201041800 六、發明說明： 【發明所屬之技術領域】 本發明係一種具長效型奈米抗菌及觸媒效果的多孔性碳材及其製 作方法，該方法係利用溫差作用所產生的滲透效應，使得含氧化鋅奈 米粒子及氨化銀錯離子的水溶液能順利地滲入多孔性碳材的表面及内 邛氆集分佈的孔洞，以在該多孔性碳材經高溫乾燥處理完全乾燥後， 在其表面及孔洞内壁形成氧化鋅及銀的奈米粒子複合膜，使得該多孔 &性碳材具備長效型抗菌、防腐及觸媒效果。 【先前技術】 早在18世紀前，人類即發現炭的吸附性能，而利用於糖的脫色， 2〇世紀時，因活性碳(activated carb〇n)製造技術的開發成功，活性碳遂 取代炭’而逐漸被廣泛地躺紅業上，活性碳具有優異的吸附特性， 能作為_或各種物魏雜吸_紐，_廣泛，除已廣為各種 工業採用’如：在化學品、食品及醫藥品的生產製程中用以進行產品 屯脫色、去毋、除氯及溶劑回收等用途外，近年來，社會環保意 識的抬頭，亦使活性礙被大量使用於廢水處理、廢氣處理、淨水、淨 氣他氣體的純鱗梅躺，因此，活性碳市場的活絡主要是環 保摘的购’尤其是，水和线污細處理，這種現象在先進國家 中特別祕法規愈嚴苛的國家，活性碳的財也愈大，而其他 傳統用途_量，每年也以2〜3%的比例增加。 ’報兔的主成分為碳，並摻有少量喊、氧、氮、硫等物質化合 而成’為黑色且表面複雜的纽性姆，結構為碳所織的六環狀物， 4 201041800 粒形可由圓柱形粗顆粒到細粉末粒子，具有6〜12〇網目粒度的不規則 顆粒’粒徑一般為“酿，長度約為粒徑的〇7〜4倍，活性碳無臭、 …、味不冷於水和有機溶劑，對有機高分子物質有很強的吸附力，且 對液相中的微里成分、色素、臭氣物質等具有高度的去除能力。幾乎 所有的含碳物質均可經過不同的加工程序製成活性竣，加工程序包括 反化(Carbonization)製程及活化(Activati〇n)製程，其中碳化製程係將原 料加熱在攝氏170至600度下乾燥，使原有的有機物大約8〇%碳化， Ο兔化是在魏及冑溫雜件下進行，續祕祕（加恤）形成 多裂孔性的結構體，在碳化期間大部分的非礙元素，如：氮和氧，會 藉由原料之裂解程序，而成為揮發性氣體被去除，由於，碳化物祕 原子組合’屬於芳香族環之片狀結構，非常不規則，故會形成一些裂 隙，該等獅會在後序活化製財，形毅發達·洞結構，由於， 在碳化製程所形成的碳氫化合物會附著在活性炭邊緣的碳原子上，堵 ❾塞了料裂隙’進而影響其吸附能力’故必需藉由後續的活化製程， 來，加孔洞的形成；活化製程係利用蒸氣或化學物質來清除碳化過程 積蓄在裂隙結構中的焦油物質及裂解產物，且利用活化反應中產生的 CO及H2喊的混合氣體’峨域碳化物錢當的温度（約攝氏_ 至1000度），以燒除其中所有的可分解物質，產生發達的孔洞結構及 巨大的比表面積’使其具触強的_能力，因此，潍碳應被稱之 為經過活化製程的含碳物質。至於，竹碳或備長碳等碳材，由於係由 植物碳化熱解而成，故無需額外的活化製程’本身即已具備發達的孔 洞結構及巨大的絲面積，形雜_吸_力，故本發明在以下所 5 201041800 述及的「多孔性碳材」，係泛指活性碳、竹碳或備長碳等材料的顆粒， 合先陳明。 按，多孔性碳材的吸附能力大致可分為下列兩種： ⑴附著能力4孔性碳材裡財料麵微小細，其比表面積愈 大’即代表纽性碳材的孔洞愈多，附魏力愈好，故當雜質進入 多孔性碳材的孔洞後，就會卡在孔洞中出不來，亦不能用一般的水 洗方法將雜質洗出，_，無論液態、氣態或_、的歸，一般都 Ο具有不_粒徑大小，但唯有與多·碳_·糊者，才能附 著在多孔性碳材的孔洞中，粒徑太大或太小者則不行，因此，水或 空氣中粒徑太小的細菌、黴菌和病毒等有機物仍會通過多孔性碳材 的孔洞’而無法被附著在多孔性礙材中； (2)吸引成力.多孔性碳材表面帶正電，故能吸引一些帶負電的微小 物貝如.細囷、黴菌和病毒等有機物，多孔性碳材本身雖可再生， 〇 T般在高壓1GGBAR及攝氏遍度下’可將多孔性竣材中吸附的物質 趕出，稱之為「脫附」’惟，經脫附處理再生的多孔性碳材的吸附 月匕力僅為原先的4〇〜6〇% 0 近年來，隨著物質文明的進步，人類生活環境中的水及空氣污染 的問題亦日盈嚴重’各式淨水據芯、空氣濾網及口罩已成為住家及辦 公至中用以改善水及空氣品質不可或缺的消耗品。尤其是，台灣地處 亞熱帶，屬於長年潮濕高溫的氣候型態，細菌、黴菌和病毒等有機物 特別各易孳生’因此，淨水系統、空調通風系統及口罩中的淨水濾芯、 空氣濾網及濾材必需經常性地進行清理及更換，否則，該等淨水濾芯、 6 201041800 空氣濾網及口罩反而會成為水及空氣中滋生黴菌、細菌及病菌的溫 床，對人體健康造成的危害，實不容小覷。 有鐾於此，近年來，許多業者已將多孔性碳材應用至淨水濾芯、 空氣濾、網及口罩等渡材的設計及製造中，以期藉由多孔性礙材強大的 吸附能力，吸附水及空氣中的各種懸浮微粒，惟，由於徽菌、細菌及 病菌等微生物為懸浮微粒中體積最小者，且普遍存在於自然界中，故， 無庸置疑，對人體造成的危害(如：引起過敏、感染或毒性反應)亦最 〇為快速且明顯’甚至產生致命性的殺傷力。按，現今被廣泛使用的該 等多孔性碳材製成的濾材，雖能吸附水及空氣中的懸浮微粒及微生 物，惟，其本身卻完全不具備抗菌及殺菌的效果，故某些粒徑太小的 細囷、黴菌和病毒等有機物仍會通過多孔性碳材的孔洞，對人體造成 的危害’另’當多孔性碳材中累積吸附的懸浮微粒及微生物達到一定 數量時，反而會因有機懸浮微粒及微生物的蓄積，盡失其應有的濾淨 效果，且成為黴菌、細菌及病菌滋生的溫床。 ❿因此，如何設計出一種新穎的多孔性碳材，使得以該多孔性碳材 製成的淨水濾芯、空氣濾網及口罩等濾材，除能吸附水及空氣中的懸 淨微粒及微生物外，尚能在有光或無光的環境下，產生光觸媒及觸媒 作用只現對細菌、病毒及黴菌等有機物的降解，以產生絕佳的抗菌 及滅菌效果’即成為本發明在此欲探討的一重要課題。 【發明内容】 有鍰於前述傳統淨水濾芯、空氣濾網及口罩等濾材存在的諸多問 7 201041800 題’發明人經過長久努力研究與實驗，終於開發設計出本發明的—種 具長效型奈米抗菌及觸媒效果的多孔性碳材及其製作方法，以期使該 多孔性碳材製成的各式濾材除能吸附水及空氣中的懸浮微粒及微生物 外’尚能具備抗菌及殺菌的效果。 本發明之一目的，係在提供一種具長效型奈米抗菌及觸媒效果的 多孔性碳材的製作方法，該方法係將氧化辞奈米粒子及銀鹽粉末(如： 硝酸銀(AgN〇3)及醋酸銀(CHfooAg)等），以一預定的重量百分比， ^添加至一水溶液中，使二者在該水溶液中均句混合，並令該水溶液保 持在第一溫度’該水溶液係由水(如：去離子水或純水等)、鹼液(如k〇h 或NaOH水溶液）、氨水(或氨氣）、水溶性壓克力粉末及水性黏著劑 等成份’依預定的重量百分比’均勻混合而成，該鹼液係將銀鹽轉化 成為氫氧化銀’由於氫氧化銀會在該水溶液中形成棕色沉殿，無法均 f地分散在水溶液中’故尚必須在水溶射添純水(或減），以將 氮氧化銀的沉澱，離子化成為氨化銀錯離子(Ag(NH3)+2)，該水溶性壓 克力粉祕-水雜分制，其_録簡於水愤，能使氧化辞 以絲粒子及氨化銀錯離子均句且分散地懸浮在水溶液中，該水溶性黏 者劑的作用係在氧化鋅奈米粒子及氨化銀錯離子被均句混合至該水溶 ^，祕覆在氧化鋅奈綠子域化銀錯離子絲面上；將多孔性 反材(如.