CN113854314A - Photocatalytic antibacterial material, preparation method thereof and photocatalytic antibacterial agent - Google Patents
Photocatalytic antibacterial material, preparation method thereof and photocatalytic antibacterial agent Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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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- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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Abstract
The application discloses a photocatalytic antibacterial material, a preparation method thereof and a photocatalytic antibacterial agent. The photocatalytic antibacterial material comprises a visible-light-driven photocatalyst base body and a conductive sub-additive, wherein the conductive sub-additive is used for separating electrons and holes after the visible-light-driven photocatalyst base body corresponds to visible light, and the conductive sub-additive is loaded on the visible-light-driven photocatalyst base body. The photocatalytic antibacterial material has a synergistic effect by virtue of the conductive auxiliary and the visible-light-driven photocatalyst matrix, so that the photocatalytic antibacterial material is endowed with high-efficiency, stable and long-acting antibacterial disinfection effects. The photocatalytic antibacterial material prepared by the preparation method of the photocatalytic antibacterial material has stable performances such as antibacterial and antiviral effects, high efficiency and reduced economic cost. The photocatalytic antibacterial agent contains the photocatalytic antibacterial material.
Description
Technical Field
The application belongs to the technical field of photocatalytic antibacterial agents, and particularly relates to a photocatalytic antibacterial material, a preparation method thereof and a photocatalytic antibacterial agent.
Background
People pay more and more attention to environmental sanitation, and the sterilization and disinfection awareness of common people is obviously enhanced. In addition, the abusive use of antibiotics in human beings leads to the increase of drug resistance of bacteria, the development speed of antibacterial materials is difficult to cope with the increase of drug resistance of bacteria, the human society may face the danger that large-scale bacterial infection cannot be cured, and the design and development of novel antibacterial materials are urgently needed.
The antibacterial material is a novel functional material with bacteriostatic or bactericidal performance. The antimicrobial properties of the antimicrobial material can be achieved by adding an appropriate amount of antimicrobial agent to the polymeric material, or otherwise introducing antimicrobial groups into the carrier material. The prepared antibacterial material has the functions of inhibiting and eliminating harmful microorganisms, and can effectively prevent the breeding of the harmful microorganisms. Antibacterial agents are chemical components highly sensitive to some microorganisms, and are core components of antibacterial materials, and the types of antibacterial agents that have been developed and used at present are: electron-conducting assistant, organic antibacterial agent and composite antibacterial agent. Among them, nano silver has attracted much attention as an important bactericide, and can be used as a textile material, a coating, a food additive, etc. for eliminating microorganisms. At present, the bactericidal mechanism of silver is not consistent, and most of the research results attribute the broad-spectrum antibacterial property of silver to silver ions dissociated from nano-silver, namely, the silver ions kill bacteria by mechanisms such as membrane damage, DNA damage and the influence of Reactive Oxygen Species (ROS) generated in the dissociation process on cell metabolism. However, the use of silver ions or silver complexes as a bactericide alone is highly likely to cause adverse effects on normal cells. And the metal element ion antibiosis has the hidden trouble of secondary pollution caused by noble metal ion diffusion, and also has the defects of high product preparation cost, poor stability and the like.
In contrast, photocatalytic antibacterial materials have characteristics of good antibacterial property, photocatalytic performance, low manufacturing cost, stability and the like, and thus have attracted extensive attention in the antibacterial and photocatalytic fields. The photocatalytic antibacterial agent can absorb the energy of external photoelectrons, and electrons in the valence band jump to the conduction band to excite the conduction bandSuperoxide anion (O) formed by oxygen and water on the surface of the antimicrobial agent and in the surrounding environment2 -) And hydroxyl radical (. OH) has strong oxidation-reduction capability, can decompose protein and lipid of microorganism, promote biochemical reaction disorder of microorganism organism, destroy division and reproduction capability of pathogenic microorganism cells, and further inhibit or kill harmful microorganism. Since the membrane proteins of the microorganisms cannot be recovered after being damaged, the photocatalytic-type antibacterial agent also has a durable antibacterial effect.
The current commonly used photocatalytic antibacterial material is TiO2The photocatalyst has the advantages of good bacteriostatic effect, high thermal stability, low price, no pollution and the like, and is widely applied to the field of photocatalytic bacteriostatic. For example, Kayano Sunada et al annealed with a titanium isopropoxide solution at 500 deg.C2TiO for ultraviolet irradiation of film2When the photocatalyst kills escherichia coli, endotoxin in cells is effectively degraded. Feyza Dundar Aresoy et al will reduce TiO to 10 wt%2Incorporated into the chemistry matrix, over 95% of E.coli and up to 80% of S.aureus were inactivated under 1 hour of UV irradiation. Thus, TiO2When the photocatalyst is used as a photocatalytic antibacterial material, the corresponding catalytic effect needs to be performed under ultraviolet light, but in a solar spectrum, the ultraviolet light energy only accounts for about 5%. Thus, TiO2The photocatalytic antibacterial material is limited in use conditions.
Disclosure of Invention
The application aims to overcome the defects in the prior art, and provides a photocatalytic antibacterial material, a preparation method thereof and a photocatalytic antibacterial agent so as to solve the technical problem that the use condition of the existing photocatalytic antibacterial material is limited.
