TW201912242A - Photocatalyst material with antibacterial effect, preparation method thereof and photocatalytic member - Google Patents
Photocatalyst material with antibacterial effect, preparation method thereof and photocatalytic member Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 97
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 50
- 230000001699 photocatalysis Effects 0.000 title description 15
- 238000002360 preparation method Methods 0.000 title description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000002245 particle Substances 0.000 claims abstract description 44
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 21
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 43
- 239000004408 titanium dioxide Substances 0.000 claims description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000084 colloidal system Substances 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002344 surface layer Substances 0.000 abstract 4
- 239000000243 solution Substances 0.000 description 38
- 239000002131 composite material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 241000588724 Escherichia coli Species 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- DKYDUFWOIUKRGU-UHFFFAOYSA-N [Ag+].[O-2].[Ce+3].[O-2] Chemical compound [Ag+].[O-2].[Ce+3].[O-2] DKYDUFWOIUKRGU-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000005202 decontamination Methods 0.000 description 4
- 230000003588 decontaminative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 241000186359 Mycobacterium Species 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229910001923 silver oxide Inorganic materials 0.000 description 3
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
-
- B01J35/39—
-
- B01J35/393—
-
- B01J35/396—
Abstract
Description
本發明涉及一種光觸媒、其製備方法與應用，特別是涉及一種具有抗菌效果的光觸媒材料、其製備方法與光觸媒構件。 The invention relates to a photocatalyst, a preparation method and application thereof, and in particular, to a photocatalyst material having an antibacterial effect, a preparation method thereof, and a photocatalyst member.
光觸媒就是經過光的照射，可以促進化學反應的物質。光觸媒擅長於光催化處理空氣中低濃度的有害化學物質，且本身不會釋出有害物質，因此也是極優異的環境淨化用觸媒。目前常用來作為光觸媒的物質有金屬氧化物，其中二氧化鈦(TiO2)因為具有強大的氧化能力、高化學穩定度及無毒等特性而最常被使用。 Photocatalysts are substances that can promote chemical reactions after being irradiated with light. Photocatalysts are good at photocatalytically treating low concentrations of harmful chemicals in the air, and do not release harmful substances themselves, so they are also excellent catalysts for environmental purification. At present, the materials commonly used as photocatalysts are metal oxides. Among them, titanium dioxide (TiO 2 ) is most often used because of its strong oxidation ability, high chemical stability, and non-toxicity.
所謂光催化處理程序的光分解機制，指的是通過紫外光或太陽光激發光觸媒，使光觸媒產生電子與電洞，以將吸附在其表面上的物質氧化，並分解為小分子。以二氧化鈦為例，其於波長400nm的光照射下開始反應(因為二氧化鈦的能階差約為3.1eV，而波長400nm的光能量約為3.1eV)，二氧化鈦吸收光能量並產生電子與電洞，其中的電洞具有相當強的氧化力，可以將表面上的汙染物分子直接氧化分解，或者將表面上的水分子分解為氫氧自由基。原本的大分子汙染物通過光觸媒反應而裂解為小分子，即達到清除汙染物的目的。 The so-called photodecomposition mechanism of the photocatalytic treatment program refers to the excitation of the photocatalyst by ultraviolet light or sunlight, so that the photocatalyst generates electrons and holes to oxidize the substance adsorbed on its surface and decompose it into small molecules. Take titanium dioxide as an example, it starts to react under the irradiation of light with a wavelength of 400nm (because the energy level difference of titanium dioxide is about 3.1eV and the light energy at a wavelength of 400nm is about 3.1eV), titanium dioxide absorbs light energy and generates electrons and holes. The holes have a strong oxidizing power, which can directly oxidize and decompose pollutant molecules on the surface, or decompose water molecules on the surface into hydroxyl radicals. The original macromolecular pollutants are cracked into small molecules by photocatalytic reaction, that is, the purpose of removing the pollutants is achieved.
二氧化鈦一般會搭載於載體上使用，以增加光線的照射面積。然而，二氧化鈦須在300℃至500℃的溫度進行煅燒，始能 形成銳鈦礦結晶(anatase)，此種型鈦的結晶才具有光催化效果，但是有些載體例如布料、皮革等，並無法耐受高溫。此外，二氧化鈦本身並不具備抗菌、抑菌的能力，因此在應用上會受到一定的限制，為了解決此問題，目前較常見的作法，是將二氧化鈦與銀複合。然而，所形成的複合材料僅能提升一部分的抗菌性能，對一般常見的菌種(如大腸桿菌、金黃色葡萄球菌等)有優異的抗菌效果，但是對較頑強的菌種(如分枝桿菌等)則無法有效抑制其生長，抗菌效果不佳。此外，這類複合材料在經過一段時間的使用後，奈米銀表面常會有生物膜附著，造成抗菌效果降低。 Titanium dioxide is generally used on a carrier to increase the area illuminated by light. However, titanium dioxide must be calcined at a temperature of 300 ° C to 500 ° C before anatase crystals can be formed. This type of titanium crystals have photocatalytic effects, but some carriers such as cloth and leather are not resistant. Subject to high temperature. In addition, titanium dioxide itself does not have antibacterial and bacteriostatic capabilities, so it will be limited in application. To solve this problem, a more common practice at present is to combine titanium dioxide with silver. However, the formed composite material can only enhance a part of the antibacterial performance, and has excellent antibacterial effect on common common bacteria (such as E. coli, Staphylococcus aureus, etc.), but on more tenacious bacteria (such as mycobacterium Etc.) cannot effectively inhibit its growth, and the antibacterial effect is not good. In addition, after such composite materials are used for a period of time, biofilms often adhere to the surface of nano-silver, which reduces the antibacterial effect.
