WO2016184324A1 - Use of photocatalytic composite material, antibacterial and deodorant insoles, shoes, and preparation method thereof - Google Patents

Use of photocatalytic composite material, antibacterial and deodorant insoles, shoes, and preparation method thereof Download PDF

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Publication number
WO2016184324A1
WO2016184324A1 PCT/CN2016/081451 CN2016081451W WO2016184324A1 WO 2016184324 A1 WO2016184324 A1 WO 2016184324A1 CN 2016081451 W CN2016081451 W CN 2016081451W WO 2016184324 A1 WO2016184324 A1 WO 2016184324A1
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WIPO (PCT)
Prior art keywords
photocatalytic material
composite photocatalytic
graphene
sterilizing
deodorizing
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PCT/CN2016/081451
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French (fr)
Chinese (zh)
Inventor
杨与畅
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宝峰时尚国际控股有限公司
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Publication of WO2016184324A1 publication Critical patent/WO2016184324A1/en

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    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts

Definitions

  • the invention relates to an insole, in particular to an application of a composite photocatalytic material and a sterilization deodorizing insole, a shoe and a preparation method thereof.
  • the foot is a very important part of the human body. It is covered with abundant capillaries and important acupuncture points. The health treatment of the feet can eliminate the fatigue of the whole body. Because the amount of foot movement is large, sweating is more, and the environment inside the shoe is closed, it is easy to breed bacteria, which is easy to adversely affect the health of the foot, such as easy infection of various skin diseases such as athlete's foot, sweat, feet. Stinky is a common disease in daily life. It is a skin disease caused by fungal infection, which brings inconvenience to people's daily life.
  • the present invention aims to provide a composite photocatalytic material, a sterilizing and deodorizing insole, a shoe and a preparation method thereof, wherein the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide.
  • the composite photocatalytic material is used for preparing a sterilizing and deodorizing insole, so that the insole has an efficient sterilizing function, and aims to solve the problem that the bacteria in the shoe easily breed bacteria and affect the health of the foot.
  • composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide, and the composite photocatalytic material is used for preparing a sterilization deodorizing insole or a shoe.
  • a sterilizing and deodorizing insole wherein the sterilizing and deodorizing insole comprises a composite photocatalytic material, and the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide.
  • the sterilizing and deodorizing insole wherein the sterilizing and deodorizing insole comprises a functional layer and a bottom layer, wherein the functional layer is filled with the composite photocatalytic material, and the functional layer and the bottom layer are connected by sewing.
  • a sterilizing and deodorizing shoe comprises a middle bottom plate, wherein the middle bottom plate comprises a composite photocatalytic material, and the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide.
  • the composite photocatalytic material of graphene and titanium dioxide is configured into a suspension having a concentration of 3 to 10 wt% by using one of alcohol, acetone or isopropanol, and ultrasonically dispersed;
  • the fabric is taken out and dried, and the fabric is dried by heating.
  • the method for preparing a sterilizing and deodorizing insole wherein the material of the woven fabric is ordinary cotton or hemp; the heating and drying process is baking in a drying box at 60 to 80 ° C for 45 to 55 minutes.
  • the method for preparing a sterilizing and deodorizing insole, wherein the composite photocatalytic material of graphene and titanium dioxide is prepared by the following method:
  • the reduced graphene powder is poured into absolute ethanol, ultrasonic dispersion for 1-3h, to obtain a concentration of 0.1-2wt% of graphene anhydrous ethanol dispersion;
  • step c Add an appropriate amount of concentrated nitric acid to the graphene anhydrous ethanol dispersion to adjust the pH to 3-4; slowly add n-butyl titanate to the mixture while magnetic stirring, and add the amount of absolute ethanol used in step b. 20%-30% of the volume; after the completion of the dropwise addition of n-butyl titanate, stirring is continued for 1-3 hours to obtain a uniformly mixed colloid;
  • the uniformly mixed colloid is centrifuged, washed with absolute ethanol, and vacuum dried;
  • the solid obtained in the previous step is calcined at 380-530 ° C for 2-3 hours under nitrogen protection to obtain a composite photocatalytic material of graphene and titanium dioxide.
  • the preparation method of the sterilizing and deodorizing insole wherein, in the step a, the mass ratio of the graphite powder to the anhydrous sodium nitrate is 1:1 to 2:1.
  • step a The preparation method of the sterilizing and deodorizing insole, wherein, in step a, the condition of vacuum dehydration drying is 40-60 ° C for 18-30 hours;
  • step c the conditions of vacuum drying are dried at 40-60 ° C for 18-30 h.
  • the method for preparing a sterilizing and deodorizing insole wherein in the step a, the hydrogen peroxide is a hydrogen peroxide having a volume fraction of 30%.
  • the present invention provides a composite photocatalytic material, a sterilizing and deodorizing insole, a shoe and a preparation method thereof, wherein the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide, and the composite photocatalytic material is used for preparing sterilization Deodorant insole makes the insole have an efficient sterilization function.
  • the composite photocatalytic material can also be used to prepare a sterilization deodorizing shoe, and the composite photocatalytic material is coated on the middle bottom plate of the shoe to make the shoe have an efficient sterilization function.
  • the composite photocatalytic material has no selectivity in killing the fungus produced by the foot, can remove more than 97% of the fungal species, has low cost, simple process, natural environmental protection, and is completely harmless to the human body.
  • FIG. 1 is a schematic cross-sectional structural view of a sterilization and deodorizing insole provided by the present invention
  • the present invention provides a composite photocatalytic material application, a sterilizing and deodorizing insole, a shoe and a preparation method thereof.
  • the present invention will be further described in detail below in order to make the objects, technical solutions and effects of the present invention more clear and clear. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • the invention provides a composite photocatalytic material which is a composite photocatalytic material of graphene and titanium dioxide, and the composite photocatalytic material is used for preparing a sterilization deodorizing insole, so that the insole has high efficiency sterilization.
  • the composite photocatalytic material can also be used to prepare a sterilizing and deodorizing shoe, and the composite photocatalytic material is coated on the bottom plate of the shoe to make the shoe have the function of sterilization and deodorization.
  • the composite photocatalytic material not only utilizes the photocatalytic effect of titanium dioxide by utilizing the combination of graphene and powdered titanium dioxide materials, but also fully utilizes the unique electron transport characteristics of graphene, and greatly improves the photocatalytic efficiency of titanium dioxide.
  • the composite photocatalytic material can be well applied in the production process of the sterilization deodorizing insole or the fungus purification box, because it has an efficient sterilization function, and the sterilization is realized by utilizing the decomposition effect of the catalyst on the fungus, and no special light source is needed.
