WO2023035451A1 - 光催化抗菌材料及其制备方法和光催化抗菌剂 - Google Patents

光催化抗菌材料及其制备方法和光催化抗菌剂 Download PDF

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WO2023035451A1
WO2023035451A1 PCT/CN2021/137298 CN2021137298W WO2023035451A1 WO 2023035451 A1 WO2023035451 A1 WO 2023035451A1 CN 2021137298 W CN2021137298 W CN 2021137298W WO 2023035451 A1 WO2023035451 A1 WO 2023035451A1
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visible light
photocatalytic antibacterial
antibacterial material
photocatalytic
light catalyst
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French (fr)
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薛冬峰
王鑫
王晓明
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the application belongs to the technical field of photocatalytic antibacterial agents, and in particular relates to a photocatalytic antibacterial material, a preparation method thereof, and a photocatalytic antibacterial agent.
  • Antibacterial materials are a new class of functional materials with antibacterial or bactericidal properties.
  • the antibacterial properties of antibacterial materials can be achieved by adding an appropriate amount of antibacterial agents to polymer materials, or introducing antibacterial groups into carrier materials in other ways.
  • the prepared antibacterial material itself has the function of inhibiting and eliminating harmful microorganisms, and can effectively prevent the breeding of harmful microorganisms.
  • Antibacterial agents are chemical components that are highly sensitive to some microorganisms, and are the core components of antibacterial materials.
  • photocatalytic antibacterial materials have received extensive attention in the fields of antibacterial and photocatalysis due to their good antibacterial properties, photocatalytic performance, low cost and stability.
  • the photocatalytic antibacterial agent can absorb external photoelectron energy, and the electrons in the valence band jump to the conduction band, which excites the oxygen and water on the surface of the antibacterial agent and in the surrounding environment, forming superoxide anions (O 2 - ) and hydroxyl radicals ( OH) has a strong redox ability, which can decompose the protein and lipid of microorganisms, promote the disorder of biochemical reactions of microorganisms, destroy the division and reproduction ability of pathogenic microorganism cells, and then inhibit or kill harmful microorganisms. Since the membrane proteins of microorganisms cannot be recovered after being damaged, photocatalytic antibacterial agents also have long-lasting antibacterial effects.
  • the commonly used photocatalytic antibacterial material is TiO 2 , which is widely used in the field of photocatalytic antibacterial because of its good antibacterial effect, high thermal stability, low price and no pollution.
  • TiO 2 which is widely used in the field of photocatalytic antibacterial because of its good antibacterial effect, high thermal stability, low price and no pollution.
  • KayanoSunada et al prepared a TiO2 film by annealing a titanium isopropoxide solution at 500°C.
  • Escherichia coli was killed with TiO2 photocatalyst by ultraviolet irradiation, the endotoxin in the cells was also effectively degraded.
  • FeyzaDundarArisoy et al incorporated as low as 10wt% TiO2 into a chemical matrix, and under 1 hour of UV irradiation, more than 95% of Escherichia coli and up to 80% of Staphylococcus aureus were inactivated. Therefore, when TiO 2 is used as a photocatalytic antibacterial material, it needs to perform a corresponding catalytic effect under ultraviolet light, but in the solar spectrum, the energy of ultraviolet light only accounts for about 5%. Therefore, TiO2 as a photocatalytic antibacterial material is limited due to the use conditions.
  • the purpose of this application is to overcome the above-mentioned deficiencies in the prior art, provide a photocatalytic antibacterial material and its preparation method and photocatalytic antibacterial agent, so as to solve the technical problem of limited use conditions of the existing photocatalytic antibacterial material.
  • the first aspect of the present application provides a photocatalytic antibacterial material.
  • the photocatalytic antibacterial material of the present application includes a visible light catalyst matrix, and also includes a conductive electron additive, which is used to separate electrons and holes after the visible light catalyst matrix responds to visible light, and the conductive electron additive is loaded on the visible light catalyst matrix.
  • the loading weight of the electron conduction aid in the photocatalytic antibacterial material is 0.1%-10%.
  • the electron conduction aid includes at least one of Cu and a noble metal.
  • the noble metal includes at least one of Ag, Au, Pt, Pd, Rh, Ru, and Ir.
  • the electron conduction aid is supported on the surface of the visible light catalyst substrate in the form of nanoparticles.
  • the particle size of the nanoparticle morphology is in the sub-nanometer range.
  • the material of the visible light catalyst substrate includes nitrogen oxides.
  • the material of the visible photocatalyst matrix has a band gap of 0-2eV; and/or
  • the particle size of the nitrogen oxides is in the nanometer range.
  • the photocatalytic antibacterial material also includes a surfactant, and the surfactant is modified and bound to the surface of the visible light catalyst substrate.
  • the surfactant includes at least one of polyethylene glycol, polyvinylpyrrolidone, and Tween; and/or
  • the weight percent content of the surfactant in the photocatalytic antibacterial material is 0.1wt%-10wt%.
  • the second aspect of the present application provides a method for preparing a photocatalytic antibacterial material.
  • the preparation method of the photocatalytic antibacterial material of the present application comprises the following steps:
  • the electron-conducting additive is used for the separation of electrons and holes after the visible light catalyst substrate responds to visible light.
  • the visible light catalyst is nitrogen oxide
  • the nitrogen oxide is prepared according to a method comprising the following steps:
  • Oxide precursors for the preparation of nitrogen oxides are Oxide precursors for the preparation of nitrogen oxides
  • the oxide precursor is heated in a nitrogen atmosphere to carry out nitriding treatment to obtain a nitrogen oxide-containing photocatalyst.
  • the nitriding temperature is 500-950°C.
  • the electron conduction aid includes at least one metal element in Cu and precious metals
  • the method for supporting the electron conduction aid on the surface of the photocatalyst includes the following steps:
  • the metal salt precursor of the metal element and the reducing agent are added to the sol, and the mixed treatment and reduction reaction are carried out, and the metal element is deposited in situ on the visible light catalyst.
  • the metal salt precursor is a metal ion complex.
  • the reducing agent includes at least one of NaBH 4 , sodium borohydride, hydrazine hydrate, aldehydes, hydrogen and the like.
  • the third aspect of the present application provides a photocatalytic antibacterial agent.
  • the photocatalytic antibacterial agent of the present application includes the photocatalytic antibacterial material of the present application or the photocatalytic antibacterial material prepared by the preparation method of the photocatalytic antibacterial material of the present application.
  • the photocatalytic antibacterial agent is spray, powder, film-forming agent or paint.
  • the photocatalytic antibacterial material provided by the first aspect of the present application is based on a visible light catalyst material, and its N2p orbital energy level is lower than that of the O2p orbital energy level, the band gap is narrow, and the specific surface area is large, and the active site content is abundant. It exhibits strong absorption and increases the ability of photogenerated electrons and holes.
  • the conductive electron additive contained in the photocatalytic antibacterial material can effectively transfer the electrons generated by the visible light catalyst material under the excitation of visible light, that is, effectively promote the interface charge transfer, increase the separation ability of photogenerated electrons and holes, and avoid the visible light catalyst matrix. The recombination of electrons and holes generated under visible light catalysis disappears.
  • the electron conduction additive excites the oxygen and water on the surface and the surrounding environment to generate superoxide negative ions (O 2- ) with strong redox ability. and hydroxyl radicals ( ⁇ OH).
  • the visible photocatalyst matrix with holes can also excite oxygen and water on the surface and in the surrounding environment to generate superoxide anion (O 2- ) and hydroxyl radical ( ⁇ OH) with strong redox ability.
  • the preparation method of the photocatalytic antibacterial material provided by the second aspect of the present application uses the visible light catalyst as the matrix, and the electron conduction additive is loaded on the visible light catalyst matrix to form a composite structure photocatalytic antibacterial material, so that the visible light catalyst matrix and the electron conduction additive Play a synergistic effect, endow the prepared photocatalytic antibacterial material with high-efficiency and long-term antibacterial and antiviral effects under the action of visible light, and the antibacterial and antiviral effects are stable.