In order to achieve the above object, in a first aspect of the present application, a photocatalytic antibacterial material is provided. The photocatalytic antibacterial material comprises a visible-light-driven photocatalyst matrix and a conductive electron auxiliary agent, wherein the conductive electron auxiliary agent is used for separating electrons and holes after the visible-light-driven photocatalyst matrix corresponds to visible light, and the conductive electron auxiliary agent is loaded on the visible-light-driven photocatalyst matrix.
Furthermore, the load weight of the conductive electron assistant in the photocatalytic antibacterial material is 0.1-10%.
Further, the electron conduction auxiliary agent includes at least one of Cu and a noble metal.
Further, the noble metal includes at least one of Ag, Au, Pt, Pd, Rh, Ru and Ir.
Furthermore, the conductive sub-additive is loaded on the surface of the visible light catalyst substrate in the shape of nanoparticles.
Further, the particle size of the nanoparticle morphology is in the sub-nanometer range.
Further, the material of the visible-light-catalyst base includes nitrogen oxide.
Furthermore, the band gap of the material of the visible-light-driven photocatalyst substrate is 0-2 eV; and/or
Specifically, the nitrogen oxides include C3N4、Ta3N5、TaON、CaNbO2N、BaTaO2N、BaNbO2N、 LaTaxNb1-xON2Wherein x is 0 to 1.
Further, the particle size of the nitrogen oxide is in the nanometer range.
Further, the photocatalytic antibacterial material also comprises a surfactant, and the surfactant is modified and combined on the surface of the visible light catalyst substrate.
Specifically, the surfactant comprises at least one of polyethylene glycol, polyvinylpyrrolidone and Tween; and/or
Furthermore, the weight percentage of the surfactant in the photocatalytic antibacterial material is 0.1-10 wt%.
In a second aspect of the present application, a method for preparing a photocatalytic antibacterial material is provided. The preparation method of the photocatalytic antibacterial material comprises the following steps:
providing a visible light photocatalyst;
loading a conductive electron assistant on the photocatalyst so that the conductive electron assistant is combined on the photocatalyst to obtain the photocatalytic antibacterial material;
the conductive electron assistant is used for separating electrons and holes after the visible-light-driven photocatalyst substrate corresponds to visible light.
Further, the visible light catalyst is nitrogen oxide, and the nitrogen oxide is prepared according to a method comprising the following steps:
preparing an oxide precursor of the nitrogen oxide;
and heating the oxide precursor in a nitrogen atmosphere to perform nitridation treatment, thereby obtaining the photocatalyst containing the nitrogen oxide.
Further, the temperature of the nitridation treatment is 500-950 ℃.
Further, the electron conduction auxiliary agent comprises at least one metal simple substance of Cu and precious metal, and the method for loading the electron conduction auxiliary agent on the surface of the photocatalyst comprises the following steps:
preparing a mixed solution from visible light and a surfactant, and carrying out surface modification treatment on a visible light catalyst to form sol;
and adding a metal salt precursor of the metal simple substance and a reducing agent into the sol, mixing, carrying out reduction reaction, and depositing the metal simple substance on the visible light catalyst in situ.
Further, the metal salt precursor is a metal ion complex.
Still further, the reducing agent comprises NaBH4Sodium borohydride, hydrazine hydrate, aldehydes, hydrogen gas, and the like.
In a third aspect of the present application, a photocatalytic antimicrobial agent is provided. The photocatalytic antibacterial agent comprises the photocatalytic antibacterial material or the photocatalytic antibacterial material prepared by the preparation method of the photocatalytic antibacterial material.
Further, the photocatalytic antibacterial agent is spray, powder, film-forming agent or paint.
Compared with the prior art, the method has the following technical effects:
the photocatalytic antibacterial material provided by the first aspect of the application takes a visible light catalyst material as a substrate, the N2p orbital level of the photocatalytic antibacterial material is lower than the O2p orbital level, the band gap is narrow, the specific surface area is large, the active site content is rich, and the photocatalytic antibacterial material is applied to the sunThe light visible region shows stronger absorption, and the capability of generating electrons and holes is increased. The conductive electron assistant contained in the photocatalytic antibacterial material can effectively transfer electrons generated by the visible-light-induced photocatalyst material under the excitation of visible light, namely effectively promote interface charge transfer, increase the separation capacity of photo-generated electrons and holes, and avoid the disappearance of the recombination of the electrons and the holes generated by the visible-light-induced photocatalyst substrate under the catalysis of the visible light. As the electron conduction auxiliary agent generates the conduction and transfer function of electrons on the visible light catalyst substrate, the electron conduction auxiliary agent is conducted to excite oxygen and water on the surface and in the surrounding environment to generate superoxide anions (O) with strong redox capability2-) And a hydroxyl radical (. OH). The visible light catalyst substrate with the cavities can also excite oxygen and water on the surface and in the surrounding environment to generate superoxide anions (O) with strong redox capability2-) And a hydroxyl radical (. OH). Therefore, the conductive electron auxiliary agent and the visible light catalyst substrate play a synergistic effect, and the synergistic effect of the conductive electron auxiliary agent and the visible light catalyst substrate stimulates oxygen and water on the surface and in the surrounding environment to generate a large amount of superoxide anions (O) with strong redox capacity2-) And hydroxyl radical (. OH), thereby imparting high bactericidal and antiviral properties to the photocatalytic antibacterial material, and the bactericidal and antiviral properties are stable.