  • the daily light can be 10-30 minutes, and the composite photocatalytic material has no selectivity in killing the fungus produced by the foot, and can remove more than 97% of the fungal species.
  • the invention also provides a sterilizing and deodorizing insole, wherein the sterilizing and deodorizing insole comprises the above composite photocatalytic material, and the insole has a self-cleaning, sterilizing and deodorizing because the insole contains a composite photocatalytic material with high-efficiency sterilizing function.
  • the sterilizing and deodorizing insole comprises a functional layer 12 and a bottom layer 11 , wherein the functional layer 12 is filled with the above composite photocatalytic material, and the functional layer is connected to the bottom layer in a sewn manner.
  • the functional layer 12 may be made of a fabric having a thickness of 0.5 to 1 mm, and the voids of the fabric are filled with the above composite photocatalytic material.
  • the invention also provides a preparation method of the sterilizing and deodorizing insole, comprising the following steps:
  • a composite photocatalytic material of graphene and titanium dioxide is prepared by using one of alcohol, acetone or isopropyl alcohol as a suspension having a concentration of 3 to 10% by weight, and ultrasonically dispersed for 0.5 to 1 hour.
  • the material of the fabric may be ordinary cotton or hemp.
  • the invention also provides a preparation method of the composite photocatalytic material, which comprises the following steps:
  • the dried solid was calcined at 400 ° C for 2 hours under nitrogen to obtain a graphene powder after reduction; 30 mg of graphene powder was added to 60 mL of absolute ethanol, and ultrasonically dispersed for 1 h to obtain a graphene anhydrous ethanol dispersion. 3-5 drops of concentrated nitric acid were added dropwise, then 15 mL of n-butyl titanate was slowly added dropwise to the dispersion, stirring was continued for 1 h, and the obtained mixed colloid was centrifuged, and washed with absolute ethanol for several times. The vacuum drying oven was dried at 60 ° C for 24 h, and the obtained solid was calcined at 450 ° C for 3 h under nitrogen protection to obtain a composite photocatalytic material of graphene and nano titanium dioxide.
  • the graphene and nano-titanium dioxide composite material is arranged into a suspension with a concentration of 3 wt% by alcohol, and ultrasonically dispersed for 1 hour; the prepared fabric is made of ordinary cotton or hemp, and is placed in the prepared suspension for 5 min; After the soaking, the body was taken out and left for 10 minutes, and then the fabric was baked in a drying oven at 70 ° C for 45 minutes to volatilize the solvent, and the composite material and the fabric were tightly combined to obtain a functional layer of the insole.
  • the functional layer of the insole is integrally formed with the bottom layer to form a sterilization and deodorizing insole.
  • Mr. A suffers from athlete's foot, and his feet are itchy and stinky.
  • Use the normal insole on the right foot (excluding the composite photocatalytic material or any medicine), use the sterilizing and deodorizing insole on the left foot in this embodiment, and change the shoes every day to dry the balcony for 10min-30min, wear the shoes for one week, and the right foot is itchy.
  • the stenching symptoms persist, and the left foot has no itch and stench.
  • the dried solid was calcined at 350 ° C for 3 hours under nitrogen protection to obtain reduced graphene powder; 15 mg of graphene powder was added to 60 mL of absolute ethanol, and ultrasonically dispersed for 2 hours to obtain a graphene anhydrous ethanol dispersion. 3-5 drops of concentrated nitric acid were added dropwise, then 15 mL of n-butyl titanate was slowly added dropwise to the dispersion, stirring was continued for 1 h, and the obtained mixed colloid was centrifuged, and washed with absolute ethanol for several times. The vacuum drying oven was dried at 50 ° C for 20 h, and the obtained solid was calcined at 500 ° C for 2 h under a nitrogen atmosphere to obtain a graphene and nano titanium dioxide composite material.
  • the graphene and the nano titanium dioxide composite material are arranged into a suspension having a concentration of 6 wt% with acetone, and ultrasonically dispersed for 1 hour; the prepared fabric is made of ordinary cotton or hemp, and immersed in the configured suspension for 10 min; After the soaking, the body was taken out and left for 10 minutes, and then the fabric was baked in a drying oven at 60 ° C for 50 minutes to make the solvent volatilize, and the composite material and the fabric were tightly combined to obtain a functional layer of the insole.
  • the functional layer of the insole is integrally formed with the bottom layer to form a sterilization and deodorizing insole.
  • Mr. B suffers from athlete's foot, and his feet are itchy and stinky. Use the normal insole on the right foot and the sterilized and deodorized insole on the left foot. After changing the shoes every day, the balcony will be aired for 10min-30min. The shoes will be worn continuously for one week. The symptoms of the right foot itching and odor persist, and the left foot has no itching. It hurts and smells.
  • the dried solid was calcined at 400 ° C for 2 hours under nitrogen to obtain a graphene powder after reduction; 60 mg of graphene powder was added to 60 mL of absolute ethanol, and ultrasonically dispersed for 3 hours to obtain a graphene anhydrous ethanol dispersion. 5 drops of concentrated nitric acid were added dropwise, then 15 mL of n-butyl titanate was slowly added dropwise to the dispersion, stirring was continued for 2 h, and the obtained mixed colloid was centrifuged, washed with absolute ethanol and placed in a vacuum drying. The box was dried at 60 ° C for 24 h, and the obtained solid was calcined at 400 ° C for 3 h under nitrogen protection to obtain a composite photocatalytic material of graphene and nano titanium dioxide.
  • the graphene and the nano titanium dioxide composite material are arranged into a suspension having a concentration of 10% by weight with acetone, and dispersed by ultrasonic for 1 hour; the prepared fabric is made of ordinary cotton or hemp, and is placed in the prepared suspension for 15 minutes; After the immersion was completed, it was taken out and left to stand for 10 minutes, and then the fabric was baked in a drying oven at 80 ° C for 55 minutes to make the solvent volatilize, and the composite material and the fabric were tightly combined to obtain a functional layer of the insole.
  • the functional layer of the insole is integrally formed with the bottom layer to form a sterilization and deodorizing insole.
  • Mr. C suffers from athlete's foot, and his feet are itchy and stinky.
  • the left foot uses a common insole, and the right foot uses the present embodiment to sterilize and deodorize the insole.
  • the balcony is dried for 10 minutes to 30 minutes, and the shoes are worn continuously for one week.
  • the left foot is itchy and stinky.
  • the right foot has no itching. It hurts and smells.
  • Example 1 to 3 were sent to a testing center to examine the bactericidal effect, and the results are shown in Fig. 2.