雜故、竹奴或備長碳等)置人—供箱烘烤至第二温度，其 中該第二溫度係大於該第一溫度，且溫差範圍係在攝氏⑼〜⑹度間，· 將該多孔性储私财練巾，贿—舣時_勝，使得該多 孔性碳材及水溶液間能因溫差作用，而產生渗透效應，令該水溶液得 项利地錢人該多孔性碳材的表面及内部密集分佈的孔洞 ，使得氧 8 201041800 =不米粒子及氨化銀錯離子能隨著該水溶液渗入該等孔洞；嗣，在 該水/谷2中添加一預定重量百分比的帽(HCHO)或葡萄糖，且繼續攪 '疋化間使付甲路或葡萄糖能將渗入該多孔性碳材孔洞内的氨 化銀錯離子’還原成銀奈米粒子；將該多孔性碳材自該水溶液中取出， ，行馬溫乾輯理，以在該乡錄碳材完全乾驗，使鱗孔洞中的 乳^鋅奈餘子及銀料奸能藉絲面所披覆賴水雜黏著劑， 穩定地附著在該多孔性碳材的表面及孔洞内壁，形成氧化辞及銀的奈 ❹米粒子複合膜，使得該多孔性碳材具備長效型抗菌、殺菌、防腐及 媒效果。 本發明之另-目的’係在提供_種具紐型奈米抗菌及觸媒效果 的多孔性碳材，該多孔性碳材表面及其内具有密集分佈的孔洞，氧化 鋅奈米粒子及銀奈米粒子係藉其表面所披覆的水溶性黏著劑，穩定地 _在該多孔性碳材的表面及孔洞内壁’與該多孔性碳材永久結合在 一起，形成氧化鋅及銀的奈米粒子複合膜。如此，當該多孔性碳材被 用來製作淨水遽芯、空氣濾網、口罩或其它遽材時，該多孔性碳材本 身的多孔性結構特徵，除了能吸附水或空氣中的懸浮微粒及微生物 外，該多孔性碳材表面及孔洞内壁的氧化鋅及銀的奈米粒子複合膜， 亦能在有光或無杨雜下，實麟和病料有機微生物 的抗菌及殺菌效果，此外，由於該多孔性碳材具有不會產生抗藥性、 無毒性、無刺激過敏性及不受酸驗值影響等諸多優點，且具有長效型 抗菌、殺菌、防霉及除臭等效果，故在被製作成各式遽材後，僅需被 定期清洗，即能反覆使用，符合綠色環保的要求。 為便貴審查委員能對本發明的目的、技術特徵及其功效，有更 9 201041800 進一步的認識與暸解’茲特舉一實施例，並配合圖式，詳細說明如下： 【實施方式】 按，銀奈米粒子因顆粒微細，使得整體表面積大幅增加，活性變 大’極易釋放出活性銀離子，以吸引細菌體内酶蛋白上的硫氫基，並 與其迅速結合，使含硫氫基的酵素失去活性，導致細菌死亡，且帶正 電荷的銀離子在接觸到帶負電荷的微生物細胞後，會相互吸附，穿刺 微生物的細胞外壁，使微生物内部變性，降低生長能力，讓細胞無法 ❹代謝及繁殖’直至死亡，此外，當細菌被銀離子殺死後，銀離子又會 從死去的細®上游㈣來’持續對其它活細菌做重複_作，直到所 有細菌被消滅為止’故銀奈米粒子無須光照活化，即具有絕佳的抗菌 及滅菌效果，更可抑鑛菌生長，有效達到防腐功能。氧化辞夺練 子亦因其錄尺寸與光波相當歧小，尺寸效絲致其料及價帶的 間隔增加’使其光吸收能力顯著增強，因此，在光照射下，當一個具 有-雜量的光子，或财超過轉鱗_4的光子，射入氧化辞 ❾ϋΐΓ半導體電子結構時，半導體結晶中的—個電子會從價帶激 =Γ ’留下—個具有強大氧化能力的帶正電孔洞，當電洞與水和 二乳的水分子（Η2〇)相遇時，會透過光化學反應，搶 氫氧基的電子，此時，失去雷斗的备备甘 刀于甲 失去電子的贼基立觀鮮蚊的氫氧自由 " )’不软的氫氧自由基—旦遇断來的_在氧化鋅奈米 上的械物時，會藉由搶奪對方電子的方式，使自 被氧化，而變成水和二… τ'未粒子能作為強氧化劑，實現對徽菌、細菌和病毒等 201041800 有機物的降解，以殺死黴g、細g和病毒。據上所述，銀奈米粒子及 氧化鋅奈綠子均具有長效型抗g、㈣ '不會產生抗藥性、無毒性、 無刺激過敏性及不受酸鹼值影響等諸多優點。 本發明即利用銀奈米粒子及氧化辞奈米粒子的特性，而將氧化辞 奈米粒子及銀奈米粒子等材料，應用至多孔性碳材的製作過程，使得 本發明之纽性碳材製成的各絲抑^淨核芯m網、口罩 或其它濾材）’被安裝至空調通風系統或淨水系統内黑暗的安裝位置 〇時’除能吸附空氣及水中的懸浮微粒及微生物外，亦能藉其上的氧化 鋅奈米粒子及銀奈米粒子分別在有光或無光的狀態下，實現對細菌、 病毒及黴菌等有機物的抗菌及滅菌效果。在本發明中，為了使多孔性 碳材能產生長效型抗菌及滅菌效果，必需使氧化鋅奈米粒子及銀奈米 粒子此充分地滲入多孔性碳材的多孔性結構中，本發明的製作方法包 括下列步驟，參閱第1圖所示： (101)將氧化辞奈米粒子及銀鹽粉末(如：硝酸銀(AgN〇3)及醋酸銀 (CHsCOOAg)等)以一預定的重量百分比，添加至一水溶液中，使 © 二者在該水溶液中均勻混合，並令該水溶液保持在第一溫度，該 水溶液係由水、驗液(如KOH或NaOH水溶液）、氨水(或氨氣）、 水溶性壓克力粉末及水性黏著劑等成份，依預定的重量百分比， 均勻混合而成’該鹼液係依下列化學式，將銀鹽轉化成為氫氧化 銀(AgOH):201041800 VI. Description of the Invention: [Technical Field] The present invention relates to a porous carbon material having a long-acting nano antibacterial and catalytic effect and a method for producing the same, which method utilizes a permeation effect by a temperature difference effect, The aqueous solution containing the zinc oxide nanoparticles and the silver hydride silver ions can be smoothly infiltrated into the surface of the porous carbon material and the pores of the inner enthalpy distribution, after the porous carbon material is completely dried by high temperature drying treatment, The surface of the hole and the inner wall of the hole form a composite film of zinc oxide and silver nano particles, so that the porous & carbon material has long-lasting antibacterial, antiseptic and catalytic effects. [Prior Art] As early as the 18th century, humans discovered the adsorption properties of carbon, and used it for the decolorization of sugar. In the 2nd century, the development of activated carbon (activated carb〇n) technology succeeded, and activated carbon was replaced by carbon. 