本發明所要解決的技術問題在於，針對現有技術的不足提供了一種具有抗菌效果的光觸媒材料，特別是在照光與不照光條件下都能有強效持久的抗菌能力。本發明還提供了上述光觸媒材料的製備方法與使用上述光觸媒材料的光觸媒構件。 The technical problem to be solved by the present invention is to provide a photocatalyst material with an antibacterial effect in response to the shortcomings of the prior art, in particular, it can have a strong and durable antibacterial ability under both light and non-light conditions. The invention also provides a method for preparing the photocatalyst material and a photocatalyst member using the photocatalyst material.
為了解決上述的技術問題，本發明所採用的其中一技術方案是：一種具有抗菌效果的光觸媒材料，包括多個光觸媒粒子，其中每一個所述光觸媒粒子包括一核心體以及一形成於所述核心體的表面上的外覆層。所述核心體為二氧化矽所構成，所述外覆層為二氧化鈰與銀所構成，而所述核心體與所述外覆層的重量比介於1：1至1：2之間，且所述在外覆層中二氧化鈰所佔的重量大於銀所佔的重量。 In order to solve the above technical problem, one of the technical solutions adopted by the present invention is: a photocatalyst material with antibacterial effect, including a plurality of photocatalyst particles, wherein each of the photocatalyst particles includes a core body and a core body formed on the core Overlay on the surface of the body. The core body is made of silicon dioxide, the outer cover layer is made of cerium dioxide and silver, and the weight ratio of the core body and the outer cover layer is between 1: 1 and 1: 2 And the weight of the cerium oxide in the outer coating is greater than the weight of silver.
根據本發明的一實施例，每一個所述光觸媒粒子的所述核心體呈針狀，且具有一介於1至40之間的長徑比。 According to an embodiment of the present invention, the core of each of the photocatalyst particles is needle-shaped and has an aspect ratio between 1 and 40.
根據本發明的一實施例，所述外覆層包括多個奈米二氧化鈰顆粒以及多個奈米銀顆粒，其中多個所述奈米二氧化鈰顆粒的平均粒徑介於5nm至20nm之間，多個所述奈米銀顆粒的平均粒徑介於1nm至10nm之間。 According to an embodiment of the present invention, the outer coating layer includes a plurality of nanometer cerium dioxide particles and a plurality of nanometer silver particles, wherein an average particle diameter of the plurality of nanometer cerium oxide particles is between 5 nm and 20 nm. In between, the average particle diameter of the plurality of nano silver particles is between 1 nm and 10 nm.
根據本發明的一實施例，多個所述奈米二氧化鈰顆粒佔所述 外覆層總重量的50%至75%，多個所述奈米銀顆粒佔所述外覆層總重量的25%至50%。 According to an embodiment of the present invention, a plurality of the nano-cerium dioxide particles account for 50% to 75% of the total weight of the outer cover layer, and a plurality of the nano-silver particles account for 50% to 75% of the total weight of the outer cover layer. 25% to 50%.
根據本發明的一實施例，所述外覆層以連續的形式形成於所述核心體的表面上。 According to an embodiment of the invention, the outer cover layer is formed on the surface of the core body in a continuous form.
根據本發明的一實施例，所述外覆層以分散的形式形成於所述核心體的表面上。 According to an embodiment of the present invention, the outer cover layer is formed on the surface of the core body in a dispersed form.
本發明所採用的另外一技術方案是：一種具有抗菌效果的光觸媒材料的製備方法，包括以下步驟：製備氫氧化鈦膠體，然後加入雙氧水，以形成二氧化鈦膠體溶液；以及在60℃至100℃的溫度下，向所述二氧化鈦膠體溶液加入二氧化鈰與硝酸銀，然後持溫加熱直到膠體水解消失，以形成所述具有抗菌效果的光觸媒材料，其中二氧化鈦、二氧化鈰、銀與水的重量比為0.01%-2%：0.01%-1%：0.001%-1%：96%-96.979%。 Another technical solution adopted by the present invention is: a method for preparing a photocatalyst material with antibacterial effect, comprising the following steps: preparing titanium hydroxide colloid, and then adding hydrogen peroxide to form a titanium dioxide colloid solution; and a 60 ° C to 100 ° C At the temperature, cerium dioxide and silver nitrate are added to the titanium dioxide colloid solution, and then heated at a constant temperature until the colloid is hydrolyzed to form the photocatalyst material with antibacterial effect. The weight ratio of titanium dioxide, cerium dioxide, silver and water is 0.01% -2%: 0.01% -1%: 0.001% -1%: 96% -96.979%.