According to the preparation method of the photocatalytic antibacterial material provided by the second aspect of the application, the visible light catalyst is used as the substrate, and the electron conduction auxiliary agent is loaded on the visible light catalyst substrate to form the photocatalytic antibacterial material with the composite structure, so that the visible light catalyst substrate and the electron conduction auxiliary agent have a synergistic interaction effect, the prepared photocatalytic antibacterial material has high-efficiency and long-acting antibacterial and antiviral effects under the action of visible light, and the antibacterial and antiviral effects are stable. In addition, the preparation method of the photocatalytic antibacterial material has controllable process steps and conditions, and the prepared photocatalytic antibacterial material has stable antibacterial and antiviral effects and the like, is high in efficiency and reduces economic cost.
The photocatalytic antibacterial agent that this application third aspect provided is owing to contain this application photocatalytic antibacterial material, consequently, photocatalytic antibacterial agent can have high efficiency, long-term and stable antibiotic and antiviral effect in the visible light environment, can make this application photocatalytic antibacterial agent into corresponding use dosage form according to the needs of using in addition, realizes long-term, high-efficient and stable antibiotic sterile effect.
Drawings
In order to more clearly illustrate the detailed description of the present application or the technical solutions in the prior art, the drawings needed to be used in the detailed description of the present application or the prior art description will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing a composite dielectric ceramic according to an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
In a first aspect, embodiments of the present application provide a photocatalytic antibacterial material. The photocatalytic antibacterial material comprises a visible-light-driven photocatalyst substrate and a conductive electron auxiliary agent loaded on the visible-light-driven photocatalyst substrate.
The visible light catalyst substrate contained in the photocatalytic antibacterial material in the embodiment of the application endows the photocatalytic antibacterial material in the embodiment of the application with a visible light catalytic antibacterial disinfection effect, and simultaneously plays a role of a carrier, loads the electron conduction auxiliary agent, plays an electron conduction role of the electron conduction auxiliary agent, and generates ions and functional groups with oxidation capacity and sterilization and disinfection functions.
In an embodiment, the visible light catalyst substrate comprises an oxynitride visible light catalyst material. The N2p orbital level of the visible light catalyst materials is lower than the O2p orbital level, the band gap is narrow, the specific surface area is large, the active site content is rich, the strong absorption is presented in the sunlight visible region, and the capability of photoproducing electrons and holes is improved. Wherein is producedThe electrons are conducted to the electron conduction auxiliary agent through the loaded electron conduction auxiliary agent, so that the holes left by the visible light catalyst substrate can excite the oxygen and the water on the surface of the visible light catalyst substrate and in the surrounding environment to generate superoxide anions (O) with strong oxidation reduction capability2-) And hydroxyl radical (. OH), thereby exerting bactericidal and antiviral properties, and having stable bactericidal and antiviral properties.
In the examples, the band gap of the material of the visible-light-induced photocatalyst substrate is 0 to 2 eV. The band gap is narrow in the range, and the strong absorption of the photocatalyst matrix in the sunlight visible region can be improved to enhance the capability of generating electrons and holes, so that abundant superoxide anions (O) with strong redox capability are generated2-) And hydroxyl radical (. OH) ability, thereby improving the bactericidal and antiviral effects of the photocatalytic antibacterial material according to the examples of the present application.
In a specific embodiment, the nitrogen oxide includes C3N4、Ta3N5、TaON、CaNbO2N、 BaTaO2N、BaNbO2N、LaTaxNb1-xON2Wherein, LaTaxNb1-xON2X in (1) is 0-1, and thus, LaTaxNb1-xON2Can be at least LaTaON2、LaNbON2And the like. The N2p orbital level of the nitrogen oxides is lower than the O2p orbital level, has narrow band gap, large specific surface area and rich active site content, and can generate electrons and holes more easily under the excitation of a sunlight visible region, so that the generation of superoxide anions (O) with strong redox capability is improved2-) And hydroxyl radical (. OH) ability to enhance the bactericidal and antiviral effects of the photocatalytic antibacterial material of the examples of the present application.
In the examples, the particle size of the nitrogen oxide is in the nanometer range, and in the further examples, the particle size of the nitrogen oxide is in the range of 0.5nm to 100nm, and specifically, may be a typical but non-limiting particle size such as 0.5nm, 0.1nm, 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, and the like. The particle sizes can effectively prepare the photocatalytic antibacterial material in the embodiment of the application into various application dosage forms, such as spray application dosage forms. Of course, the particle size of the nitrogen oxide can be adjusted according to the application environment of the photocatalytic antibacterial material in the embodiments of the present application.
In a further embodiment, the photocatalytic antibacterial material of the embodiment of the present application further includes a surfactant, and the surfactant is modified and combined on the surface of the visible light catalyst substrate. By modifying the surface active agent on the surface of the visible-light-induced photocatalyst substrate, the dispersibility of the photocatalytic antibacterial material in the embodiment of the application is improved, so that the dispersibility of the photocatalytic antibacterial material in the application is improved, and the antibacterial and disinfecting effects of the photocatalytic antibacterial material are fully exerted. And the photocatalytic antibacterial material can be flexibly prepared into different application formulations according to the application requirements, such as spray.