  • the sample was operated for 60 minutes in the "high-grade air volume, standard wind, negative ion on" mode, and the average kill rate of Staphylococcus aureus sprayed in the air of 20m2 closed simulated laboratory was 98.06%. At this time, the natural mortality rate of Staphylococcus aureus was It is 11.47 ⁇ 12.68%.

Abstract

Disclosed are the use of a photocatalytic composite material, antibacterial and deodorant insoles, shoes, and preparation method thereof. The photocatalytic composite material is a photocatalytic composite material of graphene and titanium dioxide for preparing antibacterial and deodorant insoles. The photocatalytic composite material can also be used to prepare a home-use fungus purification box to dispose in a home-use shoe cabinet to kill various fungi of beriberi and prevent cross-infection by beriberi. The photocatalytic composite material has no selectivity when killing foot fungi, can remove more than 97% of fungi species, and is low in cost, simple in process, environment-friendly and completely non-toxic to human body.

Description

复合光催化材料的应用和杀菌除臭鞋垫、鞋及制备方法  Application of composite photocatalytic material and sterilization deodorizing insole, shoe and preparation method thereof 技术领域Technical field
本发明涉及一种鞋垫，尤其涉及一种复合光催化材料的应用和杀菌除臭鞋垫、鞋及制备方法。 The invention relates to an insole, in particular to an application of a composite photocatalytic material and a sterilization deodorizing insole, a shoe and a preparation method thereof.
背景技术Background technique
如今随着人们的生活节奏日见加快、工作愈加繁忙，人们也越来越注重自我保健。脚部是人身非常重要的部分，其上密布着丰富的毛细血管和重要的穴位，对脚部的保健理疗可消除周身疲劳。由于脚部运动量大、出汗较多，而且鞋内的环境呈封闭状，容易滋生细菌，容易对脚部的健康产生不利影响，比如易感染上各类皮肤病，如脚气、脚汗、脚臭是日常生活中常见的病症，是由真菌感染而引起的皮肤病，给人们日常生活带来诸多不便。Nowadays, as people's life rhythm is getting faster and their work is getting more busy, people are paying more and more attention to self-care. The foot is a very important part of the human body. It is covered with abundant capillaries and important acupuncture points. The health treatment of the feet can eliminate the fatigue of the whole body. Because the amount of foot movement is large, sweating is more, and the environment inside the shoe is closed, it is easy to breed bacteria, which is easy to adversely affect the health of the foot, such as easy infection of various skin diseases such as athlete's foot, sweat, feet. Stinky is a common disease in daily life. It is a skin disease caused by fungal infection, which brings inconvenience to people's daily life.
因此，现有技术还有待发展。Therefore, the prior art has yet to be developed.
技术问题technical problem
鉴于上述现有技术的不足，本发明的目的在于提供一种复合光催化材料的应用和杀菌除臭鞋垫、鞋及制备方法，所述复合光催化材料为石墨烯与二氧化钛的复合光催化材料，将此复合光催化材料用于制备杀菌除臭鞋垫，使鞋垫具有高效的杀菌功能，旨在解决鞋内容易滋生细菌影响脚部的健康的问题。 In view of the above deficiencies of the prior art, the present invention aims to provide a composite photocatalytic material, a sterilizing and deodorizing insole, a shoe and a preparation method thereof, wherein the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide. The composite photocatalytic material is used for preparing a sterilizing and deodorizing insole, so that the insole has an efficient sterilizing function, and aims to solve the problem that the bacteria in the shoe easily breed bacteria and affect the health of the foot.
技术解决方案Technical solution
本发明的技术方案如下：The technical solution of the present invention is as follows:
一种复合光催化材料的应用，其中，所述复合光催化材料为石墨烯与二氧化钛的复合光催化材料，将所述复合光催化材料用于制备杀菌除臭鞋垫或鞋子。An application of a composite photocatalytic material, wherein the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide, and the composite photocatalytic material is used for preparing a sterilization deodorizing insole or a shoe.
一种杀菌除臭鞋垫，其中，所述杀菌除臭鞋垫中包含有复合光催化材料，所述复合光催化材料为石墨烯与二氧化钛的复合光催化材料。A sterilizing and deodorizing insole, wherein the sterilizing and deodorizing insole comprises a composite photocatalytic material, and the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide.
所述的杀菌除臭鞋垫，其中，所述杀菌除臭鞋垫包括功能层和底层，所述功能层中填充有所述复合光催化材料，功能层与底层以缝制的方式相连接。The sterilizing and deodorizing insole, wherein the sterilizing and deodorizing insole comprises a functional layer and a bottom layer, wherein the functional layer is filled with the composite photocatalytic material, and the functional layer and the bottom layer are connected by sewing.
一种杀菌除臭鞋，所述杀菌除臭鞋包括中底板，其中，所述中底板上包含有复合光催化材料，所述复合光催化材料为石墨烯与二氧化钛的复合光催化材料。A sterilizing and deodorizing shoe comprises a middle bottom plate, wherein the middle bottom plate comprises a composite photocatalytic material, and the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide.
一种如上所述的杀菌除臭鞋垫的制备方法，其中，包括以下步骤：A method for preparing a sterilizing and deodorizing insole as described above, comprising the steps of:
将石墨烯与二氧化钛的复合光催化材料用酒精、丙酮或异丙醇中的其中的一种，配置成浓度为3~10wt%的悬浮液，超声分散；The composite photocatalytic material of graphene and titanium dioxide is configured into a suspension having a concentration of 3 to 10 wt% by using one of alcohol, acetone or isopropanol, and ultrasonically dispersed;
把织物放入上述步骤所配置的悬浮液中浸泡5~15min；Soaking the fabric in the suspension configured in the above step for 5~15min;
浸泡结束后，取出晾置，将织物进行加热干燥。After the immersion is completed, the fabric is taken out and dried, and the fabric is dried by heating.
所述的杀菌除臭鞋垫的制备方法，其中，所述织物的材质为普通的棉或者麻；所述加热干燥的过程为在60~80℃的干燥箱内烘烤45~55min。The method for preparing a sterilizing and deodorizing insole, wherein the material of the woven fabric is ordinary cotton or hemp; the heating and drying process is baking in a drying box at 60 to 80 ° C for 45 to 55 minutes.