根據本發明的一實施例，所述氫氧化鈦膠體是先在0℃至15℃的溫度下，將四氯化鈦與鹽酸水溶液混合，再於所形成的混合物中加入氨水而製得。 According to an embodiment of the present invention, the titanium hydroxide colloid is prepared by mixing titanium tetrachloride with an aqueous hydrochloric acid solution at a temperature of 0 ° C to 15 ° C, and then adding ammonia water to the formed mixture.
根據本發明的一實施例，所述二氧化鈦膠體溶液中雙氧水與二氧化鈦的莫耳比介於2：1至5：1之間，且二氧化鈦的固含量介於0.01%至2%之間。 According to an embodiment of the present invention, the molar ratio of hydrogen peroxide to titanium dioxide in the titanium dioxide colloid solution is between 2: 1 and 5: 1, and the solid content of titanium dioxide is between 0.01% and 2%.
根據本發明的一實施例，所述具有抗菌效果的光觸媒材料具有一介於6.5至10之間的pH值。 According to an embodiment of the invention, the photocatalyst material with antibacterial effect has a pH value between 6.5 and 10.
本發明所採用的再一技術方案是：一種光觸媒構件，包括一載體以及一使用上述具有抗菌效果的光觸媒材料塗佈於所述載體上而形成的光觸媒層。 Still another technical solution adopted by the present invention is: a photocatalyst member including a carrier and a photocatalyst layer formed by coating the carrier with the photocatalyst material having the antibacterial effect.
本發明的有益效果在於，本發明技術方案所提供的具有抗菌效果的光觸媒材料，其通過“每一個光觸媒粒子包括一核心體以及一形成於核心體的表面上的外覆層，其中核心體為二氧化矽所構成，外覆層為二氧化鈰與銀所構成，而核心體與外覆層的重量比 介於1：1至1：2之間，且在外覆層中二氧化鈰所佔的重量大於銀所佔的重量”的技術特徵，在可見光下能長久保持良好的抗菌效果，且當光觸媒層受到紫外光或日光燈照射時，能產生相當高的催化活性，並具有去汙、自潔與抗菌的作用。 The beneficial effect of the present invention is that the photocatalyst material with antibacterial effect provided by the technical solution of the present invention passes through "each photocatalyst particle includes a core body and an outer cover layer formed on the surface of the core body, wherein the core body is It is composed of silicon dioxide, and the outer layer is composed of cerium dioxide and silver, and the weight ratio of the core body and the outer layer is between 1: 1 and 1: 2, and the cerium dioxide accounts for the outer layer. "The weight is greater than the weight occupied by silver." It can maintain a good antibacterial effect under visible light for a long time, and when the photocatalyst layer is exposed to ultraviolet light or fluorescent light, it can produce a relatively high catalytic activity. Cleansing and antibacterial effect.
為使能更進一步瞭解本發明的特徵及技術內容，請參閱以下有關本發明的詳細說明與附圖，然而所提供的附圖僅用於提供參考與說明，並非用來對本發明加以限制。 In order to further understand the features and technical contents of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are only for reference and description, and are not intended to limit the present invention.
Z‧‧‧光觸媒構件 Z‧‧‧Photocatalyst
M‧‧‧光觸媒材料 M‧‧‧Photocatalyst material
1‧‧‧光觸媒層 1‧‧‧Photocatalyst layer
10‧‧‧光觸媒粒子 10‧‧‧Photocatalyst particles
11‧‧‧核心體 11‧‧‧Core
12‧‧‧外覆層 12‧‧‧ Overlay
121‧‧‧奈米二氧化鈰顆粒 121‧‧‧Nano cerium dioxide particles
122‧‧‧奈米銀顆粒 122‧‧‧ nano silver particles
2‧‧‧載體 2‧‧‧ carrier
S100‧‧‧製備方法 S100‧‧‧Preparation method
S102、S104‧‧‧流程步驟 S102, S104‧‧‧Process steps
圖1為本發明的具有抗菌效果的光觸媒材料的製備方法的步驟流程圖。 FIG. 1 is a flowchart of steps in a method for preparing a photocatalyst material with antibacterial effect according to the present invention.
圖2為本發明的具有抗菌效果的光觸媒材料的結構示意圖(一)。 FIG. 2 is a schematic structural diagram (1) of a photocatalyst material with antibacterial effect according to the present invention.
圖3為本發明的具有抗菌效果的光觸媒材料的結構示意圖(二)。 FIG. 3 is a schematic structural diagram (2) of a photocatalyst material with antibacterial effect according to the present invention.
圖4為本發明的光觸媒構件的結構示意圖。 FIG. 4 is a schematic structural diagram of a photocatalyst member according to the present invention.
圖5為圖4中V部分的局部示意圖。 FIG. 5 is a partial schematic diagram of a V portion in FIG. 4.