'And gradually lie on the red industry, activated carbon has excellent adsorption characteristics, can be used as a _ or a variety of things Wei _ _ _ wide, in addition to widely used in various industries 'such as: in chemicals, food and In the production process of pharmaceutical products, in addition to the use of product decolorization, decanting, dechlorination and solvent recovery, in recent years, the rise of social environmental awareness has also made active use of wastewater treatment, waste gas treatment, and purified water. The pure scale plum of the gas is cleaned. Therefore, the active carbon market is mainly purchased by environmental protection, especially the water and line pollution treatment. This phenomenon is the most rigorous country in the advanced countries. The greater the amount of activated carbon, the other traditional uses, the annual increase of 2 to 3%. 'The main component of the rabbit is carbon, mixed with a small amount of shouting, oxygen, nitrogen, sulfur and other substances into a 'black and complex surface of the neon, the structure is carbon-woven six rings, 4 201041800 The shape may be from cylindrical coarse particles to fine powder particles, irregular particles having a mesh size of 6 to 12 ', the particle size is generally "wheated, the length is about 7 to 4 times the particle size, the activated carbon is odorless, ..., the taste is not It is cold to water and organic solvent, has strong adsorption capacity to organic polymer materials, and has high removal ability for micro-library components, pigments, odor substances, etc. in the liquid phase. Almost all carbonaceous materials can pass through. Different processing procedures are used to make active enthalpy. The processing procedure includes a carbonization process and an activation process. The carbonization process heats the raw materials at 170 to 600 degrees Celsius to make the original organic matter approximately 8 〇% carbonization, Ο rabbitization is carried out under the miscellaneous pieces of Wei and 胄, and the secrets (thickening) form a multi-hole structure, most of the non-intrusive elements during carbonization, such as nitrogen and oxygen, will By the cracking process of raw materials Because the volatile gas is removed, because the carbide secret atom combination 'is a sheet-like structure of the aromatic ring, it is very irregular, so some cracks will be formed. These lions will be activated in the post-order, and the shape will be developed. The structure, because the hydrocarbon formed in the carbonization process will adhere to the carbon atoms at the edge of the activated carbon, blocking the cracks of the material and affecting its adsorption capacity, so it is necessary to add holes by the subsequent activation process. Forming; the activation process uses steam or chemicals to remove the tar substances and cracking products accumulated in the fracture structure during the carbonization process, and utilizes the CO and H2 generated in the activation reaction to ignite the temperature of the mixture. About _ _ to 1000 degrees), in order to burn out all of the decomposable substances, resulting in a developed pore structure and a large specific surface area 'to make it strong _ ability, therefore, 潍 carbon should be called activation process As for the carbonaceous material, as the carbon material such as bamboo carbon or long carbon is formed by pyrolysis of plant carbonization, there is no need for an additional activation process. The "porous carbon material" referred to in the following paragraph 5 201041800 refers to particles of activated carbon, bamboo carbon or long carbon, etc., in the structure of the pores and the large area of the wire. Heming Chen Ming. According to the adsorption capacity of porous carbon materials, it can be roughly divided into the following two types: (1) Adhesion ability: The surface of the carbon material is fine and the larger the specific surface area is, the more the pores of the new carbon material are attached. The better Wei Li is, so when impurities enter the pores of the porous carbon material, they will get stuck in the holes, and they can't be washed out by ordinary water washing methods, _, regardless of liquid, gaseous or _, return, generally Tudor has a size of not _ particle size, but only with the multi-carbon _· paste, can be attached to the pores of porous carbon material, the particle size is too large or too small, it is not, therefore, water or air in the grain Organic substances such as bacteria, molds, and viruses that are too small in diameter will still pass through the pores of the porous carbon material and cannot be attached to the porous barrier material. (2) Attraction force. The surface of the porous carbon material is positively charged, so Attracting some negatively-charged micro-objects such as fine mites, molds and viruses, the porous carbon material itself can be regenerated, and it can absorb substances in porous slabs under high pressure 1GGBAR and Celsius. Eviction, called "desorption", but after desorption The adsorption capacity of the porous carbon material is only 4〇~6〇% of the original 0 In recent years, with the advancement of material civilization, the problem of water and air pollution in the human living environment is also serious. Water cores, air filters and masks have become indispensable consumables for home and office work to improve water and air quality. In particular, Taiwan is located in the subtropical zone and belongs to the climatic pattern of long-term humid and high temperature. Organic substances such as bacteria, molds and viruses are particularly prone to growth. Therefore, water purification filters, air filters and air filters in water purification systems, air conditioning ventilation systems and masks are Filter media must be cleaned and replaced frequently. Otherwise, these water purification filters, 6 201041800 air filters and masks will become hotbeds of mold, bacteria and germs in water and air, which will not cause harm to human health. Xiao Yan. In view of this, in recent years, many manufacturers have applied porous carbon