所述的杀菌除臭鞋垫的制备方法，其中，所述石墨烯与二氧化钛的复合光催化材料采用以下方法制备得到：The method for preparing a sterilizing and deodorizing insole, wherein the composite photocatalytic material of graphene and titanium dioxide is prepared by the following method:
a、把石墨粉和无水硝酸钠缓慢倒入冰浴中的浓硫酸，边搅拌溶液边加入高锰酸钾，再加入双氧水还原剩余的二氧化锰；将所得混合液过滤，并用离子水洗涤数次，真空脱水干燥；将所得干燥所得的固体在氮气保护下350~400℃煅烧2~3小时，得到还原后的石墨烯粉末；a. Slowly pour graphite powder and anhydrous sodium nitrate into concentrated sulfuric acid in an ice bath, add potassium permanganate while stirring the solution, and then add hydrogen peroxide to reduce the remaining manganese dioxide; filter the mixture and wash it with ionized water. Several times, vacuum dehydration and drying; the obtained solid obtained by drying is calcined at 350 to 400 ° C for 2 to 3 hours under nitrogen protection to obtain a graphene powder after reduction;
b、将还原后的石墨烯粉末倒入无水乙醇中，超声分散1-3h，得到浓度为0.1-2wt%的石墨烯无水乙醇分散液；b, the reduced graphene powder is poured into absolute ethanol, ultrasonic dispersion for 1-3h, to obtain a concentration of 0.1-2wt% of graphene anhydrous ethanol dispersion;
c、在石墨烯无水乙醇分散液中加入适量浓硝酸，调节其pH至3-4；磁力搅拌的同时向其中缓慢滴加钛酸正丁酯，滴加量为步骤b中所用无水乙醇体积的20%-30%；待钛酸正丁酯滴加结束后，继续搅拌1-3h，得到均匀混合的胶体；c. Add an appropriate amount of concentrated nitric acid to the graphene anhydrous ethanol dispersion to adjust the pH to 3-4; slowly add n-butyl titanate to the mixture while magnetic stirring, and add the amount of absolute ethanol used in step b. 20%-30% of the volume; after the completion of the dropwise addition of n-butyl titanate, stirring is continued for 1-3 hours to obtain a uniformly mixed colloid;
d、将均匀混合的胶体进行离心分离，用无水乙醇进行洗涤，真空干燥；d, the uniformly mixed colloid is centrifuged, washed with absolute ethanol, and vacuum dried;
e、将前一步骤所得固体在氮气保护下380-530℃煅烧2-3h，得到石墨烯与二氧化钛的复合光催化材料。e. The solid obtained in the previous step is calcined at 380-530 ° C for 2-3 hours under nitrogen protection to obtain a composite photocatalytic material of graphene and titanium dioxide.
所述的杀菌除臭鞋垫的制备方法，其中，步骤a中，石墨粉和无水硝酸钠的质量比为1:1~2:1。The preparation method of the sterilizing and deodorizing insole, wherein, in the step a, the mass ratio of the graphite powder to the anhydrous sodium nitrate is 1:1 to 2:1.
所述的杀菌除臭鞋垫的制备方法，其中，步骤a中，真空脱水干燥的条件为40-60℃干燥18-30h；The preparation method of the sterilizing and deodorizing insole, wherein, in step a, the condition of vacuum dehydration drying is 40-60 ° C for 18-30 hours;
步骤c中，真空干燥的条件为40-60℃干燥18-30h。In step c, the conditions of vacuum drying are dried at 40-60 ° C for 18-30 h.
所述的杀菌除臭鞋垫的制备方法，其中，步骤a中，双氧水为体积分数为30%的双氧水。The method for preparing a sterilizing and deodorizing insole, wherein in the step a, the hydrogen peroxide is a hydrogen peroxide having a volume fraction of 30%.
有益效果Beneficial effect
有益效果：本发明提供一种复合光催化材料、杀菌除臭鞋垫、鞋及制备方法，所述复合光催化材料为石墨烯与二氧化钛的复合光催化材料，将此复合光催化材料用于制备杀菌除臭鞋垫，使鞋垫具有高效的杀菌功能。也可将所述复合光催化材料用于制备杀菌除臭鞋，在鞋子的中底板上涂覆所述复合光催化材料，使鞋子具有高效的杀菌功能。所述复合光催化材料在杀灭脚部产生的真菌时没有选择性，能够去除97%以上的真菌种类，且成本低，工艺简单，自然环保，对人体完全无害。 Advantageous Effects: The present invention provides a composite photocatalytic material, a sterilizing and deodorizing insole, a shoe and a preparation method thereof, wherein the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide, and the composite photocatalytic material is used for preparing sterilization Deodorant insole makes the insole have an efficient sterilization function. The composite photocatalytic material can also be used to prepare a sterilization deodorizing shoe, and the composite photocatalytic material is coated on the middle bottom plate of the shoe to make the shoe have an efficient sterilization function. The composite photocatalytic material has no selectivity in killing the fungus produced by the foot, can remove more than 97% of the fungal species, has low cost, simple process, natural environmental protection, and is completely harmless to the human body.
附图说明DRAWINGS
图1为本发明提供的杀菌除臭鞋垫的剖面结构示意图；1 is a schematic cross-sectional structural view of a sterilization and deodorizing insole provided by the present invention;
图2为本发明实施例1~3提供的样品杀菌效果对比图。2 is a comparison diagram of the sterilization effect of the samples provided in Examples 1 to 3 of the present invention.
本发明的实施方式Embodiments of the invention
本发明提供一种复合光催化材料的应用和杀菌除臭鞋垫、鞋及制备方法，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention provides a composite photocatalytic material application, a sterilizing and deodorizing insole, a shoe and a preparation method thereof. The present invention will be further described in detail below in order to make the objects, technical solutions and effects of the present invention more clear and clear. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
本发明中提供一种复合光催化材料的应用，所述复合光催化材料为石墨烯与二氧化钛的复合光催化材料，将此复合光催化材料用于制备杀菌除臭鞋垫，使鞋垫具有高效的杀菌功能。也可将所述复合光催化材料用于制备杀菌除臭鞋子，在鞋子的中底板涂覆上所述复合光催化材料，使鞋子具有杀菌除臭的功能。所述复合光催化材料通过把石墨烯与粉末状的二氧化钛材料相互复合，不仅利用了二氧化钛的光催化效果，而且充分利用了石墨烯独特的电子传输特性，极大地提高了二氧化钛的光催化效率。该复合光催化材料可以很好地应用在杀菌除臭鞋垫或真菌净化盒的生产工艺中，因为其具有高效的杀菌功能，其杀菌是利用了催化剂对真菌的分解作用而实现，不需要特殊光源，日常光照10-30min即可，及且该种复合光催化材料在杀灭脚部产生的真菌时没有选择性，能够去除97%以上的真菌种类。The invention provides a composite photocatalytic material which is a composite photocatalytic material of graphene and titanium dioxide, and the composite photocatalytic material is used for preparing a sterilization deodorizing insole, so that the insole has high efficiency sterilization. Features. The composite photocatalytic material can also be used to prepare a sterilizing and deodorizing shoe, and the composite photocatalytic material is coated on the bottom plate of the shoe to make the shoe have the function of sterilization and deodorization. The composite photocatalytic material not only utilizes the photocatalytic effect of titanium dioxide by utilizing the combination of graphene and powdered titanium dioxide materials, but also fully utilizes the unique electron transport characteristics of graphene, and greatly improves the photocatalytic efficiency of titanium dioxide. The composite photocatalytic material can be well applied in the production process of the sterilization deodorizing insole or the fungus purification box, because it has an efficient sterilization function, and the sterilization is realized by utilizing the decomposition effect of the catalyst on the fungus, and no special light source is needed. The daily light can be 10-30 minutes, and the composite photocatalytic material has no selectivity in killing the fungus produced by the foot, and can remove more than 97% of the fungal species.