由於二氧化鈦(TiO2)作為光觸媒，其本身不具備抗菌抑菌的能力而使得應用範圍受限，本發明提出一種新的光觸媒材料，其通過將二氧化鈦與二氧化鈰(CeO2)和銀(Ag)複合，能獲得照光與不照光條件下良好的抗菌抑菌能力。而為了實現此光觸媒材料的大量生產與廣泛應用，本發明還提出一種創新的低溫製程，其不需要300℃以上的高溫煅燒，且所製成的光觸媒粒子的懸浮液很穩定，光觸媒粒子即便超過3年也不會聚集、產生沉澱。 As titanium dioxide (TiO 2 ) as a photocatalyst, it does not have the ability of antibacterial and bacteriostasis, which limits the application range. The present invention proposes a new photocatalyst material, which combines titanium dioxide with cerium dioxide (CeO 2 ) and silver (Ag ) Compound, can get good antibacterial and antibacterial ability under the conditions of light and no light. In order to realize the mass production and wide application of this photocatalyst material, the invention also proposes an innovative low-temperature process, which does not require high-temperature calcination above 300 ° C, and the suspension of the prepared photocatalyst particles is very stable. It will not aggregate or precipitate in 3 years.
以下是通過特定的具體實施例來說明本發明所公開有關“具有抗菌效果的光觸媒材料、其製備方法與光觸媒構件”的實施方式，本領域技術人員可由本說明書所公開的內容瞭解本發明的優點與效果。本發明可通過其他不同的具體實施例加以施行或應 用，本說明書中的各項細節也可基於不同觀點與應用，在不悖離本發明的精神下進行各種修飾與變更。另外，本發明的附圖僅為簡單示意說明，並非依實際尺寸的描繪，事先聲明。以下的實施方式將進一步詳細說明本發明的相關技術內容，但所公開的內容並非用以限制本發明的保護範圍。 The following are specific embodiments to explain the embodiments of the present invention related to "photocatalyst materials with antibacterial effects, methods for preparing them and photocatalyst members". Those skilled in the art can understand the advantages of the present invention from the contents disclosed in this specification. With effect. The present invention may be implemented or applied through other different specific embodiments, and various details in this specification may also be based on different viewpoints and applications, and various modifications and changes may be made without departing from the spirit of the present invention. In addition, the drawings of the present invention are merely a schematic illustration, and are not drawn according to actual dimensions, and are stated in advance. The following embodiments will further describe the related technical content of the present invention in detail, but the disclosed content is not intended to limit the protection scope of the present invention.
[第一實施例] [First embodiment]
請參閱圖1所示，為本發明第一實施例的具有抗菌效果的光觸媒材料的製備方法的步驟流程圖。如圖1所示，製備方法S100包括下列步驟：步驟S102，製備氫氧化鈦膠體，然後加入雙氧水，以形成二氧化鈦膠體溶液；以及步驟S104，在60℃至100℃的溫度下，向二氧化鈦膠體溶液加入二氧化鈰與硝酸銀，然後持溫加熱直到膠體水解消失，以形成具有抗菌效果的光觸媒材料。 Please refer to FIG. 1, which is a flow chart of steps in a method for preparing a photocatalyst material with antibacterial effect according to a first embodiment of the present invention. As shown in FIG. 1, the preparation method S100 includes the following steps: Step S102, preparing a titanium hydroxide colloid, and then adding hydrogen peroxide to form a titanium dioxide colloid solution; and step S104, applying a titanium dioxide colloid solution at a temperature of 60 ° C to 100 ° C. Add cerium dioxide and silver nitrate, then heat at a constant temperature until the colloid hydrolysis disappears to form a photocatalyst material with antibacterial effect.
步驟S102中，氫氧化鈦膠體是先在0℃至15℃的溫度下，將四氯化鈦與鹽酸水溶液混合，再於所形成的混合物中加入氨水而製得。於實際實施時，是先將作為鈦源的四氯化鈦緩慢加入鹽酸水溶液中，形成四氯化鈦分散液，再加入30%氨水(NH4OH)調整pH至6-12，形成含有氫氧化鈦膠體的混濁液，然後將混濁液過濾，並水洗數次，直到沒有氯離子為止(可以硝酸銀滴定直到沒有白色氯化銀沉澱為判斷依據)，即得到純度較高的氫氧化鈦膠體。之後加入雙氧水進行反應，形成二氧化鈦膠體溶液。 In step S102, titanium hydroxide colloid is prepared by mixing titanium tetrachloride with an aqueous hydrochloric acid solution at a temperature of 0 ° C to 15 ° C, and then adding ammonia water to the formed mixture. In actual implementation, titanium tetrachloride as a titanium source is slowly added to an aqueous hydrochloric acid solution to form a titanium tetrachloride dispersion, and then 30% ammonia water (NH 4 OH) is added to adjust the pH to 6-12 to form hydrogen. A turbid solution of titanium dioxide colloid, and then the turbid solution is filtered and washed several times until there are no chloride ions (it can be titrated with silver nitrate until no white silver chloride precipitates as the basis of judgment), to obtain titanium hydroxide colloid with higher purity. After that, hydrogen peroxide was added for reaction to form a titanium dioxide colloid solution.