materials to the design and manufacture of water purification filters, air filters, nets and masks, in order to absorb the strong adsorption capacity of porous materials. Various suspended particles in water and air, but because microorganisms such as bacteria, bacteria and germs are the smallest of the suspended particles, and are ubiquitous in nature, there is no doubt that the human body is harmful (such as: causing allergies) , infection or toxic reaction) is also the most rapid and obvious 'even fatal lethality. According to the filter materials made of these porous carbon materials, which are widely used today, they can adsorb suspended particles and microorganisms in water and air, but they do not have antibacterial and bactericidal effects at all, so some particle diameters Too small organic matter such as fine mites, molds and viruses will still pass through the pores of porous carbon materials, causing harm to the human body. 'When the cumulative amount of suspended particles and microorganisms accumulated in the porous carbon material reaches a certain amount, it will be caused by The accumulation of organic aerosols and microorganisms loses its proper filtration effect and becomes a breeding ground for mold, bacteria and pathogens. ❿ Therefore, how to design a novel porous carbon material, such as a water filter element, an air filter and a mask made of the porous carbon material, in addition to adsorbing suspended particles and microorganisms in water and air It is still possible to produce photocatalyst and catalyst in the environment of light or no light, and only degrade the bacteria, viruses and molds to produce excellent antibacterial and sterilization effects. An important topic. SUMMARY OF THE INVENTION There are many problems in the conventional water purification filter, air filter and mask, etc. 7 201041800 The inventor has developed and designed the long-acting type of the invention after long-term research and experiment. Nano-antibacterial and catalytic effect porous carbon material and its preparation method, in order to make the various filter materials made of the porous carbon material, in addition to adsorbing suspended particles and microorganisms in water and air, can still have antibacterial and sterilization Effect. An object of the present invention is to provide a method for producing a porous carbon material having a long-acting nano antibacterial and catalytic effect, which is to oxidize sodium nanoparticles and silver salt powder (eg, silver nitrate (AgN〇). 3) and silver acetate (CHfooAg), etc., added to an aqueous solution at a predetermined weight percentage, so that the two are uniformly mixed in the aqueous solution, and the aqueous solution is maintained at the first temperature. Water (eg deionized water or pure water, etc.), lye (such as k〇h or NaOH aqueous solution), ammonia (or ammonia), water-soluble acrylic powder and water-based adhesives, etc. 