CN115845828A - Ti-Br composite photocatalytic material, photocatalytic component, preparation method and application - Google Patents
Ti-Br composite photocatalytic material, photocatalytic component, preparation method and application Download PDFInfo
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Abstract
Hair brushThe Ti-Br composite photocatalytic material consists of visible light photosensitive material and nanometer level TiO 2 The visible light photosensitive material is eosin or TiO 2 The mass ratio of the powder to the eosin is (1-50): 1,TiO 2 2 The particle size of the powder is 10-40 nm. The Ti-Br composite photocatalytic material and the photocatalytic component obtained by the preparation method improve the light absorption range and the utilization rate of sunlight; the raw materials for preparing the material have wide sources and low cost; by loading the Ti-Br composite photocatalytic material on the attachment matrix, the preparation and attachment synchronous treatment is realized, the production process is simpler and more convenient, the problems of difficult recovery and easy loss of the photocatalytic powder are solved, and the installation is simple and convenient; meanwhile, the photocatalytic component can be assembled into different shapes, so that the integration of air purification and landscaping is realized.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a Ti-Br composite photocatalytic material, a photocatalytic component, a preparation method and application.
Background
Photocatalysis is a process of decomposing pollutant molecules into inorganic small molecules by carriers generated after a photocatalyst is excited by light, and is a technology for degrading organic matters. The technology shows unique advantages in the field of wastewater and waste gas treatment by virtue of the advantages of high treatment efficiency, no need of additional chemical agents and the like.
The reaction mechanism of the photocatalysis technology is that the photocatalyst absorbs light energy while adsorbing and catalyzing a target object, and photochemical reaction is carried out between photo-generated electrons and holes generated by light excitation and target pollutants. The photocatalysis technology can completely mineralize organic substances and part of inorganic substances harmful to human bodies and environment into CO almost without selectivity within enough reaction time 2 And H 2 O and the like.
Urban roads are complex, the traffic is busy, road isolation zones are seriously polluted, including organic and inorganic particulate matters in automobile exhaust, a mixture of rainfall and ground silt and the like, and pollutants are accumulated in isolation zones, service areas and living areas on two sides of the roads all the year round, so that the road appearance is influenced. Therefore, the above-mentioned places, especially the isolation belts, are required to be cleaned with high strength. At present, no mature treatment technology exists for purifying the air pollutants in the open environment.
(1) Semiconductor photocatalytic material
The key of the photocatalysis technology is to synthesize high-efficiency photocatalysis materials, and the most commonly used photocatalyst at the present stage is a semiconductor material. Semiconductor materials, which are substances having a conductivity between that of a conductor and an insulator, have unique optical and electrical properties because of a narrow band gap. Semiconductor materials can be further classified into intrinsic semiconductors, N-type semiconductors, and P-type semiconductors according to the difference in carriers. In an intrinsic semiconductor, an electron, when excited, jumps from the valence band to the conduction band of the material, thereby forming an equal number of holes and electrons. Such electrons and holes are called charge carriers. An extrinsic semiconductor is also called a doping type semiconductor, and in an N-type semiconductor, a donor transports electrons to a conduction band and is a material in which many electrons are present; in a P-type semiconductor, an acceptor accepts electrons in a valence band, and many of the electrons are holes.
The commonly used N-type semiconductors are mainly: tiO 2 2 、WO 3 、CdS、Fe 2 O 3 ZnO and SnO, etc., wherein TiO 2 The semiconductor oxide has the advantages of rich and easily available raw materials, low cost, high chemical stability, excellent photocatalytic performance and the like, and is one of the most widely researched and used semiconductor oxides at present.
(2) Coating catalysis technology for photocatalytic material
Literature I (Guo Yin Chuan, jie Shi, shen Aiqin, zhang Youhua, coating type composite nano photocatalytic material tunnel tail gas degradation research [ J]Silicate report, 2019,38 (08): 2563-2569) discloses that the tail gas in a tunnel is taken as a research object, and the structure depth of a composite nano photocatalytic material coating and the tail gas degradation performance of nano photocatalytic materials with different doping amounts are researched. The coating type composite nano photocatalytic material has a certain effect on the tail gas degradation of the tunnel steel slag asphalt mixture and has a certain influence on the construction depth. The result shows that the modified nano photocatalytic material is applied to the surface of the tunnel steel slag asphalt mixture in a coating way, and when nano TiO is used 2 And nano CeO 2 When the doping ratio relative to the coating dosage reaches 5% and 10% respectively, the peak value of degradation efficiency can be obtained, the degradation efficiency of HC and NO can reach 41.7% and 68.7%, and the tail gas degradation rate within 30min can reach 78.5ppm/min and 333.9ppm/min respectively.
(3) Photocatalytic road stabilizer
Document II (Xueshi method, li Sitong, li Shufei, li Zhi, li Junzhong, niuyanjun. Automobile exhaust gas degradation material road stabilizer development and performance evaluation [ J]The Chinese highway journal, 2019,32 (04): 114-121) discloses that a pavement fog sealing layer and a sand-containing fog sealing layer are used as photocatalytic carriers to develop a pavement-used photocatalyst, and the treatment of harmful gases in automobile exhaust is one of the directions of photocatalyst development. Researchers develop cellulose high-molecular polymer stabilizers with polyacrylamide chain grafting based on self-developed nitrogen-doped titanium dioxide-based degradation materials, and provide stability evaluation methods and evaluation indexes. The result shows that the stabilizer can obviously improve the compatibility and stability between the degradation material and the carrier, the stability coefficient is not more than 5.5 percent under the conditions of 2 percent of doping amount and 180 hours of storage time, the requirement of engineering application is met, and the stabilizer can treat NO in tail gas x The degradation rates of HC and CO are respectively improved by more than 20%, 11% and 7%.
