CN108855188B - Modified titanium dioxide printing process and preparation method of modified titanium dioxide printing material - Google Patents
Modified titanium dioxide printing process and preparation method of modified titanium dioxide printing material Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a printing process of modified titanium dioxide and a preparation method of a modified titanium dioxide printing material, wherein the printing process comprises the following steps: 1) introducing amino ions and metal simple substances into titanium dioxide to obtain a printing material at least containing modified titanium dioxide; 2) and printing the printing material on a base fabric by using a printing device, wherein the base fabric is a fabric at least comprising profiled fibers. The fabric is made of profiled fibers, particularly fibers shaped like Chinese characters 'mi', the microstructure of the fibers has a groove body along the axial direction, modified titanium dioxide particles in the printing material enter the groove body, and the modified titanium dioxide particles with micro-nano sizes can be firmly combined with the fiber structure; by introducing amino cation into the titanium dioxide, the bonding firmness between the modified titanium dioxide and the fabric is ensured; the addition of metals such as silver can expand the spectral range of light absorption, so that the fabric has a good response effect under sunlight. The fiber and fabric obtained by printing has antibacterial and antistatic properties.
Description
Technical Field
The invention relates to a preparation method of a photocatalytic material, in particular to a preparation method of multi-element doped modified titanium dioxide powder photocatalysis with high visible light response and high catalytic efficiency and a printing process using the modified titanium dioxide dye.
Background
The nano titanium dioxide is used as an important inorganic transition metal oxide material, and has high catalytic activity, good weather resistance and excellent ultraviolet resistance. In recent years, the research on titanium dioxide nano materials is increasing, and the titanium dioxide nano materials are receiving attention in the fields of wastewater treatment, sun protection and skin care, coatings, sensors, photocatalysts and the like. Compared with other transition metal oxides, the nano titanium dioxide can absorb ultraviolet rays, reflect the ultraviolet rays and transmit visible light, and is an ultraviolet protective agent with excellent performance and great development prospect. However, the pure nano titanium dioxide semiconductor material as a catalyst has some defects: firstly, the forbidden band width of the solar energy collector is wide (Eg is 3.2ev), and the solar energy collector only can absorb ultraviolet light with the wavelength less than 387nm and does not have effect on visible light which accounts for most of sunlight; secondly, the recombination probability of electron-hole is high, the survival time of effective photon is short, the quantity is small, and the nano titanium dioxide can not fully exert the catalytic performance.
In order to improve the application of the nano titanium dioxide in the field of photocatalysis, a large number of reports show that doping the nano titanium dioxide to reduce the forbidden bandwidth or improve the absorption of visible light is an effective method. The doping method relates to metal and nonmetal doping, ion doping, semiconductor compounding, surface modification and the like, wherein the noble metal doping effect is the best, and the doping method comprises an ultraviolet light reduction method, a chemical reduction method, an electrochemical deposition method and the like. When the modified nano titanium dioxide is excited by light, electrons generated in the valence band flow to metal with lower Fermi energy, so that photoproduction electrons and holes are separated, the quantum efficiency is improved, and the photocatalysis performance of the nano titanium dioxide is further improved. Common metals are doped with Pt, Ag, Pd and various rare metals, metal ions and metal oxides, but the utilization of visible light by metal doping is still low. The nonmetal doping mainly takes N doping as a main part, but the N doping also easily causes the recombination of electrons and holes, and reduces the photocatalytic efficiency. Therefore, the titanium dioxide particles doped with metal and nonmetal can act synergistically, so that the visible light region is effectively expanded, the photocatalytic efficiency is improved, and the photocatalytic material which can be widely applied is prepared.
The photocatalytic performance of the nano titanium dioxide is greatly related to the form of the nano titanium dioxide, and the existing forms of the nano titanium dioxide include spheres, rods, linearity and the like. The preparation method of the titanium dioxide nano-particles comprises a sol-gel method, a microemulsion method, a solvent method and a hydrothermal reaction method, and generally the titanium dioxide particles are prepared firstly and then are prepared by hydrothermal method. The size, the size distribution and the reaction conditions of the nano titanium dioxide particles prepared by the methods directly influence the surface appearance and the size uniformity of the titanium dioxide particles, and the two-step synthesis method has high energy consumption and serious pollution and does not meet the production requirements of low energy consumption and green production.