'Uniformly mixed, the alkali liquid converts the silver salt into silver hydroxide. Because the silver hydroxide forms a brown sink in the aqueous solution, it cannot be uniformly dispersed in the aqueous solution. Therefore, it is necessary to add pure water in the water. (or minus) to ionize the precipitation of silver oxynitride into a silver halide stionic ion (Ag(NH3)+2), the water-soluble acrylic powder secret-water heterogeneous system, which is simply recorded in water Indignation, can make the oxidized words of silk particles and silver amide silver ions uniformly and dispersedly Floating in an aqueous solution, the water-soluble adhesive acts as a mixture of zinc oxide nanoparticles and silver amide silver ions in a water-soluble solution, and is secretly coated on the zinc oxide nano-green domain silver-doped ion surface. Putting a porous anti-material (such as miscellaneous, bamboo or long carbon) into a box for baking to a second temperature, wherein the second temperature is greater than the first temperature, and the temperature difference is in Celsius (9) ~ (6) degrees, · The porous storage of private money training towel, bribe - 舣 _ _ win, so that the porous carbon material and the aqueous solution can be caused by the temperature difference, resulting in a osmotic effect, so that the aqueous solution is profitable The densely distributed pores on the surface and inside of the porous carbon material, so that oxygen 8 201041800 = non-rice particles and silver ammonia mis-ion ions can penetrate into the pores with the aqueous solution; 嗣, added in the water/valley 2 a predetermined weight percentage of cap (HCHO) or glucose, and continue to stir the 'deuteration zone to enable the road or glucose to reduce the silver ammonia mis-ion infiltrated into the pores of the porous carbon material into silver nanoparticles; The porous carbon material is taken out from the aqueous solution, and the horse is warmed and dried. In order to completely test the carbon material in the township, the milk, zinc, and silver in the scale hole can be adhered to the porous carbon material by the surface of the porous carbon material. The surface and the inner wall of the hole form a composite film of oxidized and silver nanometer particles, so that the porous carbon material has long-acting antibacterial, antiseptic, antiseptic and medium effects. Another object of the present invention is to provide a porous carbon material having an antibacterial and catalytic effect of a nano-type nano-carbon having a densely distributed pore, a zinc oxide nanoparticle and a silver. The nanoparticle is stably bonded to the porous carbon material by the water-soluble adhesive coated on the surface thereof to form a zinc oxide and silver nanoparticle on the surface of the porous carbon material and the inner wall of the pore. Particle composite membrane. Thus, when the porous carbon material is used to make a water purification core, an air filter, a mask or other coffin, the porous carbon material itself has a porous structural feature, in addition to adsorbing suspended particles in water or air. In addition to the microorganisms, the surface of the porous carbon material and the zinc oxide