The applicant found through the research of the prior art that the following defects exist:
(1) Narrow spectral response range
The absorption value of pure titanium dioxide is 387nm, the light absorption range is limited to an ultraviolet region, the ultraviolet light in sunlight only accounts for about 5%, and the quantum efficiency of titanium dioxide is very low and basically does not exceed 20%, so that the utilization rate of the titanium dioxide to solar energy is only about 1%.
(2) Easy recombination of photon-generated carriers and low quantum efficiency
The lifetime of the photogenerated electron-hole in titanium dioxide is ns level, and the recombination is easy to occur, so that the photon yield is very low.
(3) The powder photocatalyst is easy to run off and difficult to recover
The catalytic activity of the catalyst is strongly related to the particle size. The smaller the particle size, the better the catalytic effect, but the photocatalyst with small particle size is dispersed in the treatment system and is easy to run off along with the discharge of the treated fluid.
(4) Products not directed to open environment fluid treatment
At present, no photocatalytic product for purifying open environment atmosphere in tunnels, expressways, refuse landfills, chemical plants and the like exists, and only photocatalytic research and development materials taking tunnels as application situations and photocatalytic additives added into pavement building materials are reported in documents. Therefore, the construction convenience and universality of the site in the prior art and research and development samples are not solved.
Disclosure of Invention
The invention aims to provide a Ti-Br composite photocatalytic material, a photocatalytic component, a preparation method and application, and solves the problems of low titanium dioxide light utilization rate, easy loss of photocatalytic powder, construction convenience of photocatalytic products, universality of use scenes and the like in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a Ti-Br composite photocatalytic material, which is prepared from a visible light photosensitive material and nano-scale TiO 2 The visible light photosensitive material is eosin and TiO 2 The mass ratio of the powder to the eosin is (1-50): 1,TiO 2 2 The particle size of the powder is 10-40 nm.
The visible light photosensitive material eosin and the nanoscale titanium dioxide powder are compounded to prepare the Ti-Br composite photocatalytic material capable of absorbing sunlight visible light and ultraviolet light.
In a second aspect, the invention provides a preparation method of the above Ti-Br composite photocatalytic material, which comprises the following steps: weighing eosin, putting the eosin into pure water, stirring the mixture evenly in a dark place to prepare an eosin solution with the concentration of 0.25 to 10g/L, and adding TiO with the weight of 1 to 50 times of that of the eosin into the eosin solution 2 The powder is put in a dark water bath at 30 ℃ and stirred evenly to obtain TiO 2 Eosin solution, dried and dehydrated. The preparation method is easy to operate and can ensure that eosin and TiO are mixed 2 The powder is uniformly dispersed, and the photocatalysis effect is fully exertedAnd (5) fruit.
In a third aspect, the invention provides a photocatalytic component, which comprises an attachment substrate, wherein the surface of the attachment substrate is attached with the Ti-Br composite photocatalytic material. The adhesion matrix plays a role in loading, and the problem that the photocatalytic powder is difficult to recycle and easy to run off is solved by loading the Ti-Br composite photocatalytic material on the adhesion matrix, so that the subsequent construction and installation are facilitated.
Preferably, the attachment substrate is an iron-based mesh, an aluminum-based mesh, or a stainless steel-based mesh. The mesh structure matrix made of the plate-shaped material can load a large amount of Ti-Br composite photocatalytic materials, so that a good photocatalytic effect is provided, and rapid construction and installation are facilitated.
Further, a frame is fixed to the outer periphery of the attachment substrate. Therefore, the photocatalytic components can be spliced and assembled into plates of different sizes by utilizing the frame or fixedly installed on the surfaces of the anti-collision fences, structures and the like, the assembly and installation are very convenient, and the construction convenience and the use scene universality are good. Preferably, the frame is made of aluminum alloy.
Furthermore, a buckle is arranged on the frame, and the adjacent photocatalytic assemblies are spliced through the buckle. Therefore, the two photocatalytic assemblies can be spliced, connected and fixed together conveniently.
Or, a through hole is formed in the frame, and the adjacent photocatalytic assemblies are locked and connected at the through hole through a fastener. Preferably, the fastener is a bolt. The two photocatalytic assemblies can be conveniently connected and fixed together in a bolt mode.
Or, the adjacent photocatalytic assemblies are hinged through hinges, and two blades of each hinge are fixedly connected with the corresponding photocatalytic assemblies respectively. Through the hinge joint of the hinge, the two photocatalytic assemblies can be conveniently spliced and fixed together, and the photocatalytic assemblies can also be rotated and placed according to a specific angle for construction and fixation.
In a fourth aspect, the present invention provides a method for preparing the above photocatalytic module, comprising the following steps:
s1, weighing eosin, putting the eosin into pure water, and stirring the eosin in a dark place until the eosin is uniform to prepare an eosin solution with the concentration of 0.25-10 g/L;
s2, adding TiO with the weight of 1-50 times that of eosin into the eosin solution 2 Powder to form TiO 2 Eosin solution, taking the adhesion matrix immersed in the TiO formed 2 Eosin solution, in a dark water bath at 30 ℃, stirred and heated to 80 ℃, and then kept at the temperature for 1.5h;
s3, taking out the TiO adhered 2 And adhering matrix of eosin, and oven drying.
Further, in step S2, the adhering substance is pretreated with an acidic cleaning solution and an alkaline cleaning solution, respectively, before being immersed and adhered. Thus, tiO can be made 2 And eosin can be firmly attached to the attachment matrix.
Preferably, the acidic cleaning solution is 1M citric acid solution or hydrochloric acid, the alkaline cleaning solution is 1M NaOH solution, and the cleaning time of both the acidic cleaning solution and the alkaline cleaning solution is 15min.
Further, in step S2, the stirring temperature-raising process is: stirring at 200r/min for 10min, and heating at 5 deg.C/min.
Further, in step S3, the drying process is: will be adhered with TiO 2 And the adhering substrate of eosin was dried in a drying oven at 100 ℃ for 1h in dark.
In a fifth aspect, the invention provides an application of the Ti-Br composite photocatalytic material or the photocatalytic component in catalytic degradation of air pollutants under irradiation of visible light and/or ultraviolet light.