The photocatalysis property of the modified nano titanium dioxide is also related to the state, structure, content, distribution and the like of the dopant. For example, when a metal simple substance, especially a gold simple substance, is doped, the catalytic activity of the gold simple substance is influenced by the size, the loading amount and the like of the nano gold particles. Research shows that when the size of gold particles is less than 10nm, the gold particles show higher catalytic activity; when the loading of the gold simple substance is less than 5%, small-size gold particles can be easily obtained. In addition, the specific surface area of the nano titanium dioxide and the interaction with the gold particles also affect the activity of the composite catalyst. When the load is too large, the recombination of electrons and holes is accelerated, and the catalytic efficiency is reduced. In conclusion, the size of the metal particles and the controllable distribution on the nano titanium dioxide are important in the process of loading the metal particles. In addition, the simple, convenient and efficient preparation process is adopted, the processing time is shortened, the cost is saved, and the method is also a development direction of the future technology.
The plane material, especially the textile plane material can obviously improve the catalytic activity, good weatherability and excellent ultraviolet resistance of the plane material after loading the modified nano titanium dioxide.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a printing process which is simple and can realize better modified titanium dioxide printing material and a method for preparing co-doped modified titanium dioxide printing materials such as N-Au or/and N-Ag. The N-Au or/and N-Ag co-doped titanium dioxide powder prepared by the method has the advantages of antibiosis, ultraviolet resistance, high catalytic activity, environmental protection and no pollution, and can be widely applied to the aspects of textile, gas purification, sewage treatment, solar cells and the like.
The first technical scheme of the invention is as follows: a printing process of modified titanium dioxide comprises the following steps:
(1) preparing a printing material: introducing amino ions and metal simple substances into titanium dioxide to obtain a printing material at least containing modified titanium dioxide;
(2) printing treatment: and printing the printing material on a base fabric by using a printing device, wherein the base fabric is a fabric at least comprising profiled fibers.
Furthermore, the cross section of the profiled fiber is in a cross-shaped structure, an x-shaped structure or a meter-shaped structure.
Further, the metal in the metal simple substance is Au, Ag or Cu.
Further, the printing material also comprises a printing dye.
The printing of the invention is not limited to the printing process aiming at the cloth appearance and design in the prior art, but also comprises a mode of transferring the modified titanium dioxide printing material to the base cloth by spraying, painting, spraying and the like, and aims to attach the modified titanium dioxide printing material to the surface of the base cloth in a certain mode and endow the base cloth with certain antibacterial, ultraviolet-resistant and high catalytic activity.
The second technical scheme of the invention is as follows: a preparation method of a modified titanium dioxide printing material comprises the following steps:
(a) adding tetrabutyl titanate solution into the acidic solution, stirring and standing the solution to convert the solution into a gel-like substance, namely titanium dioxide gel;
(b) mixing a solution containing a gold simple substance or a silver simple substance with a solution of an amino-terminated hyperbranched polymer;
(c) fully mixing the titanium dioxide gel obtained in the step (a) with the mixed solution obtained in the step (b), keeping the temperature in the range of 180-240 ℃ for a period of time, and drying to obtain modified titanium dioxide powder;
(d) and (c) dissolving the modified titanium dioxide powder obtained in the step (c) in water or an organic solvent to obtain the modified titanium dioxide printing material.
The third technical scheme of the invention is as follows: a preparation method of a modified titanium dioxide printing material comprises the following steps:
adding tetrabutyl titanate solution into acid solution, stirring and standing to convert into gel-like substance, namely titanium dioxide gel;
(II) adding chloroauric acid solution or silver nitrate or copper sulfate into the hyperbranched polymer solution, and heating to boil;
(III) adding the solution containing the gold simple substance or the silver simple substance in the step (II) into the solution of the amino-terminated hyperbranched polymer, and uniformly mixing;
(IV) fully mixing the titanium dioxide gel obtained in the step (I) with the mixed solution obtained in the step (III), and keeping the temperature of the mixed solution at 180-240 ℃ for a period of time; then washing and drying to obtain modified titanium dioxide powder;
and (V) dissolving the modified titanium dioxide powder obtained in the step (IV) in water to obtain the modified titanium dioxide printing material.
Further, the concentration of the tetrabutyl titanate solution is 50-150 g/L.
Furthermore, the concentration of the amino-terminated hyperbranched polymer solution is 10-100 g/L.
Further, the mass ratio of the titanium dioxide gel to the mixed solution is 1: 5-1: 10.