  • the process steps and conditions of the preparation method of the photocatalytic antibacterial material of the present application are controllable, and the prepared photocatalytic antibacterial material has stable antibacterial and antiviral properties, high efficiency, and reduced economic costs.
  • the photocatalytic antibacterial agent provided by the third aspect of the present application contains the photocatalytic antibacterial material of the present application, so the photocatalytic antibacterial agent can have efficient, long-term and stable antibacterial and antiviral effects in the visible light environment, and can be used according to the needs of the application
  • the photocatalytic antibacterial agent of the present application is made into a corresponding dosage form to achieve long-lasting, efficient and stable antibacterial and disinfection effects.
  • FIG. 1 is a schematic flow chart of a method for preparing a composite dielectric ceramic according to an embodiment of the present application.
  • the term "and/or” describes the association relationship of associated objects, indicating that there may be three relationships, for example, A and/or B may mean: A exists alone, A and B exist simultaneously, and B exists alone Condition. Among them, A and B can be singular or plural.
  • the character "/" generally indicates that the contextual objects are an "or" relationship.
  • At least one means one or more, and “multiple” means two or more.
  • At least one of the following” or similar expressions refer to any combination of these items, including any combination of single or plural items.
  • at least one item (unit) of a, b, or c or “at least one item (unit) of a, b, and c” can mean: a, b, c, a-b( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.
  • sequence numbers of the above-mentioned processes do not mean the order of execution, and some or all steps may be executed in parallel or sequentially, and the execution order of each process shall be based on its functions and The internal logic is determined and should not constitute any limitation to the implementation process of the embodiment of the present application.
  • the weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components.
  • the scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application.
  • the mass described in the description of the embodiments of the present application may be ⁇ g, mg, g, kg and other well-known mass units in the chemical industry.
  • the embodiment of the present application provides a photocatalytic antibacterial material.
  • the photocatalytic antibacterial material of the embodiment of the present application includes a visible light catalyst substrate and an electron conduction aid supported on the visible light catalyst substrate.
  • the visible light catalyst matrix contained in the photocatalytic antibacterial material of the embodiment of the application endows the photocatalytic antibacterial material of the embodiment of the application with visible light catalytic antibacterial and disinfection effects, and at the same time acts as a carrier, supporting the conduction aid and exerting the conduction aid. Electron conduction of agents and generation of ions and functional groups with oxidizing ability and sterilization.
  • the visible light catalyst substrate includes a nitrogen oxide visible light catalyst material.
  • the N2p orbital energy level of these visible photocatalyst materials is lower than the O2p orbital energy level, the band gap is narrow, and the specific surface area is large, the active site content is rich, and it shows strong absorption in the visible region of sunlight, increasing the ability of photogenerated electrons and holes. .
  • the generated electrons will be conducted to the conduction aid through the supported electron conduction aid. Therefore, the holes left by the visible light catalyst matrix will excite oxygen and water on its surface and in the surrounding environment, forming a strong oxidation-reduction ability.
  • Superoxide negative ions (O 2- ) and hydroxyl radicals ( ⁇ OH) can exert bactericidal and antiviral properties, and the bactericidal and antiviral properties are stable.
  • the material of the visible light catalyst substrate has a band gap of 0-2eV. This range has a narrow band gap, which can improve the strong absorption of the photocatalyst matrix in the visible region of sunlight to enhance the ability to generate electrons and holes, thereby producing abundant superoxide negative ions (O 2- ) and Hydroxyl radical ( ⁇ OH) ability, thereby improving the bactericidal and antiviral effect of the photocatalytic antibacterial material of the embodiment of the present application.
  • the N2p orbital energy level of these nitrogen oxides is lower than the O2p orbital energy level, with narrow band gap, large specific surface area, and rich active site content, which can generate electrons and holes more easily under the excitation of the visible region of sunlight ability, thereby improving the ability to generate superoxide anion (O 2- ) and hydroxyl radical ( ⁇ OH) with strong redox ability, so as to improve the bactericidal and antiviral effects of the photocatalytic antibacterial material of the embodiment of the present application.
  • the particle size of nitrogen oxides is in the nanometer range. In a further embodiment, the particle size of nitrogen oxides is 0.5nm-100nm, specifically 0.5nm, 0.1nm, 1nm, 5nm, 10nm, 15nm, Typical but non-limiting particle sizes of 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, etc.
  • particle sizes can effectively prepare the photocatalytic antibacterial material of the embodiment of the present application into various application dosage forms, such as preparing the photocatalytic antibacterial material of the embodiment of the present application into a spray application dosage form.
  • particle size of nitrogen oxides can also be adjusted according to the application environment of the photocatalytic antibacterial material in the embodiment of the present application.
  • the photocatalytic antibacterial material in the embodiment of the present application further includes a surfactant, and the surfactant is modified and bonded to the surface of the visible light catalyst substrate.
  • a surfactant is modified and bonded to the surface of the visible light catalyst substrate.
  • the weight percentage of the surfactant in the photocatalytic antibacterial material is 0.1wt% to 10wt%, specifically 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt% , 6wt%, 7wt%, 8wt%, 9wt%, 10wt% and other typical but non-limiting contents.
  • the modification effect of the surfactant on the surface of the visible light catalyst matrix is improved, thereby improving the dispersibility of the photocatalytic antibacterial material.
  • the surfactant includes at least one of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and Tween. These surfactants can effectively improve the dispersibility of the photocatalytic antibacterial material in the solvent, thereby improving the antibacterial and disinfection effect of the photocatalytic antibacterial material.
  • PEG polyethylene glycol
  • PVP polyvinylpyrrolidone
  • Tween Tween
  • the electron conduction additive contained in the photocatalytic antibacterial material of the embodiment of the present invention is loaded on the visible light catalyst matrix. Due to the existence of the electron-conducting additive, it acts as a conduction transfer function for the generation of electrons on the visible light catalyst matrix, and the electron-conducting additive excites oxygen and water on the surface and the surrounding environment to generate superoxide with strong redox ability. Negative ions (O 2- ) and hydroxyl radicals ( ⁇ OH), so that the electron conduction additive also has the effect of antibacterial and disinfection.
  • the synergistic effect between the electron conduction additive and the visible light catalyst matrix stimulates the oxygen and water in the surface and the surrounding environment to generate a large amount of Superoxide anion (O 2- ) and hydroxyl radical ( ⁇ OH) with strong redox ability endow the photocatalytic antibacterial material with efficient bactericidal and antiviral properties, and the bactericidal and antiviral properties are stable.
  • the photocatalytic antibacterial material of the embodiment of the present application can endow the photocatalytic antibacterial material of the embodiment of the present application with efficient, long-term and stable antibacterial and antiviral effects through the synergistic effect of the visible light catalyst matrix and the electronic conductivity additive, and overcome the existing TiO 2 can only play an antibacterial and disinfecting role in a specific environment of ultraviolet light, which leads to the problem of limited use. Moreover, it also avoids the massive use of Ag antibacterial agents, avoids secondary pollution, and reduces costs.
  • the loading weight of the conductive electron additive in the photocatalytic antibacterial material is 0.1%-10%, specifically 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6% , 7%, 8%, 9%, 10% and other weight content.
  • the electron conduction aid is supported on the visible light catalyst substrate in the form of particles, such as growing on the surface of the visible light catalyst substrate in situ.
  • the particle size of the electron-conducting additive is in the sub-nanometer range, such as the formed sub-nanometer particle clusters.
  • the uniformity of the conductive additives loaded on the visible light catalyst matrix is improved, and the synergistic effect of antibacterial and disinfection between the conductive additives and the visible light catalyst matrix is improved.
  • the particle size of the photocatalytic antibacterial material of the embodiment of the present application is adjusted together with the visible light catalyst matrix, and the application range of the photocatalytic antibacterial material of the embodiment of the application is improved.
  • the electron conduction additive includes at least one of Cu and a noble metal.
  • the noble metal includes at least one of Ag, Au, Pt, Pd, Rh, Ru, Ir.
  • the conductive electron additive When the conductive electron additive is Ag, such as when in a visible light environment, it can play an electron conduction role, and can play a synergistic effect on antibacterial disinfection with the visible light catalyst matrix, and improve the antibacterial disinfection of the photocatalytic antibacterial material of the embodiment of the present application. role.