In the embodiment, the weight percentage of the surfactant in the photocatalytic antibacterial material is 0.1 wt% to 10 wt%, and specifically, may be a typical but non-limiting content such as 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%. The content of the surfactant is controlled, so that the modification effect of the surfactant on the surface of the visible-light-driven photocatalyst matrix is improved, and the dispersibility of the photocatalytic antibacterial material is improved.
In a specific embodiment, the surfactant comprises at least one of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and tween. The surfactants can effectively improve the dispersibility of the photocatalytic antibacterial material in a solvent, thereby improving the antibacterial and disinfecting effects of the photocatalytic antibacterial material.
The conductive electron assistant contained in the photocatalytic antibacterial material provided by the embodiment of the invention is loaded on the visible light catalyst substrate. Due to the existence of the electron conduction auxiliary agent, the electron conduction auxiliary agent plays a role in conducting and transferring electrons generated on the visible light catalyst substrate, and is conducted with the electron conduction auxiliary agent to excite oxygen and water on the surface and in the surrounding environment to generate superoxide anions (O) with strong oxidation reduction capability2-) And hydroxyl radicals (. OH), so that the electron-conducting agent also has an antimicrobial actionThe function of (1). At the moment, the synergistic effect between the conductive electron auxiliary agent and the visible-light-induced photocatalyst substrate stimulates oxygen and water on the surface and in the surrounding environment to generate a large amount of superoxide anions (O) with strong redox capacity through the synergistic effect of the conductive electron auxiliary agent and the visible-light-induced photocatalyst substrate2-) And hydroxyl radical (. OH), thereby imparting high bactericidal and antiviral properties to the photocatalytic antibacterial material, and the bactericidal and antiviral properties are stable. Therefore, the photocatalytic antibacterial material in the embodiment of the application endows the photocatalytic antibacterial material with high-efficiency, long-acting and stable antibacterial and antiviral effects through the synergistic effect of the visible-light-driven photocatalyst substrate and the electron-conducting assistant, and overcomes the defects of the existing TiO2Can only play the role of antibiosis and disinfection in the ultraviolet light special environment, thereby causing the problem of limited use. But also avoids using a large amount of Ag antibacterial agent, avoids secondary pollution and reduces the cost.
In an embodiment, the supporting weight of the electron conduction assistant in the photocatalytic antibacterial material is 0.1% to 10%, and specifically, the supporting weight may be 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, and the like. By controlling the content of the conductive auxiliary agent, the synergistic effect of the antibacterial and disinfection between the conductive auxiliary agent and the visible-light-driven photocatalyst matrix is improved, and the antibacterial and disinfection effects of the photocatalytic antibacterial material in a visible-light environment are improved.
In the embodiment, the electron conduction assistant is loaded on the visible light catalyst substrate in a particle shape, for example, grown in situ on the surface of the visible light catalyst substrate. And the detection shows that the smaller the particle size of the electron conductive agent is, the stronger the synergistic interaction between the electron conductive agent and the visible light catalyst substrate is, and the more excellent the antibacterial and disinfection effects of the photocatalytic antibacterial material are. In further embodiments, the particle size of the electron conduction aid in the particle morphology is controlled to be in a sub-nanometer range, such as a formed sub-nanometer particle cluster. By controlling the morphology and the particle size of the conductive electron assistant load, the uniformity of the conductive electron assistant load on the visible light catalyst substrate is improved, the antibacterial disinfection synergistic effect between the conductive electron assistant and the visible light catalyst substrate is improved, the particle size of the photocatalytic antibacterial material in the embodiment of the application is adjusted together with the visible light catalyst substrate, and the application range of the photocatalytic antibacterial material in the embodiment of the application is widened.
In a specific embodiment, the electron conduction auxiliary agent comprises at least one of Cu and a noble metal. In a specific embodiment, the noble metal comprises at least one of Ag, Au, Pt, Pd, Rh, Ru, Ir. The conductive electron assistants have good electronic conductivity, the antibacterial and disinfection synergistic effect between the conductive electron assistants and the visible-light-driven photocatalyst matrix is improved, and the antibacterial and disinfection effect of the photocatalytic antibacterial material in a visible-light environment is improved. For example, when the electron conduction auxiliary agent is Ag, the Ag is loaded on the visible light catalyst substrate in a sub-nanometer silver cluster shape. When the conductive auxiliary agent is Ag, for example, in a visible light environment, the conductive auxiliary agent can play a role in electron conduction, can play a role in synergy of antibacterial and disinfection with a visible light catalyst substrate, and improves the antibacterial and disinfection effects of the photocatalytic antibacterial material in the embodiment of the application. Ag is also capable of performing bactericidal and antiviral, i.e., antibacterial and disinfectant, effects when in a non-visible environment. At the moment, the Ag and the visible light catalyst substrate have a synergistic effect, so that the photocatalytic antibacterial material provided by the embodiment of the application has high-efficiency, long-acting and stable antibacterial and antiviral effects, and is not influenced by the use environment.