本发明中还提供一种杀菌除臭鞋垫，所述杀菌除臭鞋垫中包含有上述复合光催化材料，由于鞋垫中含有具有高效杀菌功能的复合光催化材料，使得鞋垫具有自我清洁、杀菌除臭、治疗脚气的功效。具体地，如图1所示，所述杀菌除臭鞋垫包括功能层12和底层11，所述功能层12的中填充有上述复合光催化材料，功能层与底层以缝制的方式相连接。所述功能层12可以由厚度为0.5-1mm的织物制成，织物的空隙中填充有上述复合光催化材料。The invention also provides a sterilizing and deodorizing insole, wherein the sterilizing and deodorizing insole comprises the above composite photocatalytic material, and the insole has a self-cleaning, sterilizing and deodorizing because the insole contains a composite photocatalytic material with high-efficiency sterilizing function. To treat the effects of athlete's foot. Specifically, as shown in FIG. 1 , the sterilizing and deodorizing insole comprises a functional layer 12 and a bottom layer 11 , wherein the functional layer 12 is filled with the above composite photocatalytic material, and the functional layer is connected to the bottom layer in a sewn manner. The functional layer 12 may be made of a fabric having a thickness of 0.5 to 1 mm, and the voids of the fabric are filled with the above composite photocatalytic material.
本发明中还提供所述杀菌除臭鞋垫的制备方法，包括以下步骤：The invention also provides a preparation method of the sterilizing and deodorizing insole, comprising the following steps:
（1）将石墨烯与二氧化钛的复合光催化材料用酒精、丙酮或异丙醇其中的一种，配置成浓度为3~10wt%的悬浮液，超声分散0.5-1h。(1) A composite photocatalytic material of graphene and titanium dioxide is prepared by using one of alcohol, acetone or isopropyl alcohol as a suspension having a concentration of 3 to 10% by weight, and ultrasonically dispersed for 0.5 to 1 hour.
（2）把制作好的织物，放入上述步骤（1）所配置的悬浮液中浸泡5~15min。所述织物的材质可以为普通的棉或者麻。(2) Soak the prepared fabric in the suspension configured in the above step (1) for 5 to 15 minutes. The material of the fabric may be ordinary cotton or hemp.
（3）浸泡结束后，取出晾置10-20min，然后将织物放入60~80℃的干燥箱内烘烤45~55min。经过干燥后，使织物中的溶剂挥发，同时复合光催化材料与织物之间能紧密结合。(3) After soaking, take out and leave for 10-20min, then put the fabric into a drying oven at 60~80 °C for 45~55min. After drying, the solvent in the fabric is volatilized, and the composite photocatalytic material is tightly bonded to the fabric.
本发明中还提供所述复合光催化材料的制备方法，具体包括以下步骤：The invention also provides a preparation method of the composite photocatalytic material, which comprises the following steps:
（1）把石墨粉和无水硝酸钠缓慢倒入冰浴中的浓硫酸，边搅拌溶液边加入高锰酸钾，再加入体积分数为30%的双氧水还原剩余的二氧化锰；将所得混合液过滤，并用去离子水洗涤数次，放入真空箱内脱水干燥40-60℃干燥18-30h；将干燥所得的固体在氮气保护下于350~400℃煅烧2~3小时，得到还原后的石墨烯粉末。其中，石墨粉和无水硝酸钠的质量比为1:1~2:1。石墨粉和高锰酸钾的质量比约为1:2~1:4。所述双氧水的用量为使剩余的二氧化锰还原完毕即可。所述浓硫酸的用量为适量，几滴即可。(1) Slowly pouring graphite powder and anhydrous sodium nitrate into concentrated sulfuric acid in an ice bath, adding potassium permanganate while stirring the solution, and adding 30% by volume of hydrogen peroxide to reduce the remaining manganese dioxide; The solution is filtered and washed several times with deionized water, dried in a vacuum box and dried at 40-60 ° C for 18-30 h; the dried solid is calcined at 350-400 ° C for 2 to 3 hours under nitrogen protection to obtain a reduction. Graphene powder. Among them, the mass ratio of graphite powder to anhydrous sodium nitrate is 1:1~2:1. The mass ratio of graphite powder to potassium permanganate is about 1:2 to 1:4. The amount of the hydrogen peroxide is such that the remaining manganese dioxide is reduced. The concentrated sulfuric acid is used in an appropriate amount, and a few drops are sufficient.
（2）将上述所得石墨烯粉末倒入无水乙醇中，超声分散1-3h，得到浓度为0.1%-2%（wt%）的石墨烯无水乙醇分散液。(2) The graphene powder obtained above was poured into absolute ethanol and ultrasonically dispersed for 1-3 hours to obtain a graphene anhydrous ethanol dispersion having a concentration of 0.1% to 2% by weight.
（3）在上述氧化石墨的无水乙醇分散液中加入几滴（3-5滴左右）浓硝酸，调节其pH为3-4，磁力搅拌的同时向其中缓慢滴加钛酸正丁酯，滴加量为步骤（2）中所加入无水乙醇体积的20%-30%，待钛酸正丁酯滴加结束后继续搅拌1-3h，得到均匀混合的胶体。(3) adding a few drops (about 3-5 drops) of concentrated nitric acid to the anhydrous ethanol dispersion of the above graphite oxide, adjusting the pH to 3-4, and slowly adding n-butyl titanate thereto while magnetic stirring. The amount of dropwise addition is 20%-30% of the volume of anhydrous ethanol added in the step (2), and stirring is continued for 1-3 hours after the dropwise addition of n-butyl titanate to obtain a uniformly mixed colloid.
（4）将（3）步骤所得混合物进行离心分离，用无水乙醇进行洗涤，40-60℃下真空干燥18-30h。(4) The mixture obtained in the step (3) is centrifuged, washed with absolute ethanol, and vacuum dried at 40-60 ° C for 18-30 h.
