows Au-TiO obtained in the example2Scanning electron microscope image of MWCNTs composite photocatalyst shows that Au nanoparticles and TiO2The nano particles are uniformly distributed on the one-dimensional MWCNTs carrier and form a compact composite structure with the MWCNTs.
The obtained Au-TiO2The MWCNTs composite photocatalyst is placed in an ethanol system for ultrasonic dispersion treatment for 2 hours, a transmission electron microscope is used for observing a sample after the dispersion treatment, the result is shown in figure 2, figure 2 is a transmission electron microscope image of the sample after the ultrasonic dispersion treatment in the embodiment, and it can be seen that Au nanoparticles and TiO nanoparticles are dispersed for 2 hours2The nano particles are still tightly combined with the MWCNTs carrier and are not peeled off due to ultrasonic dispersion; presumably, Au/TiO2Chemical bonds may be formed with the MWCNTs. The obtained Au-TiO2In the-MWCNTs composite photocatalyst, Au/TiO2The close interface relation with MWCNTs is very favorable for photo-generated electrons to be formed by Au/TiO2The surface is transferred to MWCNTs, and then the separation efficiency and the photocatalysis efficiency of photon-generated carriers are improved.
For the obtained Au-TiO2-MWCNTs composite photocatalyst, TiO2 and Au-TiO2The results of the respective Raman spectroscopy measurements are shown in FIG. 3, where FIG. 3 shows TiO2、Au-TiO2And Au-TiO obtained in this example2Raman spectrum comparison chart of MWCNTs (Au/TiO 2@ CNTs in FIG. 3 is Au-TiO 2@ CNTs2-MWCNTs，Au/TiO2Namely Au-TiO2) In the figure, Au-TiO2The shift of the characteristic peak of the MWCNTs composite photocatalyst further proves that Au/TiO2And MWCNTs form chemical bonds.
The obtained Au-TiO is utilized under the simulated solar illumination2The catalytic degradation test of the MWCNTs composite photocatalyst on styrene shows that Au-TiO2The MWCNTs composite photocatalyst has stronger degradation and mineralization capacity on styrene, and the maximum value of the MWCNTs composite photocatalyst on the styreneThe adsorption rate reaches 80%, the degradation efficiency of the styrene is stabilized at 75% within 300min of continuous degradation, the degradation trend is not obviously reduced, the mineralization efficiency of the styrene reaches 50%, the obtained photocatalyst can effectively promote the formation rate of oxidation free radicals such as hydroxyl free radicals and superoxide free radicals, effectively promote the degradation and mineralization of the styrene enriched on the surface of the photocatalyst, and simultaneously avoid the problems of product accumulation, catalyst inactivation and the like caused by the interface mass transfer problem.
Example 2
1.1 preparation of samples
8L of 11% ethanol water solution and air are used as media, a micro-nano bubble generator provided with a high-pressure micro-nano nozzle is used for processing, the working pressure is 0.40MPa, the air inflow is 3L/min, and micro-nano bubble water is obtained after processing. Placing 80mL of micro-nano bubble water in a 250mL conical flask, and mixing the obtained product according to the mass ratio of MWCNTs: TiO22Adding 83.2mg of MWCNTs and 4mmol of TiCl into the micro-nano bubble water in turn (26 percent)4And placing the conical flask in an ultrasonic instrument for ultrasonic treatment for 15min to obtain uniform dispersion liquid. Gradually dropwise adding 2.6% diluted ammonia water solution into the dispersion liquid until sol state appears, and then continuing hydrolysis reaction at room temperature of 30 ℃ for 13h to obtain hydrolysate. To the resulting hydrolyzate was added HAuCl in an amount of 0.018mmol4Irradiating the micro-nano bubble aqueous solution by 10mL under a 300W xenon lamp light source for 12min, and then placing the micro-nano bubble aqueous solution in an oil bath to react for 12h at 90 ℃ to obtain a dark gray reaction product. The obtained dark gray reaction product is calcined and insulated for 2 hours at the temperature of 420 ℃ after being frozen and dried to obtain Au-TiO2-MWCNTs composite photocatalyst.
1.2 characterization and Performance testing of the samples
The obtained Au-TiO was subjected to the characterization method of example 12The micro-morphology of the MWCNTs composite photocatalyst is characterized, and the result shows that Au nanoparticles and TiO2The nano particles are uniformly distributed on the one-dimensional MWCNTs carrier and form a compact composite structure with the MWCNTs.