For example, the Ti-Br composite photocatalytic material or the photocatalytic component containing the Ti-Br composite photocatalytic material can be applied to places such as tunnels, expressways, refuse landfills or chemical plants for photocatalytic degradation of pollutants. Specifically, the photocatalytic component can be installed and fixed on a roadbed, an anti-collision belt, an anti-collision wall, an anti-collision fence, a building wall surface and a building surface through fasteners such as bolts, fixing strips or supporting frames; or can be fixed on the surface of the tree and the surface of the lamp post; or, different font models, sign models or pattern models are formed by combining and splicing, and a good text and travel modeling effect is achieved.
Compared with the prior art, the invention provides a Ti-Br composite photocatalytic material, a photocatalytic component, a preparation method and application, and has the following beneficial effects:
(1) According to the invention, the visible light photosensitive material eosin is compounded with the nano-scale titanium dioxide powder to prepare the Ti-Br composite photocatalytic material, the light absorption range comprises ultraviolet light and visible light, the utilization rate of sunlight is improved, and the absorption effect of the sunlight on the visible light and the ultraviolet light is good; meanwhile, the raw materials for preparation are wide in source and low in cost.
(2) According to the invention, the Ti-Br composite photocatalytic material is loaded on the adhesion substrate, so that the preparation and adhesion synchronous treatment is realized, the production process is simpler and more convenient, and the problems that the photocatalytic powder is difficult to recycle and easy to run off are solved.
(3) The photocatalytic component provided by the invention is simple and convenient to install and is convenient for subsequent on-site rapid construction and installation.
(4) The photocatalytic component can be assembled into different shapes, thereby playing a role in catalyzing and purifying air pollutants and meeting the requirements of scene construction on site; the device has low requirement on installation places, and can be installed on different objects such as road anti-collision barriers, isolation belts, forests, lamp posts and the like. Meanwhile, the assembly and field installation form of the photocatalytic component integrates travel elements, and air purification and beautification of public places such as traffic and the like are integrated.
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, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic structural view of a photocatalytic assembly according to the present invention;
FIG. 2 is a schematic view of two adjacent photocatalytic assemblies connected by a fastener;
FIG. 3 is a schematic view of two adjacent photocatalytic assemblies hinged together by a hinge;
FIG. 4 is a schematic view of the application of the photocatalytic module to the anti-collision wall;
FIG. 5 is a schematic view of the application of the photocatalytic component laid and fixed on the anti-collision fence;
FIG. 6 is a schematic diagram of the application of the photocatalytic components to form a font;
FIG. 7 is a schematic diagram of the application of the photocatalytic assembly to lay and splice the photocatalytic assembly into a logo shape;
FIG. 8 is a schematic diagram of the application of the photocatalytic assembly to lay and splice the photocatalytic assembly into a pattern;
FIG. 9 is a Fourier transform infrared absorption spectrum of the Ti-Br composite photocatalytic material;
FIG. 10 is a scanning electron micrograph of titanium dioxide;
FIG. 11 is a scanning electron microscope image of a Ti-Br composite photocatalytic material;
FIG. 12 is a graph showing the effect of the photocatalytic degradation treatment on ciprofloxacin in accordance with the present invention;
FIG. 13 is a graph showing the effect of the photocatalytic degradation treatment on volatile organic compounds according to the present invention.
Reference numerals: 10. a photocatalytic component; 1. attaching a substrate; 2. a frame; 21. a through hole; 3. a bolt; 4. loose leaves; 5. an anti-collision wall; 6. anticollision fence.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The starting materials used in the present invention are all commercially available. TiO 2 2 The powder is TitaniuDioxide (TiO) from ACS MATERIAL 2 ) P25, particle size of 10-40 nm.
The present invention will be described in further detail below by way of detailed embodiments in conjunction with the accompanying drawings.
Example 1
This example provides a composite photocatalytic Ti-Br material prepared from visible light photosensitive material eosin and nanoscale TiO 2 Is prepared by compounding powder and is TiO 2 The mass ratio of powder to eosin is 50:1, tiO 2 The particle size of the powder is 10-40 nm.
Specifically, the preparation method of the Ti-Br composite photocatalytic material of the embodiment includes the following steps: weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in a dark place at the speed of 300r/min to prepare an eosin stock solution with the concentration of 10 g/L; diluting an eosin stock solution to obtain an eosin use solution with a concentration of 0.25g/L, and adding TiO with an amount of 50 times of the weight of eosin into the eosin use solution 2 Powder, water bath is carried out in a dark place at 30 ℃, and TiO is obtained after uniform stirring 2 Drying and dehydrating the eosin solution to obtain a powder sample, namely the Ti-Br composite photocatalytic material.
Example 2
This example provides a Ti-Br composite photocatalytic material prepared from visible light photosensitive material eosin and nano-scale TiO 2 Is prepared by compounding powder and is TiO 2 The mass ratio of powder to eosin is 10:1,TiO 2 2 The particle size of the powder is 10-40 nm.
Specifically, the preparation method of the Ti-Br composite photocatalytic material of the embodiment includes the following steps: weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in a dark place at the speed of 300r/min to prepare an eosin stock solution with the concentration of 10 g/L; diluting the eosin stock solution to obtain an eosin use solution with a concentration of 0.50g/L, and adding TiO with an amount of 10 times of the weight of the eosin into the eosin use solution 2 Powder, water bath is carried out in a dark place at 30 ℃, and TiO is obtained after uniform stirring 2 Drying and dehydrating the eosin solution to obtain a powder sample, namely the Ti-Br composite photocatalytic material.
Example 3
This example provides a composite photocatalytic Ti-Br material prepared from visible light photosensitive material eosin and nanoscale TiO 2 The powder is prepared by compounding TiO 2 The mass ratio of powder to eosin is 5:1,TiO 2 2 The particle size of the powder is 10-40 nm.