In a second aspect, embodiments of the present application provide a method for preparing the above photocatalytic antibacterial material. The preparation method of the photocatalytic antibacterial material in the embodiment of the application has the process flow as shown in fig. 1, and comprises the following steps:
s01: providing a visible light photocatalyst;
s01: and (3) loading the conductive electron assistant on the photocatalyst, so that the conductive electron assistant is combined on the photocatalyst to obtain the photocatalytic antibacterial material.
Thus, in the preparation method of the photocatalytic antibacterial material in the embodiment of the application, the visible light catalyst is used as the visible light catalyst substrate, and the electron conduction additive is loaded on the visible light catalyst substrate to form the photocatalytic antibacterial material with a composite structure, so that the visible light catalyst substrate and the electron conduction additive play a role in synergy, the prepared photocatalytic antibacterial material has efficient and continuous antibacterial and antiviral effects, and the antibacterial and antiviral effects are stable.
Wherein, the photocatalyst in the step S01 is the visible light photocatalyst matrix contained in the photocatalytic antibacterial material. Therefore, the photocatalyst includes the nitrogen oxide contained in the above photocatalytic antibacterial material. For the sake of brevity, the photocatalyst in step S01 will not be described in detail herein.
In an example, when the visible light catalyst is nitrogen oxide, the photocatalyst in the step S01 is prepared according to a method comprising the steps of:
s011: preparing an oxide precursor of the photocatalyst;
s012: and heating the oxide precursor in a nitrogen atmosphere to perform nitridation treatment, thereby obtaining the photocatalyst containing the nitrogen oxide.
Among them, the oxide precursor in step S011 should be an oxide precursor for preparing the above nitrogen oxide. Such as when the nitrogen oxides comprise C as above3N4、Ta3N5、TaON、CaNbO2N、BaTaO2N、 BaNbO2N、LaTaxNb1-xON2At least one of them, then the oxide precursors in step S011 are respectively form C3N4、Ta3N5、TaON、CaNbO2N、BaTaO2N、BaNbO2N、LaTaxNb1-xON2The corresponding oxide. In a specific embodiment, the oxynitride is LaTaxNb1-xON2Then the oxide may be LaKNaTaxNb1-xO5. In addition, each oxide precursor can be prepared separately according to a conventional method corresponding to each oxide or a method modified based on the conventional method. Such as, but not limited to, hydrothermal synthesis of the oxide precursor.
In the nitriding treatment process in the step S012, under the action of high temperature, nitrogen atoms replace part of elements in the oxide precursor, so as to generate the nitrogen oxide with narrow band gap and antibacterial and disinfection effects under the excitation of visible light. In the embodiment, the temperature of the nitridation treatment is 500-950 ℃, and specifically, the temperature of the nitridation treatment can be typically, but not limited to, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ and 950 ℃. Within this temperature range of the nitriding treatment, the efficiency of the nitriding treatment can be effectively improved. The nitriding treatment in this temperature range should be sufficient, and may be, for example, 0.5 to 10 hours, and further 0.5 to 4 hours.
The conductive sub-additive deposited in step S02 is the conductive sub-additive contained in the photocatalytic antibacterial material and supported on the surface of the visible-light-induced photocatalyst substrate. If the electron conduction sub-additive includes at least one metal element of Cu and precious metal, the electron conduction sub-additive formed in step S02 has a shape similar to that of the electron conduction sub-additive contained in the photocatalytic antibacterial material.
In an embodiment, when the electron conduction promoter includes at least one metal element of Cu and a noble metal, the method for supporting the electron conduction promoter on the surface of the photocatalyst in step S02 includes the following steps:
s021: preparing a mixed solution from a photocatalyst and a surfactant, and carrying out surface modification treatment on the photocatalyst to form sol;
s022: and adding a metal salt precursor of the metal simple substance and a reducing agent into the sol, mixing, carrying out reduction reaction, and depositing the metal simple substance on the surface of the photocatalyst in situ.
The surface modification treatment in step S021 may be performed by controlling the conditions according to the type of the surfactant, for example, water bath ultrasound may be used. In the examples, the photocatalyst and the surfactant are mixed in the mixed solution of S021 at a mass ratio of 100 (10 to 0.05), and specific examples thereof may include typical but not limited mass ratios such as 100:0.05, 100:0.1, 100:0.15, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, and 100: 10. By controlling the mixing ratio of the photocatalyst and the surfactant, the surface of the photocatalyst is fully modified, and the dispersibility of the prepared photocatalytic antibacterial material is improved. Of course, the photocatalyst particles can be controlled, and after the surface modification treatment, a non-sol dispersion solution can be generated.
In embodiments, the surfactant is at least one of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), tween, and like agents as described above.
The metal salt precursor in step S022 should be a metal salt corresponding to a simple metal forming at least one of Cu and a noble metal, such as an Ag salt, a Cu salt, and the like. In an embodiment, the metal salt precursor is added in the form of a metal ion complex, for example, the complex should be any complex capable of forming a metal ion complex with a metal salt, such as Glutathione (GSH) complex, but not limited thereto. The metal salt precursor is added in the form of metal ion complex, so that the morphology and size of the conductive electron assistant formed by precipitation can be effectively controlled, for example, Ag formed by precipitation is controlled to be in the sub-nanometer silver cluster morphology.