The Au-TiO compound obtained was subjected to the test method of example 12Performing ultrasonic dispersion treatment and observation on-MWCNTs composite photocatalystThe result of the treated sample shows that after 2h of dispersion treatment, Au nanoparticles and TiO2The nano particles are still tightly combined with the MWCNTs carrier and are not stripped off due to ultrasonic dispersion, and Au/TiO2The nanoparticles and MWCNTs carriers form stable and firm combination.
The Au-TiO compound obtained was subjected to the test method of example 12The catalytic degradation test of styrene by using the MWCNTs composite photocatalyst is shown in FIG. 4, and FIG. 4 shows the Au-TiO obtained in the example2A catalytic degradation curve diagram of the MWCNTs composite photocatalyst for styrene. As can be seen, Au-TiO2The MWCNTs composite photocatalyst has strong degradation and mineralization capacity on styrene, the highest adsorption rate of the MWCNTs composite photocatalyst on the styrene reaches 81.4%, the degradation efficiency of the styrene is stabilized at 80% within 300min of continuous degradation, no obvious decline trend exists, the mineralization efficiency of the styrene reaches a higher level of 72.3%, the obtained photocatalyst can effectively promote the formation rate of oxidative free radicals such as hydroxyl free radicals and superoxide free radicals, effectively promote the degradation and mineralization of the styrene enriched on the surface of the photocatalyst, and simultaneously avoid the problems of product accumulation, catalyst inactivation and the like caused by interface mass transfer problems.
Example 3
1.1 preparation of samples
8L of 11% ethanol water solution and air are used as media, a micro-nano bubble generator provided with a high-pressure micro-nano nozzle is used for processing, the working pressure is 0.40MPa, the air inflow is 3L/min, and micro-nano bubble water is obtained after processing. Placing 80mL of micro-nano bubble water in a 250mL conical flask, and mixing the obtained product according to the mass ratio of MWCNTs: TiO22Adding 12.8mg of MWCNTs and 4mmol of TiOSO into the micro-nano bubble water in sequence of 4.04 percent4And placing the conical flask in an ultrasonic instrument for ultrasonic treatment for 30min to obtain uniform dispersion liquid. Gradually dropwise adding 2.6% diluted ammonia water solution into the dispersion liquid until sol state appears, and then continuing hydrolysis reaction at room temperature of 30 ℃ for 13h to obtain hydrolysate. To the resulting hydrolyzate was added HAuCl in an amount of 0.004mmol4Irradiating the micro-nano bubble aqueous solution with a 300W xenon lamp light source for 12min by 10mL, and thenThe reaction mixture was placed in an oil bath at 85 ℃ for 12h to give a dark gray reaction product. The obtained dark gray reaction product is calcined and insulated for 2 hours at the temperature of 420 ℃ after being frozen and dried to obtain Au-TiO2-MWCNTs composite photocatalyst.
1.2 characterization and Performance testing of the samples
The obtained Au-TiO was subjected to the characterization method of example 12The micro-morphology of the MWCNTs composite photocatalyst is characterized, and the result shows that Au nanoparticles and TiO2The nano particles are uniformly distributed on the one-dimensional MWCNTs carrier and form a compact composite structure with the MWCNTs.
The Au-TiO compound obtained was subjected to the test method of example 12The MWCNTs composite photocatalyst is subjected to ultrasonic dispersion treatment and a treated sample is observed, and the result shows that after 2 hours of dispersion treatment, Au nanoparticles and TiO nanoparticles2The nano particles are still tightly combined with the MWCNTs carrier and are not stripped off due to ultrasonic dispersion, and Au/TiO2The nanoparticles and MWCNTs carriers form stable and firm combination.
The Au-TiO compound obtained was subjected to the test method of example 12The catalytic degradation test of the MWCNTs composite photocatalyst on styrene shows that Au-TiO2The MWCNTs composite photocatalyst has strong degradation and mineralization capacity on styrene, the highest adsorption rate of the MWCNTs composite photocatalyst on the styrene reaches 78%, the degradation efficiency of the styrene is stabilized at 77% within 300min of continuous degradation, no obvious decline trend exists, the mineralization efficiency of the styrene reaches 45%, the obtained photocatalyst can effectively promote the formation rate of oxidative free radicals such as hydroxyl free radicals and superoxide free radicals, effectively promote the degradation and mineralization of the styrene enriched on the surface of the photocatalyst, and simultaneously avoid the problems of product accumulation, catalyst inactivation and the like caused by the problem of interface mass transfer.