（5）将上述所得固体在氮气保护下380-530℃煅烧2-3h，得到石墨烯与纳米二氧化钛复合材料。(5) The solid obtained above was calcined at 380-530 ° C for 2-3 hours under nitrogen protection to obtain a composite material of graphene and nano titanium dioxide.
以下通过具体的实施例对本发明做进一步说明。The invention is further illustrated by the following specific examples.
实施例1Example 1
将250mL的反应瓶置于冰浴中，加入适量的浓硫酸，边搅拌边加入2g石墨粉和2g硝酸钠的固体混合物，再加入6g高锰酸钾，搅拌反应40min，然后加入2mL的30%的双氧水，继续搅拌10min，趁热过滤，并用去离子水洗涤三次，真空干燥箱内60℃干燥24h。将干燥所得的固体在氮气保护下于400℃煅烧2小时，得到还原后的石墨烯粉末；取30mg石墨烯粉末加入60mL无水乙醇中，超声分散1h，得到石墨烯无水乙醇分散液，先滴加3-5滴浓硝酸，然后将15mL钛酸正丁酯缓慢滴加入该分散液中，继续搅拌1h，再将上述所得混合胶体进行离心分离，并用无水乙醇进行多次洗涤后放入真空干燥箱60℃干燥24h，所得固体在氮气保护下450℃煅烧3h，得到石墨烯与纳米二氧化钛复合光催化材料。Place a 250 mL reaction flask in an ice bath, add an appropriate amount of concentrated sulfuric acid, add a solid mixture of 2 g of graphite powder and 2 g of sodium nitrate with stirring, add 6 g of potassium permanganate, stir the reaction for 40 min, and then add 2 mL of 30%. The hydrogen peroxide was stirred for 10 min, filtered while hot, washed three times with deionized water, and dried in a vacuum oven at 60 ° C for 24 h. The dried solid was calcined at 400 ° C for 2 hours under nitrogen to obtain a graphene powder after reduction; 30 mg of graphene powder was added to 60 mL of absolute ethanol, and ultrasonically dispersed for 1 h to obtain a graphene anhydrous ethanol dispersion. 3-5 drops of concentrated nitric acid were added dropwise, then 15 mL of n-butyl titanate was slowly added dropwise to the dispersion, stirring was continued for 1 h, and the obtained mixed colloid was centrifuged, and washed with absolute ethanol for several times. The vacuum drying oven was dried at 60 ° C for 24 h, and the obtained solid was calcined at 450 ° C for 3 h under nitrogen protection to obtain a composite photocatalytic material of graphene and nano titanium dioxide.
将石墨烯与纳米二氧化钛复合材料用酒精配置成浓度为3wt%的悬浮液，超声分散1h；把制作好的织物，其材质为普通的棉或者麻，放入所配置的悬浮液中浸泡5min；浸泡结束后，取出晾置10min，然后将织物放入70℃的干燥箱内烘烤45min，使溶剂挥发的同时，复合材料与织物之间紧密结合，制得鞋垫的功能层。The graphene and nano-titanium dioxide composite material is arranged into a suspension with a concentration of 3 wt% by alcohol, and ultrasonically dispersed for 1 hour; the prepared fabric is made of ordinary cotton or hemp, and is placed in the prepared suspension for 5 min; After the soaking, the body was taken out and left for 10 minutes, and then the fabric was baked in a drying oven at 70 ° C for 45 minutes to volatilize the solvent, and the composite material and the fabric were tightly combined to obtain a functional layer of the insole.
将鞋垫的功能层与底层缝制成一体，制成杀菌除臭鞋垫。A先生患脚气，脚部痒痛、发臭。右脚用普通鞋垫（不含复合光催化材料或任何药物），左脚用本实施例杀菌除臭鞋垫，每日换下鞋子后阳台晾晒10min-30min，连续穿该鞋子一周，右脚痒痛发臭症状持续中，左脚已无痒痛发臭现象。The functional layer of the insole is integrally formed with the bottom layer to form a sterilization and deodorizing insole. Mr. A suffers from athlete's foot, and his feet are itchy and stinky. Use the normal insole on the right foot (excluding the composite photocatalytic material or any medicine), use the sterilizing and deodorizing insole on the left foot in this embodiment, and change the shoes every day to dry the balcony for 10min-30min, wear the shoes for one week, and the right foot is itchy. The stenching symptoms persist, and the left foot has no itch and stench.
实施例2Example 2
将250mL的反应瓶置于冰浴中，加入适量的浓硫酸，边搅拌边加入2g石墨粉和1g硝酸钠的固体混合物，再加入6g高锰酸钾，搅拌反应40min，然后加入2mL的30%的双氧水，继续搅拌5min，趁热过滤，并用去离子水洗涤三次，真空干燥箱内60℃干燥24h。将干燥所得的固体在氮气保护下于350℃煅烧3小时，得到还原后的石墨烯粉末；取15mg石墨烯粉末加入60mL无水乙醇中，超声分散2h，得到石墨烯无水乙醇分散液，先滴加3-5滴浓硝酸，然后将15mL钛酸正丁酯缓慢滴加入该分散液中，继续搅拌1h，再将上述所得混合胶体进行离心分离，并用无水乙醇进行多次洗涤后放入真空干燥箱50℃干燥20h，所得固体在氮气保护下500℃煅烧2h，得到石墨烯与纳米二氧化钛复合材料。Place a 250 mL reaction flask in an ice bath, add an appropriate amount of concentrated sulfuric acid, add a solid mixture of 2 g of graphite powder and 1 g of sodium nitrate with stirring, add 6 g of potassium permanganate, stir the reaction for 40 min, then add 2 mL of 30%. The hydrogen peroxide was stirred for 5 min, filtered while hot, washed three times with deionized water, and dried in a vacuum oven at 60 ° C for 24 h. The dried solid was calcined at 350 ° C for 3 hours under nitrogen protection to obtain reduced graphene powder; 15 mg of graphene powder was added to 60 mL of absolute ethanol, and ultrasonically dispersed for 2 hours to obtain a graphene anhydrous ethanol dispersion. 3-5 drops of concentrated nitric acid were added dropwise, then 15 mL of n-butyl titanate was slowly added dropwise to the dispersion, stirring was continued for 1 h, and the obtained mixed colloid was centrifuged, and washed with absolute ethanol for several times. The vacuum drying oven was dried at 50 ° C for 20 h, and the obtained solid was calcined at 500 ° C for 2 h under a nitrogen atmosphere to obtain a graphene and nano titanium dioxide composite material.