In an embodiment, the reducing agent in step S022 comprises NaBH4Sodium borohydride, hydrazine hydrate, aldehydes, hydrogen gas, and the like. The addition amount of the reducing agent should ensure that all metal ions are reduced to generate a metal simple substance to be precipitated, that is, the reducing agent should be excessive relative to the metal ions, for example, in an embodiment, the metal salt precursor and the reducing agent are added and mixed according to a mass ratio of 100 (1-20), which may be a typical but non-limiting mass ratio of 100:1, 100:3, 100:5, 100:7, 100:10, 100:12, 100:14, 100:15, 100: 17, 100:18, 100:20, and the like.
Therefore, the preparation method of the photocatalytic antibacterial material in each embodiment can effectively prepare the photocatalytic antibacterial material with the composite structure, and can control and condition the particle size of the prepared photocatalytic antibacterial material, the morphology and the content of the loaded electron-conducting assistant and the like by controlling the preparation conditions, so that the visible light catalyst substrate and the electron-conducting assistant are improved to play a synergistic role, and the antibacterial and antiviral effects of the photocatalytic antibacterial material are improved. In addition, the preparation method of the photocatalytic antibacterial material in the embodiment of the application has controllable process steps and conditions, and the prepared photocatalytic antibacterial material has stable antibacterial and antiviral effects and other performances, is high in efficiency and reduces economic cost.
In a third aspect, the present examples provide the use of the photocatalytic antimicrobial agent described above. In particular to a photocatalytic antibacterial agent. The photocatalytic antibacterial agent in the embodiment of the application is the photocatalytic antibacterial material. Therefore, the photocatalytic antibacterial agent in the embodiment of the application has high-efficiency, continuous and stable antibacterial and antiviral effects in a visible light environment and a non-visible light environment, and can be prepared into corresponding use dosage forms according to application requirements, so that the long-acting, high-efficiency and stable antibacterial and disinfection effects are realized.
As in the examples, the photocatalytic antibacterial agent of the present application is in the form of a spray, a powder, or a coating for film formation. That is, the photocatalytic antibacterial material can be prepared into spray, powder or paint according to the application requirement.
In a specific embodiment, when the formulation of the photocatalytic antibacterial agent in the embodiment of the present application is a spray, the size of the particles of the photocatalytic antibacterial material is controlled to prepare a spray of sol dispersion, and an ultrathin and stable coating or film can be formed along with the rapid volatilization of the solvent in the spraying process, so that the effect of long-term antibacterial disinfection is achieved, and the stability is good, so that the photocatalytic antibacterial agent is convenient for industrial application. Therefore, the problems of high preparation cost of the traditional antibacterial agent, poor antibacterial effect caused by easy volatilization of the alcohol aerosol sterilizing spray and the like are effectively solved.
The photocatalytic antibacterial agent and the preparation method thereof according to the embodiments of the present application will be described below by way of examples.
Examples 1 to 5
Examples 1 to 5 provide a photocatalytic antibacterial agent and a method for preparing the same, respectively. The photocatalytic antibacterial agent is Ag-LaTaxNb1-xON2(x is 0-1) is LaTaxNb1-xON2As photocatalytic antibacterial matrix in LaTaxNb1-xON2The surface of the photocatalytic antibacterial substrate is combined with a PEG surface modifier and a sub-nano silver cluster.
The preparation method of the photocatalytic antibacterial agent comprises the following steps:
S1.LaTaxNb1-xON2preparation of photocatalytic antibacterial matrixPreparing:
s11, synthesizing layered LaKNaTa by adopting hydrothermal methodxNb1-xO5Oxide precursor (x ═ 0-1):
firstly La (NO)3、TaCl5And NbCl5Adding the components into excessive saturated KOH (10 g) and NaOH (5g) solutions according to the following molar amounts respectively, then transferring the components into a hydrothermal kettle, then heating the components to 200 ℃ in a muffle furnace at a heating rate of 10K/min, keeping the temperature for 20 hours, and then cooling the components to room temperature; washing the reaction product with ultrapure water at room temperature for 3-5 times, centrifuging to remove residual NaOH and KOH, and vacuum drying the filter cake overnight to obtain LaKNaTaxNb1-xO5Powder;
wherein, in example 1, La (NO)3、TaCl5、NbCl5Sequentially adding the raw materials according to the molar weight of 5mmol, 1mmol and 5 mmol; example 2, La (NO)3、TaCl5、NbCl5Sequentially adding the raw materials according to the molar weight of 5mmol, 2mmol and 4 mmol; example 3, La (NO)3、TaCl5、NbCl5Sequentially adding the raw materials according to the molar weight of 5mmol, 3mmol and 3 mmol; in example 4, La (NO)3、TaCl5、NbCl5Sequentially adding the raw materials according to the molar weight of 5mmol, 4mmol and 2 mmol; in example 5, La (NO)3、TaCl5、NbCl5Sequentially adding the raw materials according to the molar weight of 5mmol, 5mmol and 1 mmol;