步驟S104中，是先將步驟S102中形成的二氧化鈦膠體溶液置於60℃至100℃的溫度下加熱一段時間(如1-10小時)，再向加熱後的二氧化鈦膠體溶液加入二氧化鈰與硝酸銀(AgNO3)溶液，然後持溫加熱直到膠體水解消失，即得到作為光觸媒材料的二氧化鈰-銀/二氧化鈦複合溶膠溶液；較佳地，複合溶膠溶液具有一介於6.5至10之間的pH，且複合溶膠溶液中二氧化鈦、二氧化鈰、銀與水的重量比為0.01%-2%：0.01%-1%：0.001%-1%： 96.9%-96.979%。 In step S104, the titanium dioxide colloidal solution formed in step S102 is first heated at a temperature of 60 ° C to 100 ° C for a period of time (for example, 1-10 hours), and then the ceria and silver nitrate are added to the heated titanium dioxide colloidal solution. (AgNO 3 ) solution, then heated at a constant temperature until the colloidal hydrolysis disappears, to obtain a cerium dioxide-silver / titanium dioxide composite sol solution as a photocatalyst material; preferably, the composite sol solution has a pH between 6.5 and 10, And the weight ratio of titanium dioxide, cerium oxide, silver and water in the composite sol solution is 0.01% -2%: 0.01% -1%: 0.001% -1%: 96.9% -96.979%.
請參閱圖2及圖3所示，由製備方法S100製成的光觸媒材料M，包括多個穩定懸浮於水中的光觸媒粒子10，每一個光觸媒粒子10包括一核心體11以及一形成於核心體11的表面上的外覆層12。其中核心體11為二氧化矽所構成，且為一銳鈦礦型結晶體，外覆層12為二氧化鈰與銀所構成。於實際實施時，外覆層12可以連續的形式形成於核心體11的表面上(如圖2所示)，也可以分散的形式形成於核心體11的表面上(如圖3所示)。 Please refer to FIG. 2 and FIG. 3. The photocatalyst material M made by the preparation method S100 includes a plurality of photocatalyst particles 10 stably suspended in water. Each photocatalyst particle 10 includes a core body 11 and a core body 11. The outer cover 12 on the surface. The core body 11 is composed of silicon dioxide, and is an anatase crystal, and the outer cover layer 12 is composed of cerium dioxide and silver. In actual implementation, the outer cover layer 12 may be formed on the surface of the core body 11 in a continuous form (as shown in FIG. 2), or may be formed on the surface of the core body 11 in a dispersed form (as shown in FIG. 3).
值得注意的是，每一個光觸媒粒子10的核心體11與外覆層12的重量比介於1：1至1：2之間，且外覆層12中二氧化鈰所佔的重量大於銀所佔的重量。藉此，電子電洞對轉移復合的時間得以有效延長，此現象不僅提高了光觸媒的活性，還能將激發光觸媒活性的波長從紫外光波段往可見光波段位移，使得光觸媒材料M能在可見光下長久保持良好的抗菌效果。 It is worth noting that the weight ratio of the core 11 and the outer cover 12 of each photocatalyst particle 10 is between 1: 1 and 1: 2, and the weight of the cerium dioxide in the outer cover 12 is greater than that of silver. Accounted for the weight. By this, the time for the electron hole to transfer and recombine can be effectively prolonged. This phenomenon not only improves the photocatalyst activity, but also shifts the wavelength that excites the photocatalyst activity from the ultraviolet light band to the visible light band. Maintain good antibacterial effect.
較佳地，核心體11呈針狀，且具有一介於1至40之間的長徑比。外覆層12包括多個奈米二氧化鈰顆粒121以及多個奈米銀顆粒122，其中氧化鈰顆粒121的平均粒徑介於5至20之間，且二氧化鈰顆粒121佔外覆層12總重量的50-75%，奈米銀顆粒122的平均粒徑介於1至10之間，且奈米銀顆粒122佔外覆層12總重量的25-50%。 Preferably, the core body 11 is needle-shaped and has an aspect ratio between 1 and 40. The outer cover layer 12 includes a plurality of nano-cerium oxide particles 121 and a plurality of nano-silver particles 122, wherein the average particle diameter of the cerium oxide particles 121 is between 5 and 20, and the cerium oxide particles 121 occupy the outer cover layer. 50-75% of the total weight of 12; the average particle diameter of the nano-silver particles 122 is between 1 and 10; and the nano-silver particles 122 account for 25-50% of the total weight of the outer cover layer 12.
請參閱圖4所示，為了增加可見光的利用率，可以將光觸媒材料M(即二氧化鈰-銀/二氧化鈦複合溶膠溶液)製成透明薄膜，並應用於一載體2上，以增加暴露面積，從而增加光催化效率；載體2可以是玻璃、陶瓷或塑膠材質，但不限定於此。於實際實施時，光觸媒材料M可通過浸鍍或噴鍍方式形成於載體2表面上，且形成光觸媒層1；光觸媒材料M呈中性，其不會對載體2造成腐蝕。當光觸媒層1受到紫外光或日光燈照射時，能產生相當高的催化活性，並具有去汙、自潔與抗菌的作用。 Please refer to FIG. 4, in order to increase the utilization of visible light, a photocatalyst material M (ie, cerium dioxide-silver / titanium dioxide composite sol solution) can be made into a transparent film and applied to a carrier 2 to increase the exposed area. Thus, the photocatalytic efficiency is increased; the carrier 2 may be made of glass, ceramic or plastic, but is not limited thereto. In actual implementation, the photocatalyst material M can be formed on the surface of the carrier 2 by dipping or spraying, and the photocatalyst layer 1 is formed; the photocatalyst material M is neutral, and it will not cause corrosion to the carrier 2. When the photocatalyst layer 1 is irradiated with ultraviolet light or fluorescent lamp, it can produce a relatively high catalytic activity, and has the functions of decontamination, self-cleaning and antibacterial.