Further, the concentration of the modified titanium dioxide powder dissolved in water or an organic solvent is 0.5 to 20 g/L.
The amino-terminated hyperbranched polymer is a polymer which has a spherical-like porous three-dimensional network structure, a large amount of active amino groups, high solubility and high viscosity. The polymer has a large number of gaps inside, and can be used as a nano reaction container to control the formation of nano particles with small particle size and stable appearance.
The invention utilizes the principle that the amino-terminated hyperbranched polymer can perform complex reduction on chloroauric acid, nitrate ions and the like and simultaneously control the growth of titanium dioxide particles. In the hydrothermal boiling process, metal ions are reduced into a metal simple substance by amino in the amino-terminated hyperbranched polymer, and meanwhile, the metal simple substance is stably dispersed in the solution by the three-dimensional network structure of the amino-terminated hyperbranched polymer. The special structure of the amino-terminated hyperbranched polymer provides the function of a nano reaction container, and controls the formation size of metal simple substances and titanium dioxide particles. In the high-temperature process, abundant amino can permeate into the nano titanium dioxide crystal lattice to form N doping. Through the hydrothermal high-temperature process, the gold simple substance or the silver simple substance is adhered to the titanium dioxide particles through the action of hydrogen bonds, and further the N-Au or N-Au co-doped modified titanium dioxide particles are obtained.
Compared with the prior art, the invention has the following advantages: (1) the amino-terminated hyperbranched polymer can be used for controllably obtaining composite titanium dioxide particle powder; (2) the preparation process is simple, the size of the metal single substance (preferably the gold single substance and the silver single substance) is controllable, the production efficiency is improved, and the cost is saved; (3) the concentration ratio of the chloroauric acid or the silver nitrate to the amino-terminated hyperbranched polymer is adjusted to be higher than the size of the gold nanoparticles which can be effectively controlled; (4) the doped nano gold particles are uniformly distributed on the titanium dioxide, so that the doped nano gold particles can be better applied to various fields; (5) the modified titanium dioxide printing material is processed on the surface of the fabric and in gaps among fibers by using a printing and spraying process, so that the processed surface material, particularly the fabric has the capabilities of antibiosis, ultraviolet resistance and high catalytic activity; the modified titanium dioxide printing material is coated on the surface of the fabric, so that the modified titanium dioxide in the printing material can exert the maximum efficiency; (6) the fabric is made of profiled fibers, particularly fibers shaped like Chinese characters 'mi', the microstructure of the fibers has a groove body along the axial direction, and modified titanium dioxide particles in the printing material easily enter the groove body, so that the modified titanium dioxide particles with micro-nano sizes can be firmly combined with the fiber structure, and the printing material is firmly combined with the fabric on the whole; (7) by introducing amino cation into the titanium dioxide, the amino cation has the performance of cationic dye in printing dye, can be well combined with chemical fiber, and ensures the combination firmness between the modified titanium dioxide and the fabric; (8) the addition of metals such as silver can expand the spectral range of light absorption, so that the fabric has a good response effect under sunlight. The fiber and fabric obtained by printing has antibacterial and antistatic properties.
Drawings
The invention is further explained below with reference to the figures and examples;
FIG. 1 is a transmission electron micrograph of N-Au co-doped titanium dioxide particles prepared in example 5;
FIG. 2 is an SEM image of a cross-section fiber after being sprayed with titanium dioxide.
Detailed Description
In order to clarify the technical solution and technical object of the present invention, the present invention will be further described with reference to the accompanying drawings and specific examples.
Example 1:
introducing amino ions and a gold simple substance into titanium dioxide to obtain a printing material at least containing modified titanium dioxide; printing the printing material containing the modified titanium dioxide on base cloth by using printing equipment, wherein the base cloth is a fabric at least comprising profiled fibers with a structure shaped like a Chinese character 'mi', and the metal in the metal simple substance is preferably Au.