将石墨烯与纳米二氧化钛复合材料用丙酮配置成浓度为6wt%的悬浮液，超声分散1h；把制作好的织物，其材质为普通的棉或者麻，放入所配置的悬浮液中浸泡10min；浸泡结束后，取出晾置10min，然后将织物放入60℃的干燥箱内烘烤50min，使溶剂挥发的同时，复合材料与织物之间紧密结合，制得鞋垫的功能层。The graphene and the nano titanium dioxide composite material are arranged into a suspension having a concentration of 6 wt% with acetone, and ultrasonically dispersed for 1 hour; the prepared fabric is made of ordinary cotton or hemp, and immersed in the configured suspension for 10 min; After the soaking, the body was taken out and left for 10 minutes, and then the fabric was baked in a drying oven at 60 ° C for 50 minutes to make the solvent volatilize, and the composite material and the fabric were tightly combined to obtain a functional layer of the insole.
将鞋垫的功能层与底层缝制成一体，制成杀菌除臭鞋垫。B先生患脚气，脚部痒痛、发臭。右脚用普通鞋垫，左脚用本实施例杀菌除臭鞋垫，每日换下鞋子后阳台晾晒10min-30min，连续穿该鞋子一周，右脚痒痛发臭症状持续中，左脚已无痒痛发臭现象。The functional layer of the insole is integrally formed with the bottom layer to form a sterilization and deodorizing insole. Mr. B suffers from athlete's foot, and his feet are itchy and stinky. Use the normal insole on the right foot and the sterilized and deodorized insole on the left foot. After changing the shoes every day, the balcony will be aired for 10min-30min. The shoes will be worn continuously for one week. The symptoms of the right foot itching and odor persist, and the left foot has no itching. It hurts and smells.
实施例3Example 3
将250mL的反应瓶置于冰浴中，加入适量的浓硫酸，边搅拌边加入2g石墨粉和2g硝酸钠的固体混合物，再加入6g高锰酸钾，搅拌反应40min，然后加入2mL的30%的双氧水，继续搅拌10min，趁热过滤，并用去离子水洗涤三次，真空干燥箱内60℃干燥24h。将干燥所得的固体在氮气保护下于400℃煅烧2小时，得到还原后的石墨烯粉末；取60mg石墨烯粉末加入60mL无水乙醇中，超声分散3h，得到石墨烯无水乙醇分散液，先滴加5滴浓硝酸，然后将15mL钛酸正丁酯缓慢滴加入该分散液中，继续搅拌2h，再将上述所得混合胶体进行离心分离，并用无水乙醇进行多次洗涤后放入真空干燥箱60℃干燥24h，所得固体在氮气保护下400℃煅烧3h，得到石墨烯与纳米二氧化钛复合光催化材料。Place a 250 mL reaction flask in an ice bath, add an appropriate amount of concentrated sulfuric acid, add a solid mixture of 2 g of graphite powder and 2 g of sodium nitrate with stirring, add 6 g of potassium permanganate, stir the reaction for 40 min, and then add 2 mL of 30%. The hydrogen peroxide was stirred for 10 min, filtered while hot, washed three times with deionized water, and dried in a vacuum oven at 60 ° C for 24 h. The dried solid was calcined at 400 ° C for 2 hours under nitrogen to obtain a graphene powder after reduction; 60 mg of graphene powder was added to 60 mL of absolute ethanol, and ultrasonically dispersed for 3 hours to obtain a graphene anhydrous ethanol dispersion. 5 drops of concentrated nitric acid were added dropwise, then 15 mL of n-butyl titanate was slowly added dropwise to the dispersion, stirring was continued for 2 h, and the obtained mixed colloid was centrifuged, washed with absolute ethanol and placed in a vacuum drying. The box was dried at 60 ° C for 24 h, and the obtained solid was calcined at 400 ° C for 3 h under nitrogen protection to obtain a composite photocatalytic material of graphene and nano titanium dioxide.
将石墨烯与纳米二氧化钛复合材料用丙酮配置成浓度为10wt%的悬浮液，超声分散1h；把制作好的织物，其材质为普通的棉或者麻，放入所配置的悬浮液中浸泡15min；浸泡结束后，取出晾置10min，然后将织物放入80℃的干燥箱内烘烤55min，使溶剂挥发的同时，复合材料与织物之间紧密结合，制得鞋垫的功能层。The graphene and the nano titanium dioxide composite material are arranged into a suspension having a concentration of 10% by weight with acetone, and dispersed by ultrasonic for 1 hour; the prepared fabric is made of ordinary cotton or hemp, and is placed in the prepared suspension for 15 minutes; After the immersion was completed, it was taken out and left to stand for 10 minutes, and then the fabric was baked in a drying oven at 80 ° C for 55 minutes to make the solvent volatilize, and the composite material and the fabric were tightly combined to obtain a functional layer of the insole.
将鞋垫的功能层与底层缝制成一体，制成杀菌除臭鞋垫。C先生患脚气，脚部痒痛、发臭。左脚用普通鞋垫，右脚用本实施例杀菌除臭鞋垫，每日换下鞋子后阳台晾晒10min-30min，连续穿该鞋子一周，左脚痒痛发臭症状持续中，右脚已无痒痛发臭现象。The functional layer of the insole is integrally formed with the bottom layer to form a sterilization and deodorizing insole. Mr. C suffers from athlete's foot, and his feet are itchy and stinky. The left foot uses a common insole, and the right foot uses the present embodiment to sterilize and deodorize the insole. After changing the shoes, the balcony is dried for 10 minutes to 30 minutes, and the shoes are worn continuously for one week. The left foot is itchy and stinky. The right foot has no itching. It hurts and smells.
将实施例1~3的样品送到检测中心检测其杀菌效果，其结果如图2所示。样品在“高档风量、标准风、负离子开启”模式下工作60分钟，对20m2密闭模拟实验室空气中喷染的白色葡萄球菌的平均杀灭率为98.06%，此时白色葡萄球菌的自然衰亡率为11.47~12.68%。The samples of Examples 1 to 3 were sent to a testing center to examine the bactericidal effect, and the results are shown in Fig. 2. The sample was operated for 60 minutes in the "high-grade air volume, standard wind, negative ion on" mode, and the average kill rate of Staphylococcus aureus sprayed in the air of 20m2 closed simulated laboratory was 98.06%. At this time, the natural mortality rate of Staphylococcus aureus was It is 11.47~12.68%.
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。It is to be understood that the application of the present invention is not limited to the above-described examples, and those skilled in the art can make modifications and changes in accordance with the above description, all of which are within the scope of the appended claims.

Claims (10)

  1. 一种复合光催化材料的应用，其特征在于，所述复合光催化材料为石墨烯与二氧化钛的复合光催化材料，将所述复合光催化材料用于制备杀菌除臭鞋垫或鞋子。 A composite photocatalytic material is characterized in that the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide, and the composite photocatalytic material is used for preparing a sterilization deodorizing insole or a shoe.