值得注意的是，光觸媒粒子10的核心體11具有一介於1至40之間的長徑比，所以其具有相當高的附著性與可堆疊性，從而可形成具有高附著度與致密度的光觸媒層1。實驗顯示，光觸媒層1的附著度於百格測試中可以達到5B的標準，且於泡水百格測試中也可以達到5B的標準；再者，光觸媒層1具有高致密度，根據CNS 10757標準，光觸媒層1的耐磨壽命可以達到約3000次。 It is worth noting that the core body 11 of the photocatalyst particles 10 has an aspect ratio between 1 and 40, so it has a relatively high adhesion and stackability, thereby forming a photocatalyst with high adhesion and density. Layer 1. Experiments show that the adhesion of photocatalyst layer 1 can reach the 5B standard in the 100-box test, and it can also reach the 5B standard in the soaked water 100-box test. Furthermore, the photocatalyst layer 1 has a high density, according to the CNS 10757 standard The abrasion life of the photocatalyst layer 1 can reach about 3000 times.
請複參閱圖2至圖4，更進一步的說，由載體2與光觸媒層1可以構成一具有廣泛實際應用性的光觸媒構件Z，其製作流程如下： Please refer to FIG. 2 to FIG. 4. Furthermore, the carrier 2 and the photocatalyst layer 1 can form a photocatalyst member Z with wide practical application. The manufacturing process is as follows:
一、清洗載體 First, cleaning the carrier
清洗載體2是為了讓光觸媒材料M更牢固地附著於載體2上。一旦載體2表面有油性物質或其他不潔物存在，將導致鍍膜不均勻和發生剝落。清洗載體2的步驟如下：1.將載體2靜置於中性清潔劑中，以超音波震盪清洗一小時；2.以去離子水清洗載體2表面殘留的清潔劑，並以超音波震盪清洗一小時；3.將載體2置於氫氧化鈉溶液中，以超音波震盪清洗一小時；4.以去離子水清洗殘留於載體2表面上的氫氧化鈉溶液，並以超音波震盪清洗一小時；及5.將載體2置入烘箱中乾燥並保存，以備鍍膜之用。 The carrier 2 is cleaned in order to make the photocatalyst material M adhere to the carrier 2 more firmly. Once the surface of the carrier 2 has oily substances or other impurities, it will cause uneven coating and peeling. The steps of cleaning the carrier 2 are as follows: 1. Put the carrier 2 in a neutral detergent, and wash it with ultrasonic vibration for one hour; 2. Wash the detergent remaining on the surface of the carrier 2 with deionized water, and clean it with ultrasonic vibration One hour; 3. Put the carrier 2 in the sodium hydroxide solution, and wash it with ultrasonic vibration for one hour; 4. Wash the sodium hydroxide solution remaining on the surface of the carrier 2 with deionized water, and wash it with ultrasonic vibration. Hours; and 5. Place the carrier 2 in an oven to dry and store it for coating.
二、鍍膜方法 Coating method
採用浸漬鍍膜法形成光觸媒層1，鍍膜的步驟如下：1.將光觸媒材料M的覆膜液置於拉升機台上；2.將載體2固定於拉升機上；3.將載體2浸入覆膜液中，下降速率為5-10公分/每分鐘；4.開始拉升覆膜，上升速率為5-10公分/每分鐘；5.覆膜完畢後，置於紫外光燈下照射30分鐘；6.將紫外光處理後的載體2置於烘箱中，於60-160℃下乾燥， 即完成光觸媒層1的一次覆膜工作；及7.製作多層覆膜時，須重複上述各項步驟。 The photocatalyst layer 1 is formed by the dip coating method, and the coating steps are as follows: 1. Place the coating solution of the photocatalyst material M on the drawing machine platform; 2. Fix the carrier 2 on the drawing machine; 3. Dip the carrier 2 into In the coating solution, the falling rate is 5-10 cm / minute; 4. Start to pull up the coating, and the rising rate is 5-10 cm / minute; 5. After the coating is completed, place it under UV light and irradiate 30 Minutes; 6. Put the UV-treated carrier 2 in an oven and dry it at 60-160 ° C to complete the primary coating of the photocatalyst layer 1; and 7. Repeat the above steps when making a multilayer coating step.