  • Ag When in an environment without visible light, Ag can also play the role of sterilization and anti-virus, that is, antibacterial disinfection.
  • the synergistic effect between Ag and the visible light catalyst matrix endows the photocatalytic antibacterial material of the embodiment of the present application with efficient, long-lasting and stable antibacterial and antiviral effects, and is not affected by the use environment.
  • the embodiment of the present application provides the preparation method of the above-mentioned photocatalytic antibacterial material.
  • the process flow of the preparation method of the photocatalytic antibacterial material of the embodiment of the present application is shown in Figure 1, including the following steps:
  • the preparation method of the photocatalytic antibacterial material in the embodiment of the present application uses the visible light catalyst as the visible light catalyst matrix, and the conductive electron additive is loaded on the visible light catalyst matrix to form a photocatalytic antibacterial material with a composite structure, so that the visible light catalyst matrix and the conductive electrons
  • the auxiliary agent plays a synergistic effect, endows the prepared photocatalytic antibacterial material with efficient and continuous antibacterial and antiviral effects, and the antibacterial and antiviral effects are stable.
  • the photocatalyst in step S01 is the visible light catalyst matrix contained in the above photocatalytic antibacterial material. Therefore, the photocatalyst includes the nitrogen oxide contained in the above photocatalytic antibacterial material. In order to save space, the photocatalyst in step S01 will not be described in detail here.
  • the photocatalyst in step S01 is prepared according to a method comprising the following steps:
  • S012 heat-treating the oxide precursor in a nitrogen atmosphere to perform nitriding treatment to obtain a photocatalyst containing nitrogen oxides.
  • the oxide precursor in step S011 should be the oxide precursor used to prepare the above nitrogen oxide.
  • the nitrogen oxides include at least one of the above C 3 N 4 , Ta 3 N 5 , TaON, CaNbO 2 N, BaTaO 2 N, BaNbO 2 N, LaTax Nb 1-x ON 2 .
  • the oxide precursors in are respectively forming oxides corresponding to C 3 N 4 , Ta 3 N 5 , TaON, CaNbO 2 N, BaTaO 2 N, BaNbO 2 N, and LaTax Nb 1-x ON 2 .
  • each oxide precursor can be prepared separately according to a conventional method corresponding to each oxide or an improved method based on a conventional method.
  • the oxide precursor can be synthesized by hydrothermal method, but not only.
  • the nitriding treatment temperature is 500-950°C, specifically 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C and 950°C etc.
  • Non-limiting nitriding temperature In the temperature range of the nitriding treatment, the efficiency of the nitriding treatment can be effectively improved. In addition, the nitriding treatment in this temperature range should be sufficient, such as 0.5-10 hours, further 0.5-4 hours.
  • the electron conduction aid deposited in step S02 is the electron conduction aid contained in the above photocatalytic antibacterial material and supported on the surface of the visible light catalyst substrate. If the electron conduction aid includes Cu and at least one metal element in noble metals, the morphology of the electron conduction aid formed in step S02 is the same as that of the electron conduction aid contained in the photocatalytic antibacterial material above.
  • the method for supporting the electron conduction aid on the surface of the photocatalyst in step S02 includes the following steps:
  • S021 Prepare a mixed solution of photocatalyst and surfactant, and perform surface modification treatment on photocatalyst to form a sol;
  • S022 Add metal salt precursors of simple metals and a reducing agent to the sol, perform mixed treatment and reduction reaction, and deposit simple metals on the surface of the photocatalyst in situ.
  • the surface modification treatment in step S021 can be controlled according to the type of surfactant to realize the surface modification treatment of the photocatalyst, for example, ultrasonication in a water bath can be used.
  • the photocatalyst and the surfactant are mixed according to the mass ratio of 100:(10-0.05), specifically 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, 100:10 and other typical but non-limiting mass ratios.
  • the surface of the photocatalyst can be fully modified, and the dispersibility of the prepared photocatalytic antibacterial material can be improved.
  • the surfactant is at least one of the above-mentioned reagents such as polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and Tween.
  • PEG polyethylene glycol
  • PVP polyvinylpyrrolidone
  • Tween Tween
  • the metal salt precursor in step S022 should be a metal salt corresponding to Cu and at least one metal element in noble metals, such as Ag salt and Cu salt.
  • the metal salt precursor is added in the form of a metal ion complex, such as the complex should be any complex that can form a metal ion complex with a metal salt, such as glutathione ( GSH) complexes.
  • GSH glutathione
  • Adding the metal salt precursor in the form of a metal ion complex can effectively control the morphology and size of the electron conduction additive formed by precipitation, such as controlling the morphology of the deposited Ag as a sub-nanometer silver cluster.
  • the reducing agent in step S022 includes at least one of NaBH 4 , sodium borohydride, hydrazine hydrate, aldehydes, hydrogen and the like.
  • the amount of the reducing agent added should ensure that all the metal ions are reduced to form metal elements for precipitation, that is, the reducing agent should be in excess relative to the metal ion.
  • the metal salt precursor and the reducing agent are based on a mass ratio of 100 :(1 ⁇ 20) ratio for adding and mixing, specifically 100:1, 100:3, 100:5, 100:7, 100:10, 100:12, 100:14, 100:15, 100:17 , 100:18, 100:20 and other typical but non-limiting mass ratios.
  • the preparation method of the photocatalytic antibacterial material in the above-mentioned embodiments can effectively prepare the above composite structure photocatalytic antibacterial material, and can realize the control of the particle size of the prepared photocatalytic antibacterial material, the loading of the conductive additives, and the control of the preparation conditions.
  • the morphology and content of the photocatalyst are controlled and conditions are improved to improve the synergistic effect between the visible light catalyst matrix and the conductive electron additive, so as to improve the antibacterial and antiviral effects of photocatalytic antibacterial materials.
  • process steps and conditions of the preparation method of the photocatalytic antibacterial material in the embodiment of the present application are controllable, and the antibacterial and antiviral properties of the prepared photocatalytic antibacterial material are stable, and the efficiency is high, and the economic cost is reduced.
  • the embodiment of the present application provides the application of the above-mentioned photocatalytic antibacterial agent.
  • a photocatalytic antibacterial agent is provided.
  • the photocatalytic antibacterial agent of the embodiment of the present application is the above photocatalytic antibacterial material.
  • the photocatalytic antibacterial agent of the embodiment of the present application can have high-efficiency, continuous and stable antibacterial and antiviral effects in the visible light environment and no visible light environment, and the photocatalytic antibacterial agent of the embodiment of the application can be made into a corresponding antibacterial agent according to the needs of the application.
  • the dosage form is used to achieve long-lasting, efficient and stable antibacterial and disinfection effects.
  • the dosage forms of the photocatalytic antibacterial agents in the examples of the present application are sprays, powders or coatings for film formation. That is, the above photocatalytic antibacterial materials can be formulated into sprays, powders or coatings according to the needs of the application.
  • the dosage form of the photocatalytic antibacterial agent in the embodiment of the present application is a spray
  • the particle size of the above photocatalytic antibacterial material is controlled, and the spray of the sol dispersion is prepared, and the solvent is quickly volatilized during the spraying process. It can form an ultra-thin and stable coating or film, which has a long-term antibacterial and disinfection effect, and is stable and convenient for industrial application. In this way, the problems of high preparation cost of traditional antibacterial agents and poor antibacterial effect caused by alcohol aerosol disinfecting sprays are effectively overcome.
  • the photocatalytic antimicrobial agent of the present application and its preparation method are illustrated below through a number of specific examples.
  • Embodiments 1 to 5 respectively provide a photocatalytic antibacterial agent and a preparation method thereof.
  • the surface of the antibacterial matrix is combined with PEG surface modifier and subnanometer silver clusters.