Specifically, the preparation method of the Ti-Br composite photocatalytic material of the embodiment includes the following steps: weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in a dark place at the speed of 300r/min to prepare an eosin stock solution with the concentration of 10 g/L; diluting the eosin stock solution to obtain an eosin use solution with a concentration of 0.75g/L, and adding TiO with an amount of 5 times of the weight of eosin into the eosin use solution 2 Powder, water bath is carried out in a dark place at 30 ℃, and TiO is obtained after uniform stirring 2 Drying and dehydrating the eosin solution to obtain a powder sample, namely the Ti-Br composite photocatalytic material.
Example 4
This example provides a Ti-Br composite photocatalytic material prepared from visible light photosensitive material eosin and nano-scale TiO 2 The powder is prepared by compounding TiO 2 The mass ratio of powder to eosin is 2:1,TiO 2 2 The particle size of the powder is 10-40 nm.
Specifically, the preparation method of the Ti-Br composite photocatalytic material of the embodiment includes the following steps: weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in a dark place at the speed of 300r/min to prepare an eosin stock solution with the concentration of 10 g/L; diluting an eosin stock solution to obtain an eosin use solution with a concentration of 1.00g/L, and adding TiO with an amount of 2 times of the weight of eosin into the eosin use solution 2 The powder is put in a dark water bath at 30 ℃ and stirred uniformly to obtain TiO 2 Drying and dehydrating the eosin solution to obtain a powder sample, namely the Ti-Br composite photocatalytic material.
Example 5
This example provides a Ti-Br composite photocatalytic material prepared from visible light photosensitive material eosin and nano-scale TiO 2 The powder is prepared by compounding TiO 2 The mass ratio of powder to eosin was 1.67:1,TiO 2 2 The particle size of the powder is 10-40 nm.
Specifically, the preparation method of the Ti-Br composite photocatalytic material of the embodiment includes the following steps: weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in a dark place at the speed of 300r/min to prepare an eosin stock solution with the concentration of 10 g/L; diluting the eosin stock solution to obtain 1.25g/L eosin solution, and adding into the eosin solutionTiO with 1.67 times of eosin mass 2 Powder, water bath is carried out in a dark place at 30 ℃, and TiO is obtained after uniform stirring 2 Drying and dehydrating the eosin solution to obtain a powder sample, namely the Ti-Br composite photocatalytic material.
Example 6
This example provides a Ti-Br composite photocatalytic material prepared from visible light photosensitive material eosin and nano-scale TiO 2 Is prepared by compounding powder and is TiO 2 The mass ratio of powder to eosin is 1:1,TiO 2 2 The particle size of the powder is 10-40 nm.
Specifically, the preparation method of the Ti-Br composite photocatalytic material of the embodiment includes the following steps: weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in a dark place at the speed of 300r/min to prepare an eosin stock solution with the concentration of 10 g/L; diluting an eosin stock solution to obtain an eosin use solution with a concentration of 1.50g/L, and adding TiO with the same mass as that of eosin into the eosin use solution 2 Powder, water bath is carried out in a dark place at 30 ℃, and TiO is obtained after uniform stirring 2 Drying and dehydrating the eosin solution to obtain a powder sample, namely the Ti-Br composite photocatalytic material.
Example 7
The embodiment provides a photocatalytic component which comprises an attachment substrate, wherein a Ti-Br composite photocatalytic material is attached to the surface of the attachment substrate. The Ti-Br composite photocatalytic material comprises the following components in percentage by mass: 1 nano-sized TiO 2 Powder and eosin, tiO 2 The particle size of the powder is 10-40 nm, and the adhering matrix adopts an aluminum-based net with the thickness of 30mm 8mm.
Specifically, the preparation method of the photocatalytic module of the embodiment includes the following steps:
s1, weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in the dark at the speed of 300r/min to prepare a stock solution of the eosin with the concentration of 10 g/L.
And S2, diluting the eosin stock solution to obtain an eosin use solution with the concentration of 0.25 g/L.
S3, adding TiO with the weight of 50 times that of the eosin into the eosin use solution 2 Powder to form TiO 2 Eosin solution, taking the aluminium base web completely immersed in the TiO formed 2 Eosin solution, 30 ℃ CAnd (3) carrying out water bath by using light, stirring at the rotating speed of 200r/min for 10min, heating to 80 ℃, keeping the temperature at 5 ℃/min, and then keeping the temperature for 1.5h. To make TiO 2 And eosin can be firmly attached to the aluminum-based net, and the aluminum-based net is pretreated by adopting an acid cleaning solution and an alkaline cleaning solution respectively before being immersed and attached. Wherein the acidic cleaning solution is 1M citric acid solution or hydrochloric acid, the alkaline cleaning solution is 1M NaOH solution, and the cleaning time of both the acidic cleaning solution and the alkaline cleaning solution is 15min.
S4, taking out the TiO adhered 2 And placing the eosin aluminum-based net in a drying box, drying for 1h in a dark environment at the drying temperature of 100 ℃, and drying to obtain the aluminum-based net containing the Ti-Br composite photocatalytic material, namely the photocatalytic component.
Example 8
The embodiment provides a photocatalytic component which comprises an attachment substrate, wherein a Ti-Br composite photocatalytic material is attached to the surface of the attachment substrate. The Ti-Br composite photocatalytic material comprises the following components in percentage by mass: 1 nano-sized TiO 2 Powder and eosin, tiO 2 The particle size of the powder is 10-40 nm, and the adhering matrix adopts an aluminum-based net with the thickness of 30mm 8mm.
Specifically, the preparation method of the photocatalytic module of the embodiment includes the following steps:
s1, weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in the dark at the speed of 300r/min to prepare a stock solution of the eosin with the concentration of 10 g/L.
And S2, diluting the eosin stock solution to obtain an eosin use solution with the concentration of 0.50 g/L.