s12, mixing LaKNaTaxNb1-xO5Performing nitridation treatment:
2g of LaKNaTa to be obtainedxNb1-xO5Nitriding treatment is carried out under the following conditions respectively to prepare LaTaxNb1-xON2；
The nitriding treatment temperature in example 1 was 700 ℃ and the time was 4 hours; the nitriding treatment temperature in example 2 was 750 ℃ and the time was 3 hours; the nitriding treatment temperature in example 3 was 800 ℃ and the time was 2 hours; the nitriding treatment temperature in example 4 was 850 ℃ and the time was 1 hour; the nitriding treatment temperature in example 5 was 950 ℃ and the time was 0.5 hour;
s2, in LaTaxNb1-xON2Depositing sub-nano silver clusters on the photocatalytic antibacterial substrate:
s21, taking 2g of LaTaxNb1-xON2Putting into a flask, adding 50mL of 2M PEG aqueous solution, stirring thoroughly, performing ultrasonic treatment in water bath for 2-5 hr to modify the surface with PEG to obtain LaTaxNb1-xON2Highly dispersing into water solution to obtain nitrogen oxide sol;
s22, firstly 20mg of AgNO3Mixing with 100mg GSH thoroughly to form GSH-Ag+Complex, which is subsequently added to 1g of LaTaxNb1-xON2Fully and uniformly stirring the mixture in a sol system, and then adding 0.1M NaBH4Performing in-situ reduction to controllably deposit silver clusters on the surface of the nitrogen oxide to form Ag-LaTaxNb1-xON2A colloidal solution; then evaporating the solvent in the system by using a rotary evaporator to obtain a product Ag-LaTaxNb1-xON2Photocatalytic antibacterial materials.
Detected, LaTaxNb1-xON2The grain diameter of the photocatalytic antibacterial substrate is 100 nanometers to 10 micrometers, the grain diameter of the silver cluster is 0.5nm to 20nm, and the silver cluster is arranged in Ag-LaTaxNb1-xON2The content of (B) is 0.5-5 wt%.
Example 6
The present example provides a photocatalytic antimicrobial agent and a method for preparing the same. The photocatalytic antibacterial agent is Ta3N5Is at Ta3N5In Ta as photocatalytic antibacterial matrix3N5The surface of the photocatalytic antibacterial substrate is combined with a PEG surface modifier and a sub-nanometer Rh cluster.
The preparation method of the photocatalytic antibacterial agent comprises the following steps:
S1.Ta3N5preparing a photocatalytic antibacterial matrix:
s11, preparing KTaO by adopting a solid-phase reaction method3Precursor nitriding:
mixing Ta2O5(5mmol) and K2CO3(5.25mmol) were mixed in a molar ratio of Ta to K of 1:1.05,adding excessive potassium to compensate loss caused by volatilization at high temperature, and thoroughly grinding the agate mixture in agate mortar for 90 minutes in the presence of a small amount of ethanol as a dispersing agent; after drying, the resulting mixture was transferred to an alumina crucible and calcined at 1173K for 1h, then at 1423K in static air for 10 h; KTaO obtained in this manner3Washed with ultrapure water at 343K for 2h and centrifuged twice to remove any residual K2CO3(ii) a Then heating at 343K overnight to completely dry the powder;
s12, mixing KTaO3Performing nitridation treatment:
KTaO (potassium sodium phosphate)3(0.5g) was transferred to an alumina tube and NH gas at 1173K for 100ml min3Nitriding for 0.05-4 h;
s2. in Ta3N5Depositing precious metal Rh on the photocatalytic antibacterial substrate:
taking 2g of Ta3N5Putting the mixture into a ball milling tank to be fully mixed with 5ml of ethanol and carrying out ball milling treatment for 5 hours to obtain the Ta with uniform dispersion and small size3N5The sample, ball milled product was washed centrifugally and re-dispersed into 1ml deionized water evaporating dish. Then add 200. mu.l of 1M RhCl to it3The solution is fully and evenly stirred by a glass rod to be completely dipped into Ta3N5The sample was then placed in an evaporating dish in a 60 ℃ hot plate with stirring to completely evaporate the water, and then the sample was transferred to a tube furnace and reduced with hydrogen at 200 ℃ for half an hour to give Rh-Ta3N5A photocatalytic antibacterial coating material or a film-forming agent.
Comparative example 1
This comparative example provides LaTaxNb1-xON2A photocatalyst. Compared with the example 1, the difference is that no LaTa is containedxNb1- xON2The photocatalyst does not carry silver clusters.
Comparative example 2
This comparative example provides a silver antibacterial agent having a particle diameter close to or the same as the particle diameter of the silver clusters contained in example 1.
Experiment of antibacterial and disinfecting effects
The photocatalytic antibacterial agent provided in each of examples 1 to 6 and the antibacterial agent provided in comparative example 1 described above were subjected to antibacterial sterilization experiments as follows:
we studied the antibacterial activity of photocatalytic antibacterial agents by culturing bacteria such as Escherichia coli, Bacillus subtilis, and Staphylococcus aureus. First, different types of bacterial culture media shown in Table I below were cultured and divided into 7 portions. The bacterial culture medium was then treated with the same concentration but different types of photocatalytic antimicrobial agents (examples 1-6 photocatalytic antimicrobial, comparative examples 1-2), respectively. The bacteria were then incubated at 37 ℃ for a period of time in the dark and in the sun, respectively, and the bacterial viability was recorded every five minutes for the different types of photocatalytic antibacterial agents.