  • the preparation method of photocatalytic antibacterial agent comprises the steps:
  • La(NO) 3 , TaCl 5 and NbCl 5 were added to excess KOH (10 g) and NaOH (5 g) saturated solution according to the following molar amounts respectively, then transferred to a hydrothermal kettle, and then in a muffle furnace, Heat to 200°C at a heating rate of 10K/min, and keep at this temperature for 20 hours, then cool down to room temperature; wash the reaction product with ultrapure water for 3-5 times at room temperature, and centrifuge to remove residual NaOH and KOH, The filter cake was vacuum-dried overnight to obtain LaKNaTa x Nb 1-x O 5 powder;
  • Example 1 La(NO) 3 , TaCl 5 , and NbCl 5 were added in order of 5 mmol, 1 mmol, and 5 mmol; in Example 2, La(NO) 3 , TaCl 5 , and NbCl 5 were added in order of 5 mmol, The molar amounts of 2mmol and 4mmol were added; in Example 3, La(NO) 3 , TaCl 5 , and NbCl 5 were added in sequence according to the molar amounts of 5mmol, 3mmol, and 3mmol; in Example 4, La(NO) 3 , TaCl 5 , NbCl 5 was added sequentially according to the molar quantities of 5mmol, 4mmol, and 2mmol; in Example 5, La(NO) 3 , TaCl 5 , and NbCl 5 were added sequentially according to the molar quantities of 5mmol, 5mmol, and 1mmol;
  • the nitriding treatment temperature in embodiment 1 is 700 °C, the time is 4 hours;
  • the nitriding treatment temperature in embodiment 2 is 750 °C, the time is 3 hours;
  • the nitriding treatment temperature in embodiment 3 is 800 °C, time It was 2 hours;
  • the nitriding treatment temperature in embodiment 4 was 850 °C, and the time was 1 hour;
  • the nitriding treatment temperature in embodiment 5 was 950 °C, and the time was 0.5 hour;
  • the particle size of the LaTa x Nb 1-x ON 2 photocatalytic antibacterial matrix is 100 nanometers to 10 microns, and the particle size of the silver clusters is 0.5-20nm.
  • the content of silver clusters in Ag-LaTa x Nb 1-x ON 2 0.5 to 5 wt%.
  • This embodiment provides a photocatalytic antibacterial agent and a preparation method thereof.
  • the photocatalytic antibacterial agent is Ta 3 N 5 , which uses Ta 3 N 5 as the photocatalytic antibacterial matrix, and PEG surface modifier and subnanometer Rh clusters are combined on the surface of the Ta 3 N 5 photocatalytic antibacterial matrix.
  • the preparation method of photocatalytic antibacterial agent comprises the steps:
  • Ta 2 O 5 (5mmol) and K 2 CO 3 (5.25mmol) were mixed at a Ta:K molar ratio of 1:1.05, and excess potassium was added to compensate for the loss caused by volatilization at high temperature, in the presence of a small amount of ethanol as a dispersant , the agate mixture was thoroughly ground in an agate mortar for 90 minutes; after drying, the resulting mixture was transferred to an alumina crucible and calcined at 1173 K for 1 h, followed by 1423 K in static air for 10 h; in this way The KTaO 3 was washed with ultrapure water at 343K for 2 h, and centrifuged twice to remove any residual K 2 CO 3 ; then heated at 343 K overnight to completely dry the powder;
  • KTaO 3 (0.5 g) was transferred to an alumina tube and nitriding was carried out at 1173 K under 100 ml min of gaseous NH 3 over a time span of 0.05 to 4 h;
  • This comparative example provides LaTa x Nb 1-x ON 2 photocatalyst. Compared with Example 1, the difference is that no silver clusters are loaded on the photocatalyst without LaTax Nb 1-x ON 2 .
  • This comparative example provides a silver antibacterial agent, wherein the particle diameter of the silver antibacterial agent is close to or the same as the average particle diameter of the silver clusters contained in Example 1.