S3, adding TiO with the weight 10 times that of the eosin into the eosin use solution 2 Powder to form TiO 2 Eosin solution, taking the aluminium base web completely immersed in the TiO formed 2 In eosin solution, stirring at 30 ℃ in a dark water bath at 200r/min for 10min, heating to 80 ℃ at a rate of 5 ℃/min, and then maintaining the temperature for 1.5h. To make TiO 2 And eosin can be firmly attached to the aluminum-based net, and the aluminum-based net is pretreated by adopting an acid cleaning solution and an alkaline cleaning solution respectively before being immersed and attached. Wherein the acidic cleaning solution is 1M citric acid solution or hydrochloric acid, and alkalineThe cleaning solution is 1M NaOH solution, and the cleaning time of the acidic cleaning solution and the alkaline cleaning solution is 15min.
S4, taking out the TiO adhered 2 And placing the eosin aluminum-based net in a drying box, drying for 1h in a dark environment at the drying temperature of 100 ℃, and drying to obtain the aluminum-based net containing the Ti-Br composite photocatalytic material, namely the photocatalytic component.
Example 9
The embodiment provides a photocatalytic component which comprises an attachment substrate, wherein a Ti-Br composite photocatalytic material is attached to the surface of the attachment substrate. The Ti-Br composite photocatalytic material comprises the following components in percentage by mass: 1 nano-sized TiO 2 Powder and eosin, tiO 2 The particle size of the powder is 10-40 nm, and the adhering matrix adopts an aluminum-based net with the thickness of 30mm 8mm.
Specifically, the preparation method of the photocatalytic module of the embodiment includes the following steps:
s1, weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in the dark at the speed of 300r/min to prepare a stock solution of the eosin with the concentration of 10 g/L.
And S2, diluting the eosin stock solution to obtain an eosin use solution with the concentration of 0.75 g/L.
S3, adding TiO with the weight 5 times that of the eosin into the eosin use solution 2 Powder to form TiO 2 Eosin solution, taking the aluminium base web completely immersed in the TiO formed 2 In eosin solution, stirring in a dark water bath at 30 ℃ for 10min at a speed of 200r/min, heating to 80 ℃ at a speed of 5 ℃/min, and then keeping the temperature for 1.5h. To make TiO 2 And eosin can be firmly attached to the aluminum-based net, and the aluminum-based net is pretreated by adopting an acid cleaning solution and an alkaline cleaning solution respectively before being immersed and attached. Wherein the acidic cleaning solution is 1M citric acid solution or hydrochloric acid, the alkaline cleaning solution is 1M NaOH solution, and the cleaning time of both the acidic cleaning solution and the alkaline cleaning solution is 15min.
S4, taking out the TiO adhered 2 And placing the eosin aluminum-based net in a drying box, drying for 1h in a dark environment at the drying temperature of 100 ℃, and drying to obtain the aluminum-based net containing the Ti-Br composite photocatalytic material, namely the photocatalytic component.
Example 10
The embodiment provides a photocatalytic component which comprises an attachment substrate, wherein a Ti-Br composite photocatalytic material is attached to the surface of the attachment substrate. The Ti-Br composite photocatalytic material comprises the following components in percentage by mass: 1 nano-sized TiO 2 Powder and eosin, tiO 2 The particle size of the powder is 10-40 nm, and the adhering matrix adopts an aluminum-based net with the thickness of 30mm 8mm.
Specifically, the preparation method of the photocatalytic module of the embodiment includes the following steps:
s1, weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in the dark at the speed of 300r/min to prepare a stock solution of the eosin with the concentration of 10 g/L.
And S2, diluting the eosin stock solution to obtain an eosin use solution with the concentration of 1.00 g/L.
S3, adding TiO with the weight of 2 times that of the eosin into the eosin use solution 2 Powder to form TiO 2 Eosin solution, taking the aluminium base web completely immersed in the TiO formed 2 In eosin solution, stirring in a dark water bath at 30 ℃ for 10min at a speed of 200r/min, heating to 80 ℃ at a speed of 5 ℃/min, and then keeping the temperature for 1.5h. To make TiO 2 And eosin can be firmly attached to the aluminum-based net, and the aluminum-based net is pretreated by adopting an acid cleaning solution and an alkaline cleaning solution respectively before being immersed and attached. Wherein the acidic cleaning solution is 1M citric acid solution or hydrochloric acid, the alkaline cleaning solution is 1M NaOH solution, and the cleaning time of both the acidic cleaning solution and the alkaline cleaning solution is 15min.
S4, taking out the TiO adhered 2 And placing the eosin aluminum-based net in a drying box, drying for 1h in a dark environment at the drying temperature of 100 ℃, and drying to obtain the aluminum-based net containing the Ti-Br composite photocatalytic material, namely the photocatalytic component.
Example 11
The embodiment provides a photocatalytic component which comprises an attachment substrate, wherein a Ti-Br composite photocatalytic material is attached to the surface of the attachment substrate. The Ti-Br composite photocatalytic material comprises the following components in percentage by mass of 1.67:1 nano-sized TiO 2 Powder and eosin, tiO 2 The particle size of the powder is 10-40 nm, and the powder is attached toThe matrix adopts an aluminum-based net with the thickness of 30mm 8mm.
Specifically, the preparation method of the photocatalytic module of the embodiment includes the following steps:
s1, weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in the dark at the speed of 300r/min to prepare a stock solution of the eosin with the concentration of 10 g/L.
And S2, diluting the eosin stock solution to obtain an eosin use solution with the concentration of 1.25 g/L.
S3, adding TiO with the weight of 1.67 times that of the eosin into the eosin use solution 2 Powder to form TiO 2 Eosin solution, taking the aluminium base web completely immersed in the TiO formed 2 In eosin solution, stirring in a dark water bath at 30 ℃ for 10min at a speed of 200r/min, heating to 80 ℃ at a speed of 5 ℃/min, and then keeping the temperature for 1.5h. To make TiO 2 And eosin can be firmly attached to the aluminum-based net, and the aluminum-based net is pretreated by adopting an acid cleaning solution and an alkaline cleaning solution respectively before being immersed and attached. Wherein the acidic cleaning solution is 1M citric acid solution or hydrochloric acid, the alkaline cleaning solution is 1M NaOH solution, and the cleaning time of both the acidic cleaning solution and the alkaline cleaning solution is 15min.