  2. 一种杀菌除臭鞋垫，其特征在于，所述杀菌除臭鞋垫中包含有复合光催化材料，所述复合光催化材料为石墨烯与二氧化钛的复合光催化材料。A sterilizing and deodorizing insole characterized in that the sterilizing and deodorizing insole comprises a composite photocatalytic material, and the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide.
  3. 根据权利要求2所述的杀菌除臭鞋垫，其特征在于，所述杀菌除臭鞋垫包括功能层和底层，所述功能层中填充有所述复合光催化材料，功能层与底层以缝制的方式相连接。The sterilizing and deodorizing insole according to claim 2, wherein the sterilizing and deodorizing insole comprises a functional layer and a bottom layer, the functional layer is filled with the composite photocatalytic material, and the functional layer and the bottom layer are sewn. Ways to connect.
  4. 一种杀菌除臭鞋，所述杀菌除臭鞋包括中底板，其特征在于，所述中底板上包含有复合光催化材料，所述复合光催化材料为石墨烯与二氧化钛的复合光催化材料。A sterilizing and deodorizing shoe comprises a middle bottom plate, wherein the middle bottom plate comprises a composite photocatalytic material, and the composite photocatalytic material is a composite photocatalytic material of graphene and titanium dioxide.
  5. 一种如权利要求2或3所述的杀菌除臭鞋垫的制备方法，其特征在于，包括以下步骤：A method for preparing a sterilizing and deodorizing insole according to claim 2 or 3, comprising the steps of:
    将石墨烯与二氧化钛的复合光催化材料用酒精、丙酮或异丙醇中的其中的一种，配置成浓度为3~10wt%的悬浮液，超声分散；The composite photocatalytic material of graphene and titanium dioxide is configured into a suspension having a concentration of 3 to 10 wt% by using one of alcohol, acetone or isopropanol, and ultrasonically dispersed;
    把织物放入上述步骤所配置的悬浮液中浸泡5~15min；Soaking the fabric in the suspension configured in the above step for 5~15min;
    浸泡结束后，取出晾置，将织物进行加热干燥。After the immersion is completed, the fabric is taken out and dried, and the fabric is dried by heating.
  6. 根据权利要求5所述的杀菌除臭鞋垫的制备方法，其特征在于，所述织物的材质为普通的棉或者麻；所述加热干燥的过程为在60~80℃的干燥箱内烘烤45~55min。The method for preparing a sterilizing and deodorizing insole according to claim 5, wherein the fabric is made of ordinary cotton or hemp; and the heating and drying process is baking in a drying oven at 60 to 80 ° C. ~55min.
  7. 根据权利要求5或6所述的杀菌除臭鞋垫的制备方法，其特征在于，所述石墨烯与二氧化钛的复合光催化材料采用以下方法制备得到：The method for preparing a sterilizing and deodorizing insole according to claim 5 or 6, wherein the composite photocatalytic material of graphene and titanium dioxide is prepared by the following method:
    a、把石墨粉和无水硝酸钠缓慢倒入冰浴中的浓硫酸，边搅拌溶液边加入高锰酸钾，再加入双氧水还原剩余的二氧化锰；将所得混合液过滤，并用离子水洗涤数次，真空脱水干燥；将所得干燥所得的固体在氮气保护下350~400℃煅烧2~3小时，得到还原后的石墨烯粉末；a. Slowly pour graphite powder and anhydrous sodium nitrate into concentrated sulfuric acid in an ice bath, add potassium permanganate while stirring the solution, and then add hydrogen peroxide to reduce the remaining manganese dioxide; filter the mixture and wash it with ionized water. Several times, vacuum dehydration and drying; the obtained solid obtained by drying is calcined at 350 to 400 ° C for 2 to 3 hours under nitrogen protection to obtain a graphene powder after reduction;
    b、将还原后的石墨烯粉末倒入无水乙醇中，超声分散1-3h，得到浓度为0.1-2wt%的石墨烯无水乙醇分散液；b, the reduced graphene powder is poured into absolute ethanol, ultrasonic dispersion for 1-3h, to obtain a concentration of 0.1-2wt% of graphene anhydrous ethanol dispersion;
    c、在石墨烯无水乙醇分散液中加入适量浓硝酸，调节其pH至3-4；磁力搅拌的同时向其中缓慢滴加钛酸正丁酯，滴加量为步骤b中所用无水乙醇体积的20%-30%；待钛酸正丁酯滴加结束后，继续搅拌1-3h，得到均匀混合的胶体；c. Add an appropriate amount of concentrated nitric acid to the graphene anhydrous ethanol dispersion to adjust the pH to 3-4; slowly add n-butyl titanate to the mixture while magnetic stirring, and add the amount of absolute ethanol used in step b. 20%-30% of the volume; after the completion of the dropwise addition of n-butyl titanate, stirring is continued for 1-3 hours to obtain a uniformly mixed colloid;
    d、将均匀混合的胶体进行离心分离，用无水乙醇进行洗涤，真空干燥；d, the uniformly mixed colloid is centrifuged, washed with absolute ethanol, and vacuum dried;
    e、将前一步骤所得固体在氮气保护下380-530℃煅烧2-3h，得到石墨烯与二氧化钛的复合光催化材料。e. The solid obtained in the previous step is calcined at 380-530 ° C for 2-3 hours under nitrogen protection to obtain a composite photocatalytic material of graphene and titanium dioxide.
  8. 根据权利要求7所述的杀菌除臭鞋垫的制备方法，其特征在于，步骤a中，石墨粉和无水硝酸钠的质量比为1:1~2:1。The method for preparing a sterilizing and deodorizing insole according to claim 7, wherein in the step a, the mass ratio of the graphite powder to the anhydrous sodium nitrate is 1:1 to 2:1.
  9. 根据权利要求7所述的杀菌除臭鞋垫的制备方法，其特征在于，步骤a中，真空脱水干燥的条件为40-60℃干燥18-30h；The method for preparing a sterilizing and deodorizing insole according to claim 7, wherein in step a, the condition of vacuum dehydration drying is 40-60 ° C for 18-30 hours;
    步骤c中，真空干燥的条件为40-60℃干燥18-30h。In step c, the conditions of vacuum drying are dried at 40-60 ° C for 18-30 h.
  10. 根据权利要求7所述的杀菌除臭鞋垫的制备方法，其特征在于，步骤a中，双氧水为体积分数为30%的双氧水。The method of preparing a sterilizing and deodorizing insole according to claim 7, wherein in the step a, the hydrogen peroxide is a hydrogen peroxide having a volume fraction of 30%.
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