  • the photocatalytic antibacterial material provided by the embodiment of the present application has excellent sterilization and disease resistance under sunlight conditions, and it completely kills all the bacteria in each experimental group.
  • Comparative Examples 1 and 2 cannot achieve this effect.
  • the photocatalytic antibacterial material provided by the embodiment of the application with the photocatalyst provided by Comparative Example 1 and the silver antibacterial agent of Comparative Example 2 respectively, the contained electron-conducting additive and visible light catalyst matrix of the photocatalytic antibacterial material provided by the embodiment of the application There is a synergistic effect between them, endowing the photocatalytic antibacterial material with efficient bactericidal and antiviral properties.

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Abstract

一种光催化抗菌材料及其制备方法和光催化抗菌剂。所述光催化抗菌材料包括可见光催化剂基体和导电子助剂，导电子助剂用于所述可见光催化剂基体对可见光相应后进行电子和空穴的分离，且导电子助剂负载在所述可见光催化剂基体上。所述光催化抗菌材料通过导电子助剂和可见光催化剂基体之间起到协同增效作用，从而赋予光催化抗菌材料高效、稳定和长效的抗菌消毒作用。采用所述光催化抗菌材料制备方法制备的光催化抗菌材料的抗菌和抗病毒作用等性能稳定，而且效率高，降低了经济成本。所述光催化抗菌剂含有所述光催化抗菌材料。

Description

光催化抗菌材料及其制备方法和光催化抗菌剂 技术领域
本申请属于光催化抗菌剂技术领域，具体涉及一种光催化抗菌材料及其制备方法和光催化抗菌剂。
背景技术
随着疫情的肆虐，给人类生命健康带来巨大威胁，全球公共卫生和医疗服务体系也不断面临挑战，人们对环境卫生的重视日益提高，老百姓的杀菌消毒意识也明显增强。此外，人类对抗生素的泛滥使用导致细菌的耐药性增强，抗菌材料的研发速度已经难以应对细菌耐药性和抗药性的不断增强，人类社会可能面临大规模细菌感染而无法医治的危险，新型抗菌材料设计研发迫在眉睫。
抗菌材料是一类具有抑菌或杀菌性能的新型功能材料。抗菌材料的抗菌性可以通过在高分子材料中添加适量的抗菌剂，或以其他方式将抗菌基团引入到载体材料中。所制备的抗菌材料本身具有抑制、消灭有害微生物的功能，可以有效的防止有害微生物的滋生。抗菌剂是一些微生物高度敏感的化学成分，是抗菌材料的核心成分，目前已经研发并应用的抗菌剂类型有：导电子助剂、有机抗菌剂和复合型抗菌剂三大类。其中，纳米银作为一种重要的杀菌剂受到广泛关注，可以用作纺织材料、涂料、食品添加剂等来消除微生物。目前对于银的杀菌机理说法不一，其中大多数的研究结果将银的广谱抗菌性归因于从纳米银解离出来的银离子，即银离子通过膜损伤、DNA损伤以及解离过程产生的活性氧物种(ROS)影响细胞代谢等机理杀死细菌。然而，单纯以银离子或者银络合物作为杀菌剂极易对正常的细胞产生副作用。而且金属元素离子抗菌存在着贵金属离子扩散造成二次污染的隐患，还存在产品制备成本高和稳定性差等缺点。
相比而言，光催化抗菌材料因具有良好的抗菌性、光催化性能、造价成本较低和稳定性等特点，在抗菌和光催化领域受到广泛关注。光催化型抗菌剂可以吸收外界的光电子能量，价带的电子跃迁到导带上，激发抗菌剂表面及周围环境中的氧和水，形成的超氧负离子(O 2 -)和羟基自由基(·OH)具有强氧化还原能力，能让微生物的蛋白质和脂质分解，促使微生物机体生化反应紊乱，破坏病原微生物细胞的分裂繁殖能力，进而抑制或杀灭有害微生物。由于微生物的膜蛋白收到损伤之后无法恢复，因此光催化型抗菌剂也具有持久的抗菌效果。
目前常用的光催化抗菌材料为TiO 2，由于其具有抑菌效果好、热稳定性高、价格低廉且无污染等诸多优点被广泛应用于光催化抑菌领域。如KayanoSunada等人用异丙醇钛溶液在500℃下退火制备了TiO 2膜在紫外线照射用TiO 2光催化剂杀死大肠杆菌时，细胞中的内毒素也被有效降解。FeyzaDundarArisoy等人将低至10wt％的TiO 2掺入化学基质中，在1小时的紫外线照射下，超过95％的大肠杆菌和高达80％的金黄色葡萄球菌被灭活。因此，TiO 2作为光催化抗菌材料时，其需要在紫外光下进行相应催化效果，但是在太阳能光谱中，紫外光能量仅占5％左右。因此，TiO 2作为光催化抗菌材料由于使用条件受到限制。
发明内容
本申请的目的在于克服现有技术的上述不足，提供一种光催化抗菌材料及其制备方法和光催化抗菌剂，以解决现有光催化抗菌材料使用条件受限的技术问题。
为了实现上述申请目的，本申请的第一方面，提供了一种光催化抗菌材料。本申请光催化抗菌材料包括可见光催化剂基体，还包括导电子助剂，导电子助剂用于可见光催化剂基体对可见光相应后进行电子和空穴的分离，且导电子助剂负载在可见光催化剂基体上。
进一步地，导电子助剂在光催化抗菌材料中的负载重量为0.1％-10％。
进一步地，导电子助剂包括Cu和贵重金属中的至少一种。
更进一步地，贵重金属包括Ag、Au、Pt、Pd、Rh、Ru、Ir中的至少一种。
进一步地，导电子助剂是以纳米颗粒形貌负载在可见光催化剂基体的表面。
更进一步地，纳米颗粒形貌的粒径为亚纳米范围。
进一步地，可见光催化剂基体的材料包括氮氧化物。
更进一步地，可见光催化剂基体的材料的带隙为0-2eV；和/或
具体地，氮氧化物包括C 3N 4、Ta 3N 5、TaON、CaNbO 2N、BaTaO 2N、BaNbO 2N、LaTa xNb 1-xON 2中的至少一种，其中，x＝0-1。
更进一步地，氮氧化物的颗粒粒径为纳米范围。
进一步地，光催化抗菌材料还包括表面活性剂，表面活性剂修饰结合在可见光催化剂基体的表面。
具体地，表面活性剂包括聚乙二醇、聚乙烯吡咯烷酮、吐温中的至少一种；和/或
更进一步地，表面活性剂在光催化抗菌材料的重量百分含量为0.1wt％～10wt％。
本申请的第二方面，提供了一种光催化抗菌材料的制备方法。本申请光催化抗菌材料的制备方法包括如下步骤：
提供可见光催化剂；
在光催化剂上负载导电子助剂，使得导电子助剂结合在光催化剂上，得到光催化抗菌材料；
其中，导电子助剂用于可见光催化剂基体对可见光相应后进行电子和空穴的分离。
进一步地，可见光催化剂为氮氧化物，且氮氧化物按照包括如下步骤的方法制备：
制备氮氧化物的氧化物前驱体；
将氧化物前驱体于氮气气氛中进行加热处理以进行氮化处理，得到含氮氧 化物的光催化剂。
更进一步地，氮化处理的温度为500-950℃。
进一步地，导电子助剂包括Cu和贵重金属中的至少一种金属单质，且在光催化剂表面负载导电子助剂的方法包括如下步骤：
将可见光与表面活性剂配制成混合溶液，并对可见光催化剂进行表面改性处理，形成溶胶；
向溶胶中加入金属单质的金属盐前驱体和还原剂，进行混合处理和还原反应，在可见光催化剂上原位沉积金属单质。
更进一步地，金属盐前驱体为金属离子配合物。
更进一步地，还原剂包括NaBH 4、硼氢化钠、水合肼、醛类、氢气等中的至少一种。
本申请的第三方面，提供了一种光催化抗菌剂。本申请光催化抗菌剂包括本申请光催化抗菌材料或由本申请光催化抗菌材料制备方法制备的光催化抗菌材料。
进一步地，光催化抗菌剂为喷雾剂、粉剂、成膜剂或涂料。
与现有技术相比，本申请具有如下技术效果：