S4, taking out the film with the TiO adhered thereon 2 And placing the eosin aluminum-based net in a drying box, drying for 1h in a dark environment at the drying temperature of 100 ℃, and drying to obtain the aluminum-based net containing the Ti-Br composite photocatalytic material, namely the photocatalytic component.
Example 12
The embodiment provides a photocatalytic component which comprises an attachment substrate, wherein a Ti-Br composite photocatalytic material is attached to the surface of the attachment substrate. The Ti-Br composite photocatalytic material comprises the following components in percentage by mass: 1 nano-sized TiO 2 Powder and eosin, tiO 2 The particle size of the powder is 10-40 nm, and the adhering matrix adopts an aluminum-based net with the thickness of 30mm 8mm.
Specifically, the preparation method of the photocatalytic module of the embodiment includes the following steps:
s1, weighing eosin, putting the eosin into pure water, and stirring the mixture uniformly in the dark at the speed of 300r/min to prepare a stock solution of the eosin with the concentration of 10 g/L.
And S2, diluting the eosin stock solution to obtain an eosin use solution with the concentration of 1.50 g/L.
S3, adding TiO with the same mass as the eosin into the eosin using solution 2 Powder to form TiO 2 Eosin solution, taking the aluminium base web completely immersed in the TiO formed 2 In eosin solution, stirring in a dark water bath at 30 ℃ for 10min at a speed of 200r/min, heating to 80 ℃ at a speed of 5 ℃/min, and then keeping the temperature for 1.5h. To make TiO 2 And eosin can be firmly attached to the aluminum-based net, and the aluminum-based net is pretreated by an acid cleaning solution and an alkaline cleaning solution respectively before being immersed and attached. Wherein the acidic cleaning solution is 1M citric acid solution or hydrochloric acid, the alkaline cleaning solution is 1M NaOH solution, and the cleaning time of both the acidic cleaning solution and the alkaline cleaning solution is 15min.
S4, taking out the TiO adhered 2 And placing the eosin aluminum-based net in a drying box, drying for 1h in a dark environment at the drying temperature of 100 ℃, and drying to obtain the aluminum-based net containing the Ti-Br composite photocatalytic material, namely the photocatalytic component.
Example 13
In order to facilitate the installation and fixation, this example further optimizes and improves the aluminum-based mesh containing the Ti-Br composite photocatalytic material prepared in examples 7-12.
Specifically, as shown in fig. 1, a frame 2 made of an aluminum alloy material is interposed and fixed on the outer periphery of the aluminum-based mesh, so that the photocatalytic module 10 has a rectangular plate-like modular structure. Therefore, the photocatalytic components can be spliced and assembled into plates of different sizes by utilizing the frame or fixedly installed on the surfaces of the anti-collision fences, structures and the like, the assembly and installation are very convenient, and the construction convenience and the use scene universality are good. For example, the photocatalytic component containing the Ti-Br composite photocatalytic material can be applied to places such as tunnels, expressways, landfill sites or chemical plants for photocatalytic degradation of pollutants. Because the photocatalytic component is a plate with a net structure on the whole, the photocatalytic component can be installed and fixed on a roadbed, an anti-collision belt, an anti-collision wall, an anti-collision fence, a building wall surface and a building surface through fasteners such as bolts, fixing strips or supporting frames; or can be arranged and fixed on the surface of the tree and the surface of the lamp post; or, different font models, sign models or pattern models are formed by combining and splicing, and a good text and travel modeling effect is achieved.
In some embodiments, a snap is provided on the frame 2, and the adjacent photocatalytic assemblies 10 are spliced by the snap. Through the splicing of the buckles, the two photocatalytic assemblies can be conveniently connected and fixed together.
In some embodiments, as shown in fig. 2, through holes 21 are formed along the frame 2, and the adjacent photocatalytic modules 10 are locked and connected at the through holes by fasteners. Preferably, the fastener is a bolt 3. The two photocatalytic assemblies can be conveniently connected and fixed together in a bolt mode.
In some embodiments, as shown in fig. 3, adjacent photocatalytic assemblies 10 are hinged by a hinge 4, and two blades of the hinge 4 are fixedly connected with the corresponding photocatalytic assemblies 10. Through the hinge joint of the hinge, the two photocatalytic assemblies can be conveniently spliced and fixed together, and the photocatalytic assemblies can also be rotated and placed according to a specific angle for construction and fixation.
In some specific application scenarios, as shown in fig. 4, the photocatalytic module 10 can be laid and fixed on the anti-collision wall 5 through the bolts 3, so as to perform photocatalytic degradation on exhaust pollutants generated by vehicles in the coming and going directions.
In some specific application scenarios, as shown in fig. 5, the photocatalytic component 10 can be laid and fixed on the anti-collision fence 6 of a common road or an expressway through the bolts 3, so that the photocatalytic degradation of exhaust pollutants generated by vehicles in and out can be performed.
In some specific application scenarios, as shown in fig. 6, certain travel elements are fused, specifically, the photocatalytic component 10 can be laid and spliced into a specific font shape through the fixing strip, so that a good visual effect is achieved, and air purification and beautification are fused.
In some specific application scenarios, as shown in fig. 7, certain travel elements are fused, specifically, the photocatalytic component 10 can be laid and spliced into a specific sign model through the fixing strip, so that a better visual effect is achieved, and air purification and beautification are fused.
In some specific application scenarios, as shown in fig. 8, certain travel elements are fused, specifically, the photocatalytic component 10 can be laid and spliced into a specific pattern shape through the fixing strip, so that a better visual effect is achieved, and air purification and beautification are fused.