Example 4
1.1 preparation of samples
Treating with 8L of 16% ethanol water solution and air as medium by using a micro-nano bubble generator equipped with a high-pressure micro-nano nozzle, wherein the working pressure is 0.40MPa, the air input is 3L/min, and obtaining the micro-nano bubble water after treatment. Placing 80mL of micro-nano bubble water in a 250mL conical flask, and mixing the obtained product according to the mass ratio of MWCNTs: TiO22Adding 48mg of MWCNTs and 4mmol of TiCl into the micro-nano bubble water in sequence of 15 percent4And placing the conical flask in an ultrasonic instrument for ultrasonic treatment for 15min to obtain uniform dispersion liquid. Gradually dropwise adding 2.6% diluted ammonia water solution into the dispersion liquid until sol state appears, and then continuing hydrolysis reaction at room temperature of 30 ℃ for 13h to obtain hydrolysate. To the resulting hydrolyzate was added HAuCl in an amount of 0.018mmol4Irradiating the micro-nano bubble aqueous solution by 10mL under a 300W xenon lamp light source for 12min, and then placing the micro-nano bubble aqueous solution in an oil bath to react for 12h at the temperature of 55 ℃ to obtain a dark gray reaction product. The obtained dark gray reaction product is calcined and insulated for 2 hours at the temperature of 420 ℃ after being frozen and dried to obtain Au-TiO2-MWCNTs composite photocatalyst.
1.2 characterization and Performance testing of the samples
The obtained Au-TiO was subjected to the characterization method of example 12The micro-morphology of the MWCNTs composite photocatalyst is characterized, and the result shows that Au nanoparticles and TiO2The nano particles are uniformly distributed on the one-dimensional MWCNTs carrier and form a compact composite structure with the MWCNTs.
The Au-TiO compound obtained was subjected to the test method of example 12The MWCNTs composite photocatalyst is subjected to ultrasonic dispersion treatment and a treated sample is observed, and the result shows that after 2 hours of dispersion treatment, Au nanoparticles and TiO nanoparticles2The nano particles are still tightly combined with the MWCNTs carrier and are not stripped off due to ultrasonic dispersion, and Au/TiO2The nanoparticles and MWCNTs carriers form stable and firm combination.
The Au-TiO compound obtained was subjected to the test method of example 12The catalytic degradation test of the MWCNTs composite photocatalyst on styrene shows that Au-TiO2The MWCNTs composite photocatalyst has strong degradation and mineralization capacity on styrene, the highest adsorption rate of the MWCNTs composite photocatalyst on the styrene reaches 75%, the degradation efficiency of the styrene is stabilized at 74% within 300min of continuous degradation, no obvious decline trend exists, the mineralization efficiency of the styrene reaches 52%, and the obtained photocatalyst can effectively promote oxidative free radicals such as hydroxyl free radicals and hydroxyl free radicalsThe formation rate of the superoxide radical can effectively promote the degradation and mineralization of the styrene enriched on the surface of the photocatalyst, and simultaneously, the problems of product accumulation, catalyst inactivation and the like caused by the interface mass transfer problem are avoided.
Comparative example 1
1.1 preparation of samples
Dispersing multi-walled carbon nanotubes (MWCNTs) and sodium dodecyl sulfate in 10mL of aqueous solution, wherein the concentration of the MWCNTs is 14.5mg/mL, and the concentration of the sodium dodecyl sulfate is 5mg/mL to form suspension; dispersing the obtained suspension in 20mL of absolute ethyl alcohol, and stirring for 30min to obtain Solution I. 4.45mol of titanium isopropoxide, 15mL of ethanol and 0.1mL of acetic acid were mixed and stirred to form a clear Solution II. Dropwise adding the Solution I into the Solution II under magnetic stirring, stirring for reacting for 2 hours, adjusting the pH of the mixed Solution to 9 by adopting 1mol/L ammonia water Solution, adding 10mL of ethanol, and continuously stirring for 30 minutes; centrifugally separating the obtained product, and then drying the product in a 60 ℃ drying oven for 10 hours to obtain a first product, wherein MWCNTs and TiO in the product2The mass ratio of (3) is 0.4.
A chloroauric acid solution (3mL, 32.85mM) was added to a toluene solution of tetraoctylammonium bromide (3.982mL, 49.5mM) to change the solution from yellow to colorless, a toluene solution of dodecanethiol (0.4455mL, 0.1106M) was added thereto, the mixture was stirred for 15min, and the organic phase (about 4.43mL) of the resultant product was dried at room temperature using a vacuum drier and then washed with ethanol to obtain a second product (2 to 3nm Au nanoparticles).