本申请第一方面提供的光催化抗菌材料是以可见光催化剂材料作为基体，其N2p轨道能级比O2p轨道能级低，带隙窄，而且比表面积大，活性位含量丰富，在太阳光可见区呈现较强的吸收，增加光生电子和空穴的能力。光催化抗菌材料所含的导电子助剂能够有效将可见光催化剂材料在可见光激发下产生的电子进行转移，也即是有效促进界面电荷转移，增加光生电子和空穴的分离能力，避免可见光催化剂基体在可见光催化下产生的电子和空穴复合消失。由于导电子助剂对可见光催化剂基体产生电子的传导转移作用，被传导有电子导电子助剂激发表面及周围环境中的氧和水，生成具有强氧化还原能力的超氧负离子(O 2-)和羟基自由基(·OH)。而具有空穴的可见光催化剂基体也会激发表面及周围环境中的氧和水，生成具有强氧化还原能力的超氧负离子(O 2-)和羟基 自由基(·OH)。因此，导电子助剂和可见光催化剂基体之间起到协同增效作用，通过两者的增效作用激发表面及周围环境中的氧和水生成大量的具有强氧化还原能力的超氧负离子(O 2-)和羟基自由基(·OH)，从而赋予光催化抗菌材料高效的杀菌和抗病毒特性，而且杀菌和抗病毒性稳定。
本申请第二方面提供的光催化抗菌材料制备方法将可见光催化剂作为基体，并将导电子助剂负载在可见光催化剂基体上，构成复合结构光催化抗菌材料，从而使得可见光催化剂基体与导电子助剂起到协同增效作用，赋予制备的光催化抗菌材料在可见光作用下具有高效而且长效的抗菌和抗病毒作用，而且抗菌和抗病毒作用稳定。另外，本申请光催化抗菌材料制备方法工艺步骤和条件可控，制备的光催化抗菌材料抗菌和抗病毒作用等性能稳定，而且效率高，降低了经济成本。
本申请第三方面提供的光催化抗菌剂由于含有本申请光催化抗菌材料，因此，光催化抗菌剂可以在可见光环境具有高效、长效和稳定的抗菌和抗病毒作用，而且可以根据应用的需要将本申请光催化抗菌剂制成相应的使用剂型，实现长效、高效和稳定的抗菌消毒的效果。
附图说明
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施例复合介质陶瓷的制备方法流程示意图。
具体实施方式
为了使本申请要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体 实施例仅仅用以解释本申请，并不用于限定本申请。
本申请中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。
本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a,b,或c中的至少一项(个)”，或，“a,b,和c中的至少一项(个)”，均可以表示：a,b,c,a-b(即a和b),a-c,b-c,或a-b-c，其中a,b,c分别可以是单个，也可以是多个。
应理解，在本申请的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本申请实施例的实施过程构成任何限定。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。
本申请实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本申请实施例说明书相关组分的含量按比例放大或缩小均在本申请实施例说明书公开的范围之内。具体地，本申请实施例说明书中所述的质量可以是μg、mg、g、kg等化工领域公知的质量单位。
第一方面，本申请实施例提供了一种光催化抗菌材料。本申请实施例光催化抗菌材料包括可见光催化剂基体和负载在可见光催化剂基体上的导电子助剂。
其中，本申请实施例光催化抗菌材料所含的可见光催化剂基体其赋予本申请实施例光催化抗菌材料具有可见光催化抗菌消毒作用，同时又起到载体作用， 负载导电子助剂并发挥导电子助剂的电子传导和产生具有氧化能力和杀菌消毒的离子和功能基团。
实施例中，该可见光催化剂基体包括氮氧化物可见光催化剂材料。该些可见光催化剂材的N2p轨道能级比O2p轨道能级低，带隙窄，而且比表面积大，活性位含量丰富，在太阳光可见区呈现较强的吸收，增加光生电子和空穴的能力。其中，产生的电子会通过负载的导电子助剂传导至导电子助剂，因此，可见光催化剂基体留下的空穴会激发光其表面及周围环境中的氧和水，生成具有强氧化还原能力的超氧负离子(O 2-)和羟基自由基(·OH)，从而发挥杀菌和抗病毒特性，而且杀菌和抗病毒性能稳定。
实施例中，该可见光催化剂基体的材料的带隙为0-2eV。该范围带隙窄，能够提高光催化剂基体在太阳光可见区呈现较强的吸收以增强生成电子和空穴的能力，从而产生丰富的具有强氧化还原能力的超氧负离子(O 2-)和羟基自由基(·OH)能力，从而提高本申请实施例光催化抗菌材料的杀菌和抗病毒效果。
在具体实施例中，上述氮氧化物包括C 3N 4、Ta 3N 5、TaON、CaNbO 2N、BaTaO 2N、BaNbO 2N、LaTa xNb 1-xON 2中的至少一种，其中，LaTa xNb 1-xON 2中的x＝0-1，因此，LaTa xNb 1-xON 2至少可以是LaTaON 2、LaNbON 2等。该些氮氧化物的N2p轨道能级比O2p轨道能级低，具有窄的带隙，大的比表面积，丰富的活性位含量，其能够在太阳光可见区激发下更易生成生成电子和空穴的能力，从而提高生成具有强氧化还原能力的超氧负离子(O 2-)和羟基自由基(·OH)能力，以提高本申请实施例光催化抗菌材料的杀菌和抗病毒效果。
实施例中，氮氧化物的颗粒粒径为纳米范围，进一步实施例中，氮氧化物的颗粒粒径为0.5nm-100nm，具体可以是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等典型但非限制性的粒径。该些粒径能够有效将本申请实施例光催化抗菌材料制备成各种应用剂型，如将本申请实施例光催化抗菌材料制备成喷雾应用剂型。当然，还可 以根据本申请实施例光催化抗菌材料的应用环境，对氮氧化物的颗粒粒径进行调整。
在进一步实施例中，本申请实施例光催化抗菌材料还包括表面活性剂，表面活性剂修饰结合在可见光催化剂基体的表面。通过在可见光催化剂基体表面修饰表面活性剂，提高本申请实施例光催化抗菌材料的分散性，从而提高光催化抗菌材料在应用中的分散性，充分发挥光催化抗菌材料的抗菌消毒的效果。而且还方便根据应用的需要灵活将光催化抗菌材料配制成不同应用剂型，如配制成喷剂。
实施例中，表面活性剂在光催化抗菌材料的重量百分含量为0.1wt％～10wt％，具体可以是0.1wt％、0.5wt％、1wt％、2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、9wt％、10wt％等典型但非限制性的含量。通过控制表面活性剂的含量，提高表面活性剂对可见光催化剂基体表面的改性作用，从而提高光催化抗菌材料的分散性。
具体实施例中，表面活性剂包括聚乙二醇(PEG)、聚乙烯吡咯烷酮(PVP)、吐温中的至少一种。该些表面活性剂能够有效提高光催化抗菌材料在溶剂中的分散性，从而提高光催化抗菌材料的抗菌消毒的效果。
本发明实施例光催化抗菌材料所含的导电子助剂负载在可见光催化剂基体上。由于导电子助剂的存在，其起到对可见光催化剂基体产生电子的传导转移作用，被传导有电子导电子助剂激发表面及周围环境中的氧和水，生成具有强氧化还原能力的超氧负离子(O 2-)和羟基自由基(·OH)，从而使得导电子助剂也具有抗菌消毒的作用。此时，导电子助剂和可见光催化剂基体之间起到的协同增效作用，通过导电子助剂和可见光催化剂基体两者的增效作用，激发表面及周围环境中的氧和水生成大量的具有强氧化还原能力的超氧负离子(O 2-)和羟基自由基(·OH)，从而赋予光催化抗菌材料高效的杀菌和抗病毒特性，而且杀菌和抗病毒性稳定。因此，本申请实施例光催化抗菌材料通过可见光催化剂基体和导电子助剂的协同增效作用，赋予本申请实施例光催化抗菌材料高效、 长效和稳定的抗菌和抗病毒作用，克服现有TiO 2只会在紫外光特定环境中起到抗菌消毒作用而导致使用受限的问题。而且也避免了Ag抗菌剂的大量使用，避免了二次污染，降低了成本。
实施例中，导电子助剂在光催化抗菌材料中的负载重量为0.1％-10％，具体可以是0.1％、0.5％、1％、2％、3％、4％、5％、6％、7％、8％、9％、10％等重量含量。通过对导电子助剂的含量控制，提高导电子助剂与可见光催化剂基体之间抗菌消毒的协同增效，提高光催化抗菌材料在可见光环境中的抗菌消毒作用。
实施例中，该导电子助剂是以颗粒形貌负载在可见光催化剂基体上，如原位生长在可见光催化剂基体的表面。而且经检测得知，导电子助剂的粒径越小，其与可见光催化剂基体之间的协同增效作用越强，光催化抗菌材料的抗菌消毒效果越优异。进一步实施例中，控制颗粒形貌导电子助剂的粒径为亚纳米范围，如形成的亚纳米颗粒簇。通过控制导电子助剂负载的形貌和粒径大小，提高导电子助剂的负载在可见光催化剂基体上的均匀性，提高导电子助剂与可见光催化剂基体之间的抗菌消毒协同增效作用，而且与可见光催化剂基体一起调节本申请实施例光催化抗菌材料的粒径大小，提高本申请实施例光催化抗菌材料的应用范围。