Experiment one
The Ti-Br composite photocatalytic materials prepared in examples 1 to 6 were examined to obtain a Fourier transform infrared absorption spectrum, as shown in FIG. 9. The scanning electron micrograph of titanium dioxide is shown in FIG. 10. The scanning electron micrograph of the Ti-Br composite photocatalytic material is shown in FIG. 11.
The spectrum shows the benzene ring stretching vibration and the-OH vibration (3100 cm) -1 Nearby), benzene ring-C = C-bending vibration (1600 cm) -1 Nearby), and as the eosin dosage increases during synthesis, the response of the characteristic peaks of the spectra gradually increases, indicating that eosin is present on the surface of the material, and that the density of eosin retained on the surface increases as the dosage increases during synthesis.
The Ti-Br composite photocatalytic material has the greatest advantage of strong absorption effect on light with wave bands of 1200-1800 nm and 2400-3800 nm. This demonstrates that the invention passes through TiO 2 The Ti-Br composite photocatalytic material prepared by compounding with the eosin 2 raw materials has wider utilization range of light waves and higher efficiency.
Experiment two
The Ti-Br composite photocatalytic materials prepared in examples 1 to 6 were used to perform photocatalytic degradation experiments on organic materials.
Taking glass culture dishes, adding 20ml of ciprofloxacin solution with the initial concentration of 10mg/L, adding 50mg of the Ti-Br composite photocatalytic material prepared in the embodiments 1-6 into each culture dish, placing the culture dishes on a vortex oscillator, and carrying out white light catalytic oscillation for 2 hours at the rotating speed of 500 rpm. After 2 hours, 3ml of the sample was taken, the residual concentration of ciprofloxacin was measured, and the absorbance was measured at 280nm by filtration using a 0.22 μm polyethersulfone filter. The results are shown in table 1 below:
TABLE 1 Effect of Ti-Br composite photocatalytic material on ciprofloxacin photocatalysis for 2h
The results in table 1 show that the Ti-Br composite photocatalytic material prepared by compounding titanium dioxide and eosin has good photocatalytic degradation effect on ciprofloxacin, the removal rate is over 79.5%, and particularly, when the mass of titanium dioxide is 1-2 times that of eosin, the Ti-Br composite photocatalytic material is ideal in catalytic degradation of ciprofloxacin, and the removal rate is over 90%.
Experiment three
A photocatalytic degradation experiment was performed on the organic material using the photocatalytic assembly containing the Ti-Br composite photocatalytic material prepared in example 11.
20ml of 10mg/L ciprofloxacin solution was added to a glass petri dish, and a piece of the aluminum-based mesh (i.e., photocatalyst aluminum-based mesh) containing the Ti-Br composite photocatalytic material prepared in example 11 was placed in the petri dish. The culture dish was set on a vortex shaker at 500rpm, shaken under white light source, 2ml was sampled every 30min, absorbance was measured in a 280nm spectrophotometer, and shaking was terminated after 2h.
And after the degradation reaction is finished, pouring the ciprofloxacin solution in the culture dish out, adding 20ml of ciprofloxacin solution again, and repeating the steps for the second degradation reaction for 2 hours for three times. After the reaction was completed, the data was analyzed to evaluate whether the degradation efficiency of ciprofloxacin changed in the repeated experiments. Specifically, a data statistical chart of the photocatalytic degradation treatment effect of the aluminum-based network attached with the Ti-Br composite photocatalytic material on ciprofloxacin is shown in FIG. 12.
The experimental result of fig. 4 shows that the CIP concentration in the water body rapidly decreases in the three-cycle reaction within the first 30min of the photocatalytic reaction, and the degradation rate exceeds 50%; after 30min, the rate of the photocatalytic reaction is gradually reduced, and the degradation rate of the CIP concentration within 120min exceeds 65%. In the second and third circulating reactions, the photocatalytic capacity of the photocatalyst aluminum-based network is not obviously reduced along with the increase of the reaction times, and the degradation rates of the ciprofloxacin within 120min are respectively 70.0% and 65.9%.
Experiment four
A photocatalytic degradation experiment was performed on Volatile Organic Compounds (VOCs) using the photocatalytic module containing the Ti-Br composite photocatalytic material prepared in example 11.
A piece of aluminum-based mesh (i.e., photocatalyst aluminum-based mesh) containing the Ti-Br composite photocatalytic material prepared in example 11 was placed in a headspace sample injection bottle, 10 μ g/L of VOCs-54 standard sample was added to each sample injection bottle, the sample was placed in a photocatalytic device, photocatalytic irradiation experiments were performed for 0, 5, 10, and 30min, respectively, and a set of control group without photocatalyst aluminum-based mesh was set. After the irradiation is finished, the change of the VOCs-54 components in the sample injection bottle is analyzed through GC-MS, and the photocatalytic effect of the photocatalyst aluminum-based net in the gas phase is evaluated.
(1) Detection mode
Detecting the concentration of volatile organic compounds in the headspace sample bottle reactor by using a solid adsorption/thermal desorption-gas chromatography, wherein the material of a packed column is hard glass or stainless steel, poly 2, 6-diphenyl p-phenylene ether is packed, a sampling pipe is connected into a thermal desorption instrument under the condition of normal temperature, and the adsorbed components are introduced into a gas chromatograph with a hydrogen flame ionization detector for analysis after being heated. And judging the photocatalytic degradation efficiency of the photocatalyst to the benzene series according to the concentration change of the benzene series within 6 h.
(2) Calibration
Taking a proper amount of standard stock solutions respectively, diluting the stock solutions with methanol, diluting the stock solutions to a constant volume of 1mL, preparing calibration series with mass concentrations of 5, 10, 20, 50 and 100 mu g/mL in sequence, and drawing a calibration curve according to the mass and the response value of the target component after sample injection.
(3) Measurement of
And (3) mounting the sample injection bottle on an automatic sample injector, adjusting analysis conditions, desorbing the target component, separating by using a gas chromatograph, and detecting. Retention times and corresponding values of chromatographic peaks were recorded.