Example 2:
80ml of an ethanol solution of tetrabutyl titanate having a concentration of 125g/L was added dropwise to a mixed solution composed of 10ml of formic acid and 10ml of deionized water, and the mixture was stirred until the solution became light blue. Standing and aging until the sol is in a gel state. 0.5ml of chloroauric acid ethanol solution with the concentration of 0.1mol/L is added into 10ml of amino-terminated hyperbranched polymer aqueous solution with the concentration of 30g/L, and the mixture is heated and boiled until the solution is light pink. 50ml of ethanol solution of amino-terminated hyperbranched polymer with the concentration of 60g/L is mixed and added into the solution, the solution is continuously stirred until the mixture is uniformly mixed, 10g of titanium dioxide gel is added, the mixture is uniformly mixed by a cell crusher and then is placed into a polytetrafluoroethylene reaction kettle, and the mixture is heated for 8 hours at the temperature of 200 ℃. And after cooling, washing the solution with ethanol for three times, centrifuging, washing with deionized water for three times, centrifuging, and drying to obtain the N-Au co-doped composite titanium dioxide nano catalyst with the average particle size of 26.5nm, the gold content of 1.2680% and the gold particle diameter of 10.9 nm. Dissolving the N-Au composite titanium dioxide nano particles in an aqueous solution with a certain concentration to prepare a modified titanium dioxide dye, and treating the modified titanium dioxide dye on the surface of the fabric in the shape of a Chinese character 'mi' through a printing process to obtain the titanium dioxide printing process fabric.
Example 3:
80ml of an ethanol solution of tetrabutyl titanate having a concentration of 125g/L was added dropwise to a mixed solution composed of 10ml of formic acid and 10ml of deionized water, and the mixture was stirred until the solution became light blue. Standing and aging until the sol is in a gel state. 0.30ml of silver nitrate aqueous solution with the concentration of 0.1mol/L is added into 10ml of amino-terminated hyperbranched polymer aqueous solution with the concentration of 50g/L, and the solution is heated and boiled until the solution is bright yellow. Mixing 30ml of ethanol solution of amino-terminated hyperbranched polymer with the concentration of 15g/L, adding the mixture into the solution, continuously stirring the mixture until the mixture is uniform, adding 10g of titanium dioxide gel, uniformly mixing the mixture by using a cell crusher, putting the mixture into a polytetrafluoroethylene reaction kettle, and heating the mixture for 10 hours at the temperature of 200 ℃. After cooling, the solution is washed with ethanol for three times, centrifuged, washed with deionized water for three times, centrifuged and dried to obtain the N-Au co-doped composite titanium dioxide nano catalyst with the average particle size of 33.1nm, the silver content of 0.8911% and the silver particle diameter of 6.6 nm. Dissolving the N-Au composite titanium dioxide nano particles in an aqueous solution with a certain concentration to prepare a modified titanium dioxide dye, and treating the modified titanium dioxide dye on the surface of the fabric in the shape of a Chinese character 'mi' through a printing process to obtain the titanium dioxide printing process fabric.
Example 4:
88ml of a 90g/L tetrabutyltitanate ethanol solution was added dropwise to a mixed solution composed of 15ml of formic acid and 10ml of deionized water, and the mixture was stirred until the solution became light blue. Standing and aging until the sol is in a gel state. 0.30ml of chloroauric acid ethanol solution with the concentration of 0.2mol/L is added into 10ml of amino-terminated hyperbranched polymer aqueous solution with the concentration of 80g/L, and the solution is heated and boiled until the solution is light pink. 50ml of ethanol solution of amino-terminated hyperbranched polymer with the concentration of 15g/L is mixed and added into the solution, the solution is continuously stirred until the mixture is uniformly mixed, 15g of titanium dioxide gel is added, the mixture is uniformly mixed by a cell crusher and then is placed into a polytetrafluoroethylene reaction kettle, and the mixture is heated for 6 hours at the temperature of 230 ℃. After cooling, the solution is washed with ethanol for three times, centrifuged, washed with deionized water for three times, centrifuged and dried to obtain the N-Au co-doped composite titanium dioxide nano catalyst with the average particle size of 35.7nm, the gold content of 1.0273 percent and the gold particle diameter of 6.7 nm. Dissolving the N-Au composite titanium dioxide nano particles in an aqueous solution with a certain concentration to prepare a modified titanium dioxide dye, and treating the modified titanium dioxide dye on the surface of the fabric in the shape of a Chinese character 'mi' through a printing process to obtain the titanium dioxide printing process fabric.