The results of the antibacterial sterilization test are shown in the following tables II and III.
TABLE-different types of bacterial culture media
Bacterial survival in the Presence of Table two darkness (5 min)
Bacterial survival in the Presence of the third Sun (5 minutes)
As can be seen from tables two and three, the photocatalytic antibacterial material provided in the embodiments of the present application has excellent bactericidal and disease-resistant capabilities under the sunlight condition, and completely kills all bacteria in each experimental group. And comparative examples 1 and 2 failed to achieve this effect. And comparing the photocatalytic antibacterial material provided by the embodiment with the photocatalyst provided by the comparative example 1 and the silver antibacterial agent provided by the comparative example 2, the conductive auxiliary agent and the visible light catalyst matrix contained in the photocatalytic antibacterial material provided by the embodiment of the application have a synergistic effect, and the photocatalytic antibacterial material is endowed with efficient sterilization and antiviral properties.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A photocatalytic antibacterial material comprises a visible light catalyst substrate, and is characterized in that: the visible light photocatalyst further comprises an electron conduction auxiliary agent, the electron conduction auxiliary agent is used for separating electrons and holes after the visible light photocatalyst substrate corresponds to visible light, and the electron conduction auxiliary agent is loaded on the visible light photocatalyst substrate.
2. The photocatalytic antibacterial material according to claim 1, characterized in that: the load weight of the conductive electron assistant in the photocatalytic antibacterial material is 0.1-10%; and/or
The conductive sub-additive comprises at least one of Cu and precious metal; and/or
The electron conduction auxiliary agent is loaded on the surface of the visible light catalyst substrate in a nano-particle shape; and/or
The material of the visible-light-driven photocatalyst substrate comprises nitrogen oxide; and/or
The photocatalytic antibacterial material also comprises a surfactant which is modified and combined on the surface of the visible-light-driven photocatalyst substrate.
3. The photocatalytic antibacterial material according to claim 2, characterized in that: the particle size of the nano-particle appearance is in a sub-nano range;
the noble metal comprises at least one of Ag, Au, Pt, Pd, Rh, Ru and Ir.
4. The photocatalytic antibacterial material according to claim 2 or 3, characterized in that: the band gap of the material of the visible-light-driven photocatalyst substrate is 0-2 eV; and/or
The nitrogen oxides include C3N4、Ta3N5、TaON、CaNbO2N、BaTaO2N、BaNbO2N、LaTaxNb1-xON2Wherein x is 0-1; and/or
The particle size of the nitrogen oxide is in the nanometer range.
5. The photocatalytic antibacterial material according to claim 2 or 3, characterized in that: the surfactant comprises at least one of polyethylene glycol, polyvinylpyrrolidone and Tween; and/or
The weight percentage of the surfactant in the photocatalytic antibacterial material is 0.1-10 wt%.
6. A preparation method of a photocatalytic antibacterial material comprises the following steps:
providing a visible light photocatalyst;
loading a conductive electron assistant on the photocatalyst so that the conductive electron assistant is combined on the photocatalyst to obtain a photocatalytic antibacterial material;
the electron conduction auxiliary agent is used for separating electrons and holes after the visible light catalyst substrate corresponds to visible light.
7. The method of claim 6, wherein: the visible light catalyst is nitrogen oxide, and the nitrogen oxide is prepared according to a method comprising the following steps:
preparing an oxide precursor of the nitrogen oxide;
heating the oxide precursor in a nitrogen atmosphere to perform nitridation treatment, so as to obtain the photocatalyst containing the nitrogen oxide;
and/or
The conductive electron assistant comprises at least one metal simple substance of Cu and precious metal, and the method for loading the conductive electron assistant on the surface of the photocatalyst comprises the following steps:
preparing the visible light and a surfactant into a mixed solution, and carrying out surface modification treatment on the visible light catalyst to form sol;
and adding a metal salt precursor of the metal simple substance and a reducing agent into the sol, mixing, carrying out reduction reaction, and depositing the metal simple substance on the visible light catalyst in situ.
8. The method of claim 7, wherein: the temperature of the nitriding treatment is 500-950 ℃;
the metal salt precursor is a metal ion complex;
the reducing agent comprises NaBH4At least one of sodium borohydride, hydrazine hydrate, aldehydes and hydrogen.
9. A photocatalytic antibacterial agent comprising the photocatalytic antibacterial material according to any one of claims 1 to 6 or the photocatalytic antibacterial material produced by the production method according to any one of claims 7 to 8.
10. The photocatalytic antimicrobial agent according to claim 9, characterized in that: the photocatalytic antibacterial agent is a spray, powder or a film-forming agent or a coating.
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| CN202111070967.3A CN113854314A (en) | 2021-09-13 | 2021-09-13 | Photocatalytic antibacterial material, preparation method thereof and photocatalytic antibacterial agent |
| PCT/CN2021/137298 WO2023035451A1 (en) | 2021-09-13 | 2021-12-12 | Photocatalytic antibacterial material, preparation method therefor, and photocatalytic antibacterial agent |
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