具体实施例中，该导电子助剂包括Cu和贵重金属中的至少一种。在具体实施例中，贵重金属包括Ag、Au、Pt、Pd、Rh、Ru、Ir中的至少一种。该些导电子助剂具有良好的电子传导性，提高导电子助剂与可见光催化剂基体之间的抗菌消毒协同增效作用，提高光催化抗菌材料在可见光环境中的抗菌消毒作用。如当导电子助剂为Ag时，Ag是以亚纳米银簇形貌负载在可见光催化剂基体上。当导电子助剂为Ag时，如当在可见光环境中时，其能够发挥电子传导作用，能够与可见光催化剂基体起到抗菌消毒的协同增效作用，提高本申请实施例光催化抗菌材料抗菌消毒的作用。当在无可见光环境中时，Ag也能够发挥杀菌和抗病毒也即是抗菌消毒的作用。此时，Ag与可见光催化剂基体之间协 同增效作用，赋予本申请实施例光催化抗菌材料高效、长效和稳定的抗菌和抗病毒作用，不受使用环境的影响。
第二方面，本申请实施例提供了上文光催化抗菌材料的制备方法。本申请实施例光催化抗菌材料的制备方法工艺流程如图1所示，包括如下步骤：
S01：提供可见光催化剂；
S01：在光催化剂上负载导电子助剂，使得导电子助剂结合在光催化剂上，得到光催化抗菌材料。
这样，本申请实施例光催化抗菌材料制备方法将可见光催化剂作为可见光催化剂基体，并将导电子助剂负载在可见光催化剂基体上，构成复合结构的光催化抗菌材料，从而使得可见光催化剂基体与导电子助剂起到协同增效作用，赋予制备的光催化抗菌材料具有高效而且持续的抗菌和抗病毒作用，而且抗菌和抗病毒作用稳定。
其中，步骤S01中的光催化剂为上文光催化抗菌材料所含的可见光催化剂基体。因此，该光催化剂包括上文光催化抗菌材料所含的氮氧化物。为了节约篇幅，在此不再对步骤S01中的光催化剂做赘述。
实施例中，当可见光催化剂为氮氧化物，步骤S01中的光催化剂按照包括如下步骤的方法制备：
S011：制备光催化剂的氧化物前驱体；
S012：将氧化物前驱体于氮气气氛中进行加热处理以进行氮化处理，得到含氮氧化物的光催化剂。
其中，步骤S011中的氧化物前驱体应该是用于制备上文氮氧化物的氧化物前驱体。如当氮氧化物包括如上文C 3N 4、Ta 3N 5、TaON、CaNbO 2N、BaTaO 2N、BaNbO 2N、LaTa xNb 1-xON 2中的至少一种时，那么步骤S011中的氧化物前驱体分别为形成C 3N 4、Ta 3N 5、TaON、CaNbO 2N、BaTaO 2N、BaNbO 2N、LaTa xNb 1-xON 2对应的氧化物。在具体实施例中，氮氧化物为LaTa xNb 1-xON 2时，那么此时氧化物可以是LaKNaTa xNb 1-xO 5。另外，各氧化物前驱体可以按照各氧化物对应 的常规方法或基于常规方法改进方法进行分别制备。如可以但不仅仅采用水热法合成氧化物前驱体。
步骤S012中的氮化处理过程中，在高温的作用下，实现氮原子替代氧化物前驱体中的部分元素，从而生成上文具有窄带隙和在可见光激发下具有抗菌消毒作用的氮氧化物。实施例中，氮化处理的温度为500-950℃，具体可以是500℃、550℃、600℃、650℃、700℃、750℃、800℃、850℃、900℃和950℃等典型但非限制性的氮化处理的温度。在该氮化处理的温度范围，能够有效提高氮化处理的效率。另外，该温度范围的氮化处理应该是充分的，如可以是0.5-10小时，进一步为0.5-4小时。
步骤S02中的沉积的导电子助剂为上文光催化抗菌材料所含的且负载在可见光催化剂基体表面的导电子助剂。如导电子助剂包括Cu和贵重金属中的至少一种金属单质时，步骤S02中形成的导电子助剂形貌如上文光催化抗菌材料所含的导电子助剂的形貌。
实施例中，当导电子助剂包括Cu和贵重金属中的至少一种金属单质时，步骤S02中在光催化剂表面负载导电子助剂的方法包括如下步骤：
S021：将光催化剂与表面活性剂配制成混合溶液，并对光催化剂进行表面改性处理，形成溶胶；
S022：向溶胶中加入金属单质的金属盐前驱体和还原剂，进行混合处理和还原反应，在光催化剂表面原位沉积金属单质。
其中，步骤S021中的表面改性处理可以根据表面活性剂的种类进行控制条件实现对光催化剂进行表面改性处理，如可以采用水浴超声。实施例中，在S021的混合溶液中，光催化剂与表面活性剂按照质量比为100:(10～0.05)的比例进行混合处理，具体可以是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、100:10等典型但非限制性的质量比。通过控制光催化剂与表面活性剂的混合比例，实现对光催化剂表面进行充分改性处理，提高制备的光催化抗菌材料的分散性。当然，可以对光催化剂颗 粒的控制，经表面改性处理后，还可以生成非溶胶的分散溶液。
实施例中，该表面活性剂如上文所述的聚乙二醇(PEG)、聚乙烯吡咯烷酮(PVP)、吐温等试剂中的至少一种。
步骤S022中的金属盐前驱体应该是形成Cu和贵重金属中的至少一种金属单质对应的金属盐，如Ag盐和Cu盐等。实施例中，该金属盐前驱体是以金属离子配合物的形式添加，如该配合物应该是能够与金属盐形成金属离子配合物的任何配合物，如可以但不仅仅为谷胱甘肽(GSH)配合物。将金属盐前驱体以金属离子配合物的形式添加，能够有效控制沉淀形成的导电子助剂的形貌和尺寸，如控制沉积形成的Ag为亚纳米银簇形貌。
实施例中，步骤S022中的还原剂包括NaBH 4、硼氢化钠、水合肼、醛类、氢气等中的至少一种。该还原剂的添加量应该保证金属离子全部被还原生成金属单质以沉淀，也即是还原剂应该是相对金属离子是过量的，如实施例中，金属盐前驱体与还原剂的按照质量比100:(1～20)的比例进行添加混合，具体可以是100:1、100:3、100:5、100:7、100:10、100:12、100:14、100:15、100:17、100:18、100:20等典型但非限制性的质量比。
因此，上述各实施例中光催化抗菌材料制备方法能够有效制备上文复合结构光催化抗菌材料，而且能够通过对制备条件的控制，实现对制备的光催化抗菌材料粒径、负载导电子助剂的形貌和含量等进行控制和条件，提高可见光催化剂基体与导电子助剂起到协同增效作用，以提高光催化抗菌材料抗菌和抗病毒作用。另外，本申请实施例光催化抗菌材料制备方法工艺步骤和条件可控，制备的光催化抗菌材料抗菌和抗病毒作用等性能稳定，而且效率高，降低了经济成本。
第三方面，本申请实施例提供上文光催化抗菌剂的应用。具体提供了一种光催化抗菌剂。本申请实施例光催化抗菌剂上文光催化抗菌材料。这样，本申请实施例光催化抗菌剂可以在可见光环境和无可见光环境均具有高效、持续和稳定的抗菌和抗病毒作用，而且可以根据应用的需要将本申请实施例光催化抗 菌剂制成相应的使用剂型，实现长效、高效和稳定的抗菌消毒的效果。
如实施例中，本申请实施例光催化抗菌剂的剂型为喷雾剂、粉剂或用于成膜的涂料。也即是，上文光催化抗菌材料可以根据应用的需要配制成喷雾剂、粉剂或涂料。
在具体实施例中，当本申请实施例光催化抗菌剂的剂型为喷雾剂时，控制上文光催化抗菌材料的颗粒大小，配制成溶胶分散液的喷雾剂，在喷涂过程中伴随溶剂快速挥发可形成超薄稳定的涂层或薄膜，起到长久抗菌消毒的效果，而且稳定好，便于产业化应用。这样，有效克服传统的抗菌剂制备成本高、醇类气雾消杀喷剂易挥发而造成抗菌效果差等问题。
以下通过多个具体实施例来举例说明本申请实施例光催化抗菌剂及其制备方法等。
实施例1-实施例5
本实施例1至实施例5分别提供一种光催化抗菌剂及其制备方法。光催化抗菌剂为Ag-LaTa xNb 1-xON 2(x＝0-1)，是以LaTa xNb 1-xON 2为光催化抗菌基体，在LaTa xNb 1-xON 2光催化抗菌基体表面结合有PEG表面改性剂和亚纳米银簇。
光催化抗菌剂的制备方法包括如下步骤：
S1.LaTa xNb 1-xON 2光催化抗菌基体的制备：
S11.采用水热法合成层状LaKNaTa xNb 1-xO 5氧化物前驱体(x＝0-1)：
首先将La(NO) 3、TaCl 5和NbCl 5分别按照如下摩尔量加入到过量的KOH(10g)和NaOH(5g)饱和溶液中，随后转移到水热釜中，然后在马弗炉中，以10K/min的升温速率加热至200℃，并在该温度下保持20小时，随后降温至室温；将反应产物室温下用超纯水洗涤3-5次，并离心除去残余的NaOH和KOH，将滤饼真空干燥过夜获得LaKNaTa xNb 1-xO 5粉末；
其中，实施例1中，La(NO) 3、TaCl 5、NbCl 5依次按照5mmol、1mmol、5mmol的摩尔量添加；实施例2中，La(NO) 3、TaCl 5、NbCl 5依次按照5mmol、2mmol、4mmol的摩尔量添加；实施例3中，La(NO) 3、TaCl 5、NbCl 5依次按照5mmol、 3mmol、3mmol的摩尔量添加；实施例4中，La(NO) 3、TaCl 5、NbCl 5依次按照5mmol、4mmol、2mmol的摩尔量添加；实施例5中，La(NO) 3、TaCl 5、NbCl 5依次按照5mmol、5mmol、1mmol的摩尔量添加；