Example 5:
86ml of a tetrabutyltitanate ethanol solution having a concentration of 70g/L were added dropwise to a mixed solution composed of 18ml of formic acid and 10ml of deionized water, and the mixture was stirred until the solution became light blue. Standing and aging until the sol is in a gel state. 0.30ml of silver nitrate aqueous solution with the concentration of 0.08mol/L is added into 10ml of amino-terminated hyperbranched polymer aqueous solution with the concentration of 50g/L, and the solution is heated and boiled until the solution is bright yellow. 550ml of ethanol solution of the amino-terminated hyperbranched polymer with the concentration of 18g/L is mixed and added into the solution, the solution is continuously stirred until the mixture is uniformly mixed, 8g of titanium dioxide gel is added, the mixture is uniformly mixed by a cell crusher and then is placed into a polytetrafluoroethylene reaction kettle, and the mixture is heated for 14 hours at the temperature of 220 ℃. After cooling, the solution is washed with ethanol for three times, centrifuged, washed with deionized water for three times, centrifuged and dried to obtain the N-Ag co-doped composite titanium dioxide nano catalyst with the average particle size of 20.5nm, the silver content of 1.6037% and the silver particle diameter of 6.2 nm. Dissolving the N-Ag composite titanium dioxide nano particles in an aqueous solution with a certain concentration to prepare a modified titanium dioxide dye, and treating the modified titanium dioxide dye on the surface of the fabric in the shape of a Chinese character 'mi' through a printing process to obtain the titanium dioxide printing process fabric.
Fig. 1 is a transmission electron microscope image of the composite titanium dioxide nanoparticles obtained in example 5, and it is apparent from the image that the titanium dioxide nanoparticles have good and uniform formation property, a particle diameter of about 20nm, and many particles doped on the surface. In fig. 2, cavities (grooves such as pores) are formed on the smooth surface of the foreign fiber after alkali etching, and the cavities are filled with nano titanium dioxide powder after spraying.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. 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 (8)
1. The printing process of the modified titanium dioxide is characterized by comprising the following steps:
(1) preparing a printing material: introducing amino ions and metal simple substances into titanium dioxide to obtain a printing material at least containing modified titanium dioxide; the metal in the metal simple substance is Au, Ag or Cu;
(2) printing treatment: printing the printing material on a base cloth by using printing equipment, wherein the base cloth is a fabric at least comprising profiled fibers; the cross section of the profiled fiber is in a cross structure or a rice-shaped structure.
2. The printing process according to claim 1, wherein: the printing material also comprises a printing dye.
3. The printing process according to claim 1, wherein the preparation method of the printing material of the modified titanium dioxide comprises the following steps:
(a) adding tetrabutyl titanate solution into the acidic solution, stirring and standing the solution to convert the solution into a gel-like substance, namely titanium dioxide gel;
(b) mixing a solution containing a gold simple substance or a silver simple substance with a solution of an amino-terminated hyperbranched polymer;
(c) fully mixing the titanium dioxide gel obtained in the step (a) with the mixed solution obtained in the step (b), keeping the temperature in the range of 180-240 ℃ for a period of time, and drying to obtain modified titanium dioxide powder;
(d) and (c) dissolving the modified titanium dioxide powder obtained in the step (c) in water or an organic solvent to obtain the modified titanium dioxide printing material.
4. The printing process according to claim 1, wherein the preparation method of the printing material of the modified titanium dioxide comprises the following steps:
adding tetrabutyl titanate solution into acid solution, stirring and standing to convert into gel-like substance, namely titanium dioxide gel;
(II) adding chloroauric acid solution or silver nitrate into the hyperbranched polymer solution, and heating to boil;
(III) adding the solution containing the gold simple substance or the silver simple substance in the step (II) into the solution of the amino-terminated hyperbranched polymer, and uniformly mixing;
(IV) fully mixing the titanium dioxide gel obtained in the step (I) with the mixed solution obtained in the step (III), and keeping the temperature of the mixed solution at 180-240 ℃ for a period of time; then washing and drying to obtain modified titanium dioxide powder;
and (V) dissolving the modified titanium dioxide powder obtained in the step (IV) in water to obtain the modified titanium dioxide printing material.
5. The printing process according to claim 3 or 4, wherein: the concentration of the tetrabutyl titanate solution is 50-150 g/L.
6. The printing process according to claim 3 or 4, wherein: the concentration of the amino-terminated hyperbranched polymer solution is 10-100 g/L.
7. The printing process according to claim 3 or 4, wherein: the mass ratio of the titanium dioxide gel to the mixed solution is 1: 5-1: 10.
8. The printing process according to claim 3 or 4, wherein: the concentration of the modified titanium dioxide powder dissolved in water or an organic solvent is 0.5-20 g/L.
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