實驗例1 Experimental example 1
在0℃的冰浴中，將四氯化鈦緩慢滴入5莫耳濃度(5M)的鹽酸水溶液中，再將30%的氨水緩慢加入四氯化鈦分散液，不斷攪拌直到分散液的pH值為7，經過數次離心、水洗，直到氯的濃度低於5000ppm，此時再將得到的膠體置於蒸餾水中，並加入雙氧水。所形成的膠體溶液置於三頸圓錐瓶內，接上冷凝管於90℃下加熱1小時，加入二氧化鈰與硝酸銀溶液，調整二氧化鈦、雙氧水、水、二氧化鈰溶液與硝酸銀溶液的重量比為0.02%：0.0255%：99.902%：0.05%：0.025%，再加熱2小時，得到二氧化鈰-銀/二氧化鈦複合溶膠溶液。最終形成的光催化材料中，二氧化鈦、二氧化鈰、銀與水的重量比約為0.01%-2%：0.01%-1%：0.001%-1%：96%-96.979%。 In an ice bath at 0 ° C, slowly drop titanium tetrachloride into a 5 mol (5M) hydrochloric acid aqueous solution, and then slowly add 30% ammonia water to the titanium tetrachloride dispersion, and continue to stir until the pH of the dispersion The value is 7, after several centrifugation and water washing until the concentration of chlorine is less than 5000 ppm, the colloid obtained is then placed in distilled water, and hydrogen peroxide is added. The formed colloidal solution was placed in a three-necked conical flask, connected to a condensing tube and heated at 90 ° C for 1 hour, and added cerium dioxide and silver nitrate solution to adjust the weight ratio of titanium dioxide, hydrogen peroxide, water, cerium oxide solution to silver nitrate solution. It was 0.02%: 0.0255%: 99.902%: 0.05%: 0.025%, and then heated for 2 hours to obtain a cerium dioxide-silver / titanium dioxide composite sol solution. In the final formed photocatalytic material, the weight ratio of titanium dioxide, cerium oxide, silver and water is about 0.01% -2%: 0.01% -1%: 0.001% -1%: 96% -96.979%.
比較例1 Comparative Example 1
將市售的二氧化鈦(Evonik-Degussa公司產品，奈米二氧化鈦P-25)與水混合，重量比為1/100。 Commercially available titanium dioxide (product of Evonik-Degussa, nano titanium dioxide P-25) was mixed with water at a weight ratio of 1/100.
比較例2 Comparative Example 2
在0℃的冰浴中，將四氯化鈦緩慢滴入5莫耳濃度(5M)的鹽酸水溶液中，再將30%的氨水緩慢加入四氯化鈦分散液，不斷攪拌直到溶液的pH值為7，經過數次離心、水洗，直到氯的濃度低於5000ppm，此時再將得到的膠體置於蒸餾水中，並加入雙氧水與硝酸銀，調整二氧化鈦、雙氧水、水與硝酸銀溶液的重量比為0.02%：0.0255%：99.952%：0.0025%，此溶液在三頸圓錐瓶內，接上冷凝管於90℃下加熱2小時，得到銀/二氧化鈦複合溶膠溶液。 In an ice bath at 0 ° C, slowly drop titanium tetrachloride into a 5 mol concentration (5M) hydrochloric acid aqueous solution, and then slowly add 30% ammonia water to the titanium tetrachloride dispersion, and continue to stir until the pH of the solution Is 7, after several centrifugation and water washing until the concentration of chlorine is less than 5000ppm, at this time, the obtained colloid is placed in distilled water, and hydrogen peroxide and silver nitrate are added, and the weight ratio of titanium dioxide, hydrogen peroxide, water and silver nitrate solution is adjusted to 0.02 %: 0.0255%: 99.952%: 0.0025%. This solution is in a three-necked conical flask, connected to a condenser and heated at 90 ° C for 2 hours to obtain a silver / titanium dioxide composite sol solution.
測試去汙與自潔能力 Test decontamination and self-cleaning ability
在玻璃載體上形成含有實驗例1與比較例1、2的光催化材料的光催化層，並利用亞甲烯藍光催化反應作為標準來測試去汙與自潔功效。將具有光催化層的玻璃載體浸入亞甲烯藍溶液(含10,000ppm亞甲烯藍)，周圍用波長為254nm的紫外光(2根10W的燈管)或日光燈管照射(2根10W的燈管)，每隔10分鐘取樣，離心後再用紫外光-可見光光譜儀量測波長為662nm時的吸收值，由吸收度變化情形來判斷亞甲烯藍的消失率。試驗4小時後的亞甲烯藍消失率如下。 A photocatalytic layer containing the photocatalytic materials of Experimental Example 1 and Comparative Examples 1 and 2 was formed on a glass support, and the methyleneene blue photocatalytic reaction was used as a standard to test the decontamination and self-cleaning efficacy. A glass support with a photocatalytic layer was immersed in a methylene blue solution (containing 10,000 ppm methylene blue), and the surrounding was irradiated with ultraviolet light with a wavelength of 254 nm (two 10 W lamps) or a fluorescent tube (two 10 W lamps Tube), take samples every 10 minutes, and then measure the absorption value at a wavelength of 662 nm with a UV-visible spectrometer after centrifugation, and judge the disappearance rate of methylene blue from the change of the absorbance. The disappearance rate of methylene blue after 4 hours of the test is as follows.