(4) Calculation of results
In the formula: ρ: mass concentration of the component to be measured in the gas, mg/m 3 ；
W: thermal desorption sample injection, mass of the component to be detected, ng, calculated from the calibration curve;
W 0 : mass of the measured component, ng, in the blank tube calculated from the calibration curve;
V nd : sample volume, L, in the standard state (101.325kPa, 273.15K).
20 representative organic matters in the VOCs-54 are selected for analysis, as shown in FIG. 13, most of the organic matters are rapidly degraded within the first 5min of the photocatalytic reaction, which indicates that the catalytic reaction rate of the photocatalyst aluminum-based net is higher in the gas-phase system photocatalytic system; after 10min, there was a return in the concentration of some of the organics, possibly as the photocatalytic reaction proceeded, these species were present in the degradation products of other organics, resulting in an increase in concentration. The degradation efficiency of 1,2, 4-trimethylbenzene, 1, 3-dichlorobenzene, sec-butylbenzene, 1, 4-dichlorobenzene, o-cymene, butylbenzene, 1, 2-dibromo-3-chloropropane, 1,3, 5-trichlorobenzene and naphthalene is over 80 percent, wherein the degradation efficiency of 1, 2-dibromo-3-chloropropane, 1,3, 5-trichlorobenzene and naphthalene in 5min is over 90 percent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A Ti-Br composite photocatalytic material is characterized by comprising a visible light photosensitive material and nano TiO 2 The visible light photosensitive material is eosin or TiO 2 The mass ratio of the powder to the eosin is (1-50): 1,TiO 2 2 The particle size of the powder is 10-40 nm.
2. A method for preparing the Ti-Br composite photocatalytic material according to claim 1, characterized by comprising the following steps: weighing eosin, putting the eosin into pure water, stirring the mixture evenly in a dark place to prepare an eosin solution with the concentration of 0.25 to 10g/L, and adding TiO with the weight of 1 to 50 times of that of the eosin into the eosin solution 2 Powder, water bath is carried out in the dark at 30 ℃, and TiO is obtained after even stirring 2 Eosin solution, dried and dehydrated.
3. A photocatalytic assembly, characterized by comprising an attachment substrate, wherein the surface of the attachment substrate is attached with the Ti-Br composite photocatalytic material according to claim 1, and the attachment substrate is an iron-based mesh, an aluminum-based mesh or a stainless steel-based mesh.
4. The photocatalytic assembly of claim 3, wherein a frame is affixed to the periphery of the attachment substrate.
5. The photocatalytic assembly of claim 4, wherein the frame is provided with a buckle, and adjacent photocatalytic assemblies are spliced by the buckle; or, the frame is provided with through holes, and the adjacent photocatalytic assemblies are locked and connected at the through holes through fasteners; or, the adjacent photocatalytic assemblies are hinged through hinges, and two blades of each hinge are fixedly connected with the corresponding photocatalytic assemblies respectively.
6. A method for preparing a photocatalytic module according to claim 3, characterized by comprising the steps of:
s1, weighing eosin, putting the eosin into pure water, and stirring the eosin in a dark place until the eosin is uniform to prepare an eosin solution with the concentration of 0.25-10 g/L;
s2, adding TiO with the weight of 1-50 times that of eosin into the eosin solution 2 Powder to form TiO 2 Eosin solution, taking the adhesion matrix immersed in the TiO formed 2 Eosin solution, in a dark water bath at 30 ℃, stirred and heated to 80 ℃, and then kept at the temperature for 1.5h;
s3, taking out the TiO adhered 2 And an eosin adhering matrix, and drying to obtain the product.
7. The method according to claim 6, wherein in step S2, the adhering substrate is pretreated with an acidic cleaning solution and an alkaline cleaning solution, respectively, before being immersed and adhered; the acidic cleaning solution is 1M citric acid solution or hydrochloric acid, the alkaline cleaning solution is 1M NaOH solution, and the cleaning time of both the acidic cleaning solution and the alkaline cleaning solution is 15min.
8. The preparation method according to claim 6, wherein in step S2, the stirring temperature rise process is as follows: stirring at 200r/min for 10min, and heating at 5 deg.C/min.
9. The manufacturing method according to claim 6, wherein in step S3, the drying process is: will be adhered with TiO 2 And the adhering substrate of eosin was dried in a drying oven at 100 ℃ for 1h in dark.
10. Use of the Ti-Br composite photocatalytic material according to claim 1 or the photocatalytic assembly according to any one of claims 3 to 5 for the catalytic degradation of air pollutants under the irradiation of visible light and/or ultraviolet light.
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| US20090311158A1 (en) * | 2007-02-13 | 2009-12-17 | Amita Verma | Sol-Gel Process for the Preparation of Nanocrystalline CETI2O6 Powder |
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| CN217855502U (en) * | 2022-08-29 | 2022-11-22 | 耒阳市钛唐科技有限公司 | Cloth base photocatalysis net of household air purifier |
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| US20090311158A1 (en) * | 2007-02-13 | 2009-12-17 | Amita Verma | Sol-Gel Process for the Preparation of Nanocrystalline CETI2O6 Powder |
| CN102671662A (en) * | 2012-03-28 | 2012-09-19 | 安徽大学 | Preparation and application of novel easy-to-recycle high-efficient visible light catalyst |
| CN204429098U (en) * | 2015-02-10 | 2015-07-01 | 唐春勇 | Light oxygen catalyzing deodorizing equipment |
| CN111056815A (en) * | 2019-11-28 | 2020-04-24 | 广州市北二环交通科技有限公司 | Slow-setting high-toughness magnesium phosphate cement road rapid repair material |
| CN217855502U (en) * | 2022-08-29 | 2022-11-22 | 耒阳市钛唐科技有限公司 | Cloth base photocatalysis net of household air purifier |
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| 王峭: "敏化剂改性纳米TiO2的光催化性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 10, pages 020 - 76 * |
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