Dispersing the obtained first product and 1mL of 3-mercaptopropionic acid (0.22M) in 4mL of toluene, and carrying out ultrasonic treatment for 2h to obtain a first dispersion liquid; dispersing the obtained second product in 2mL of toluene to obtain a second dispersion liquid; dropwise adding the second dispersion into the second dispersion under vigorous stirring, and continuously stirring for 5h to attach the nano Au to the TiO2/CNTs, washing with acetone for three times, drying overnight at normal temperature, then placing in a tube furnace, heating to 500 ℃ at the rate of 10 ℃/min, and keeping the temperature for 30min to obtain Au-TiO2-MWCNTs nanocomposites.
1.2 Performance testing of the samples
Pressing to realExample 1 test method for the obtained Au-TiO2The catalytic degradation test of the-MWCNTs composite material on styrene shows that the obtained Au-TiO2Although the adsorption rate of the MWCNTs composite material to the styrene can reach a level equivalent to that of the embodiment of the invention, the degradation and mineralization capacity of the MWCNTs composite material to the styrene is obviously poor, the degradation efficiency to the styrene is only 24.5% in 300min of continuous degradation, the degradation efficiency to the styrene is obviously reduced, the mineralization efficiency to the styrene is only less than 1%, and the obtained composite material shows poor photocatalytic degradation performance.
From the test effects, compared with the prior art, the preparation method provided by the invention greatly simplifies the preparation process, avoids the use of toxic organic solution and template agent, and the Au-TiO prepared by the invention2The MWCNTs composite photocatalyst has a stable and firm structure and precise spatial modification of nano Au, and further shows a better photocatalytic degradation effect.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A preparation method of a titanium dioxide-carbon nanotube composite photocatalyst modified by nanogold is characterized by comprising the following steps:
a) taking an aqueous solution of alcohol and stable gas as media, and processing by using a micro-nano bubble generator to obtain micro-nano bubble water;
b) mixing and dispersing the micro-nano bubble water, the carbon nano tube and the titanium salt to obtain a dispersion liquid;
c) mixing the dispersion liquid with an ammonia water solution, and hydrolyzing to obtain a hydrolysate;
d) mixing the hydrolysate with gold salt and micro-nano bubble water, and then sequentially carrying out illumination reduction and heating reaction to obtain a reaction product;
the temperature of the heating reaction is 25-90 ℃;
e) carrying out heat treatment on the reaction product to obtain Au-TiO2-a CNTs composite photocatalyst;
the temperature of the heat treatment is 200-450 ℃.
2. The preparation method according to claim 1, wherein in the step a), the working pressure of the micro-nano bubble generator is 0.25-0.65 MPa, the air inflow of the steady-state gas is 1.5-4.5L/min, and the water solution of the alcohol is 5-10L.
3. The method according to claim 1 or 2, wherein in the step a), the alcohol in the alcohol aqueous solution comprises one or more of ethanol and glycerol;
the mass concentration of the alcohol aqueous solution is 1-50%;
the steady state gas comprises air and N2、O2、CO2And H2One or more of them.
4. The preparation method of claim 1, wherein in the step b), the ratio of the mass of the carbon nanotube to the molar amount of the titanium salt is (12-119) mg to (2-10) mmol;
the mass ratio of the volume of the micro-nano bubble water to the carbon nano tube is (40-120) mL to (12-119) mg.
5. The preparation method according to claim 1, wherein in the step c), the mass concentration of the ammonia water solution is 1-5%;
and controlling the addition amount of the ammonia water solution until the mixed solution is in a sol state.
6. The method according to claim 1 or 5, wherein the hydrolysis time in step c) is 8-24 h.
7. The preparation method according to claim 1, wherein in the step d), the ratio of the volume of the micronano bubble water to the molar quantity of the gold salt is 10 mL: (0.004-0.032) mmol;
the molar ratio of the gold salt to the titanium salt in the step b) is (0.004-0.032) to (2-10).
8. The preparation method according to claim 1 or 7, wherein in the step d), the power of the illumination is 10-300W, and the time of the illumination reduction is 5-15 min;
the heating reaction time is 4-20 h.
9. The preparation method according to claim 1, wherein in the step e), the heat treatment time is 1.5-3 h.
10. The method of claim 1, wherein the carbon nanotubes are multi-walled carbon nanotubes; the pipe diameter of the multi-walled carbon nanotube is 8-60 nm;
the titanium salt is selected from TiCl4And TiOSO4One or more of the above;
the gold salt is selected from AuCl3And HAuCl4One or more of them.
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