測試抗菌抑菌能力 Test antibacterial and antibacterial ability
在玻璃載體上形成含有實驗例1與比較例1、2的光催化材料的光催化層，並利ISO 27447：2009所制訂的標準，分別在無光照射、紫外光照射及日光燈照射的條件下測試抗菌抑菌能力。測試菌種包括較容易處理的大腸桿菌(原始菌液濃度2.68×106CFU/ml)與較難處理的分枝桿菌(原始菌液濃度2.32×106CFU/ml)。 A photocatalytic layer containing photocatalytic materials of Experimental Example 1 and Comparative Examples 1 and 2 was formed on a glass support, and the standards established by ISO 27447: 2009 were used under the conditions of no light irradiation, ultraviolet light irradiation, and fluorescent lamp irradiation, respectively. Test antibacterial and antibacterial ability. The tested strains included E. coli (the original bacterial solution concentration of 2.68 × 106 CFU / ml) and Mycobacterium (the original bacterial solution concentration: 2.32 × 106 CFU / ml), which was easier to handle.
測試結果顯示，二氧化鈦光催化(比較例1)僅在紫外光照射的條件下，對大腸桿菌與分枝桿菌均有較好的抗菌效果，對兩種菌的抗菌率分別可以達到99%與80-90%。銀/二氧化鈦光催化(比較例2)雖然在紫外光照射的條件下，對大腸桿菌與分枝桿菌均有非常優異的抗菌效果，對兩種菌的抗菌率可高達99%，但是其在日光燈照射的條件下，對較難處理的分枝桿菌的抗菌效果有限，抗菌率只有50-60%。有別於二氧化鈦光催化與銀/二氧化鈦光催化，二氧化鈰-銀/二氧化鈦光催化(實驗例1)不僅在紫外光照射與日光燈照射的條件下，對大腸桿菌與分枝桿菌均有非常優異的抗菌效果，對兩種菌的抗菌率可高達99%，而且在照光與不照光條件下，對大腸桿菌與分枝桿菌也有一定的抗菌抑菌能力。 The test results show that titanium dioxide photocatalysis (Comparative Example 1) has good antibacterial effect on E. coli and mycobacteria only under the condition of ultraviolet light irradiation, and the antibacterial rates of the two bacteria can reach 99% and 80- 90%. Silver / titanium dioxide photocatalysis (Comparative Example 2) Although it has excellent antibacterial effect on E. coli and mycobacteria under the condition of ultraviolet light irradiation, the antibacterial rate against both bacteria can be as high as 99%, but it is exposed to fluorescent light Under the conditions, the antibacterial effect on the more difficult to treat Mycobacterium is limited, and the antibacterial rate is only 50-60%. Different from titanium dioxide photocatalysis and silver / titanium dioxide photocatalysis, cerium dioxide-silver / titanium dioxide photocatalysis (Experiment Example 1) is not only excellent in E. coli and mycobacteria under the conditions of ultraviolet light and fluorescent light irradiation. The antibacterial effect of the two bacteria can be as high as 99%, and also has certain antibacterial and antibacterial ability against E. coli and mycobacteria under the conditions of light and no light.
[實施例的有益效果] [Advantageous Effects of the Embodiment]
本發明的有益效果在於，本發明實施例所提供的具有抗菌效果的光觸媒材料，其通過“每一個光觸媒粒子包括一核心體以及一形成於核心體的表面上的外覆層，其中核心體為二氧化矽所構成，外覆層為二氧化鈰與銀所構成，而核心體與外覆層的重量比介於1：1至1：2之間，且在外覆層中二氧化鈰所佔的重量大於銀所佔的重量”的技術特徵，能獲得照光與不照光條件下良好的抗菌抑菌能力，且當光觸媒層受到紫外光或日光燈照射時，能產生相當 高的催化活性，並具有去汙、自潔與抗菌的作用。 The beneficial effect of the present invention is that the photocatalyst material with antibacterial effect provided by the embodiment of the present invention passes through "each photocatalyst particle includes a core body and an outer cover layer formed on the surface of the core body, wherein the core body is It is composed of silicon dioxide, and the outer layer is composed of cerium dioxide and silver, and the weight ratio of the core body and the outer layer is between 1: 1 and 1: 2, and the cerium dioxide accounts for the outer layer. "The weight is greater than the weight occupied by silver." It can obtain good antibacterial and antibacterial ability under light and no light conditions. When the photocatalyst layer is exposed to ultraviolet light or fluorescent light, it can produce a relatively high catalytic activity. Decontamination, self-cleaning and antibacterial effect.
承上所述，光觸媒粒子的核心體具有一介於1至40之間的長徑比，所以其具有相當高的附著性與可堆疊性，從而可形成具有高附著度與致密度的光觸媒層。 As mentioned above, the core of the photocatalyst particles has an aspect ratio between 1 and 40, so it has a relatively high adhesion and stackability, so that a photocatalyst layer with high adhesion and density can be formed.
以上所公開的內容僅為本發明的優選可行實施例，並非因此侷限本發明的申請專利範圍，所以凡是運用本發明說明書及附圖內容所做的等效技術變化，均包含於本發明的申請專利範圍內。 The content disclosed above is only the preferred and feasible embodiment of the present invention, and therefore does not limit the scope of patent application of the present invention. Therefore, any equivalent technical changes made by using the description and drawings of the present invention are included in the application of the present invention. Within the scope of the patent.
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