S12.将LaKNaTa xNb 1-xO 5进行氮化处理：
将获得的2g LaKNaTa xNb 1-xO 5分别在如下条件下进行氮化处理，分别制备LaTa xNb 1-xON 2；
实施例1中的氮化处理温度为700℃、时间为4小时；实施例2中的氮化处理温度为750℃、时间为3小时；实施例3中的氮化处理温度为800℃、时间为2小时；实施例4中的氮化处理温度为850℃、时间为1小时；实施例5中的氮化处理温度为950℃、时间为0.5小时；
S2.在LaTa xNb 1-xON 2光催化抗菌基体沉积亚纳米银簇：
S21.取2g LaTa xNb 1-xON 2放入烧瓶中，加入2M的PEG水溶液50mL，然后充分搅拌均匀后，水浴超声2-5小时，将其表面修饰PEG，使LaTa xNb 1-xON 2高度分散到水溶液中得到氮氧化物溶胶；
S22.首先20mg AgNO 3与100mg GSH充分混合形成GSH-Ag +络合物，随后将其加入到1g LaTa xNb 1-xON 2溶胶体系中充分搅拌均匀，然后加入0.1M的NaBH 4，进行原位还原，将银簇可控沉积到氮氧化物表面形成Ag-LaTa xNb 1-xON 2胶体溶液；然后利用旋转蒸发仪将体系中的溶剂蒸发，得到的产物Ag-LaTa xNb 1-xON 2光催化抗菌材料。
经检测，LaTa xNb 1-xON 2光催化抗菌基体的粒径为100纳米～10微米，银簇的粒径为0.5～20nm银簇在Ag-LaTa xNb 1-xON 2中的含量为0.5～5wt％。
实施例6
本实施例提供一种光催化抗菌剂及其制备方法。光催化抗菌剂为Ta 3N 5，是以Ta 3N 5为光催化抗菌基体，在Ta 3N 5光催化抗菌基体表面结合有PEG表面改性剂和亚纳米Rh簇。
光催化抗菌剂的制备方法包括如下步骤：
S1.Ta 3N 5光催化抗菌基体的制备：
S11.采用固相反应法制备KTaO 3氮化前驱体：
将Ta 2O 5(5mmol)和K 2CO 3(5.25mmol)以1:1.05的Ta:K摩尔比混合，添加过量的钾以补偿高温下挥发造成的损失，在少量乙醇作为分散剂的存在下，将玛瑙混合物在玛瑙砂浆中彻底研磨90分钟；干燥后，将所得混合物转移到氧化铝坩埚中，并在1173K下煅烧1h，然后在1423K下在静态空气中煅烧10h；以这种方式获得的KTaO 3在343K下用超纯水洗涤2h，并离心两次以去除任何残余K 2CO 3；然后在343K温度下加热一夜，使粉末完全干燥；
S12.将KTaO 3进行氮化处理：
将KTaO 3(0.5g)转移到氧化铝管中，并在1173K下在100ml min的气体NH 3下进行氮化，时间跨度为0.05至4h；
S2.在Ta 3N 5光催化抗菌基体上沉积贵金属Rh：
取2g Ta 3N 5放入球磨罐中与5ml乙醇充分混合并球磨处理5小时，获得分散均匀，小尺寸的Ta 3N 5样品，将球磨后的产物离心洗涤，并再次分散到1ml去离子水的蒸发皿中。随后向其入200μl 1M RhCl 3溶液，用玻璃棒充分搅拌均匀使其完全浸渍到Ta 3N 5样品，然后将蒸发皿放置于60℃加热板中一边搅拌一边加入，使水完全蒸发，随后将样品转移到管式炉中，氢气200℃还原半个小时，得到Rh-Ta 3N 5光催化抗菌涂层材料或成膜剂。
对比例1
本对比例提供LaTa xNb 1-xON 2光催化剂。与实施例1相比不同在于不含LaTa xNb 1-xON 2光催化剂上不负载银簇。
对比例2
本对比例提供银抗菌剂，其中，该银抗菌剂的粒径与实施例1中所含银簇粒径接近或平均粒径相同。
抗菌消毒效果实验
将上述各实施例1至实施例6提供的光催化抗菌剂和对比例1提供的抗菌 剂分别按照如下方法进行抗菌消毒实验：
我们通过培养大肠杆菌、枯草芽孢杆菌和金黄色葡萄球菌等细菌来研究光催化抗菌剂的抗菌活性。首先培养于下述表一中不同类型的细菌培养基，并将其均匀分成7份。随后分别用相同浓度但不同种类的光催化抗菌剂(实施例1至6光催化抗菌剂、对比例1至对比例2)来处理细菌培养基。然后分别在黑暗和太阳光下将细菌在37℃下培养一定的时间，每隔五分钟记录不同种类光催化抗菌剂的细菌存活率。
经抗菌消毒实验的结果如下表二和表三所示。
表一不同类型的细菌培养基
Figure PCTCN2021137298-appb-000001
表二黑暗存在下的细菌存活率(5分钟)
Figure PCTCN2021137298-appb-000002
表三太阳光存在下的细菌存活率(5分钟)
Figure PCTCN2021137298-appb-000003
由表二和表三可知，本申请实施例提供的光催化抗菌材料在太阳光条件下，具有优异的杀菌和抗病能力，其完全将各实验组中的细菌全部杀死。而对比例1 和2均无法达到该效果。而且对比本申请实施例提供的光催化抗菌材料分别与对比例1提供的光催化剂和对比例2银抗菌剂，本申请实施例提供的光催化抗菌材料所含的导电子助剂和可见光催化剂基体之间起到协同增效作用，赋予光催化抗菌材料高效的杀菌和抗病毒特性。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种光催化抗菌材料，包括可见光催化剂基体，其特征在于：还包括导电子助剂，所述导电子助剂用于所述可见光催化剂基体对可见光相应后进行电子和空穴的分离，且所述导电子助剂负载在所述可见光催化剂基体上。
  2. 根据权利要求1所述的光催化抗菌材料，其特征在于：所述导电子助剂在所述光催化抗菌材料中的负载重量为0.1％-10％；和/或
    所述导电子助剂包括Cu和贵重金属中的至少一种；和/或
    所述导电子助剂是以纳米颗粒形貌负载在所述可见光催化剂基体的表面；和/或
    所述可见光催化剂基体的材料包括氮氧化物；和/或
    所述光催化抗菌材料还包括表面活性剂，所述表面活性剂修饰结合在所述可见光催化剂基体的表面。
  3. 根据权利要求2所述的光催化抗菌材料，其特征在于：所述纳米颗粒形貌的粒径为亚纳米范围；
    所述贵重金属包括Ag、Au、Pt、Pd、Rh、Ru、Ir中的至少一种。
  4. 根据权利要求2或3所述的光催化抗菌材料，其特征在于：所述可见光催化剂基体的材料的带隙为0-2eV；和/或
    所述氮氧化物包括C 3N 4、Ta 3N 5、TaON、CaNbO 2N、BaTaO 2N、BaNbO 2N、LaTa xNb 1-xON 2中的至少一种，其中，x＝0-1；和/或
    所述氮氧化物的颗粒粒径为纳米范围。
  5. 根据权利要求2或3所述的光催化抗菌材料，其特征在于：所述表面活性剂包括聚乙二醇、聚乙烯吡咯烷酮、吐温中的至少一种；和/或
    所述表面活性剂在所述光催化抗菌材料的重量百分含量为0.1wt％～10wt％。
  6. 一种光催化抗菌材料的制备方法，包括如下步骤：
    提供可见光催化剂；
    在所述光催化剂上负载导电子助剂，使得所述导电子助剂结合在所述光催化剂上，得到光催化抗菌材料；
    其中，所述导电子助剂用于所述可见光催化剂基体对可见光相应后进行电子和空穴的分离。
  7. 根据权利要求6所述的制备方法，其特征在于：所述可见光催化剂为氮氧化物，且所述氮氧化物按照包括如下步骤的方法制备：
    制备所述氮氧化物的氧化物前驱体；
    将所述氧化物前驱体于氮气气氛中进行加热处理以进行氮化处理，得到含所述氮氧化物的所述光催化剂；
    和/或
    所述导电子助剂包括Cu和贵重金属中的至少一种金属单质，且在所述光催化剂表面负载导电子助剂的方法包括如下步骤：
    将所述可见光与表面活性剂配制成混合溶液，并对所述可见光催化剂进行表面改性处理，形成溶胶；
    向所述溶胶中加入所述金属单质的金属盐前驱体和还原剂，进行混合处理和还原反应，在所述可见光催化剂上原位沉积所述金属单质。
  8. 根据权利要求7所述的制备方法，其特征在于：所述氮化处理的温度为500-950℃；
    所述金属盐前驱体为金属离子配合物；
    所述还原剂包括NaBH 4、硼氢化钠、水合肼、醛类、氢气中的至少一种。
  9. 一种光催化抗菌剂，包括权利要求1-6任一项所述的光催化抗菌材料或由权利要求7-8任一项所述的制备方法制备的光催化抗菌材料。
  10. 根据权利要求9所述的光催化抗菌剂，其特征在于：所述光催化抗菌剂为喷雾剂、粉剂或、成膜剂或涂料。
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