and silver nanoparticle composite film on the inner wall of the porous hole can also have the antibacterial and bactericidal effects of the organic microorganisms of the lining and the disease material under the presence of light or no impurities. Since the porous carbon material has many advantages such as no drug resistance, no toxicity, no irritating allergy, and no acid value, and has long-acting effects of antibacterial, bactericidal, anti-mildew and deodorization, After being made into various coffins, they only need to be cleaned regularly, that is, they can be used repeatedly, in line with the requirements of green environmental protection. For the sake of the purpose of the present invention, the technical features and the efficacy of the present invention, there is a further understanding and understanding of the present invention, and in conjunction with the drawings, the details are as follows: [Embodiment] Press, silver Due to the fineness of the particles, the nano-particles have a large increase in the overall surface area, and the activity becomes larger. It is easy to release active silver ions to attract the sulfhydryl groups on the enzyme proteins in the bacteria and bind them rapidly to make the sulfhydryl-containing enzymes. Loss of activity, leading to bacterial death, and positively charged silver ions will adsorb to each other after contact with negatively charged microbial cells, puncture the outer wall of the microbe, denature the microbial internals, reduce the growth ability, and make the cells unable to metabolize and Breeding 'until death, in addition, when the bacteria are killed by silver ions, the silver ions will continue from the dead fine ® upstream (four) 'continue to repeat the other live bacteria until all the bacteria are eliminated. The particles do not need to be activated by light, which has excellent antibacterial and sterilization effects, and can inhibit the growth of ore bacteria and effectively achieve antiseptic function. The oxidative vocabulary is also quite small due to its size and light wave, and the size effect of the wire increases the spacing between the material and the valence band, so that its light absorption capacity is significantly enhanced. Therefore, under light irradiation, when there is a -hetery amount When a photon, or a photon that exceeds the scale _4, is injected into the electronic structure of the oxidized sputum semiconductor, an electron in the semiconductor crystal will be excited from the valence band = Γ 'left--a positively charged hole with strong oxidizing power. When the hole meets the water and the water molecules of the second milk (Η2〇), it will pass through the photochemical reaction and grab the electrons of the hydroxyl group. At this time, the thief-based knives that lose the thunder Observing the hydrogen and oxygen free of fresh mosquitoes") 'The softer hydroxyl radicals—when they are interrupted, they are oxidized by robbing each other’s electrons. , and become water and two... τ' non-particles can be used as a strong oxidant to degrade the 201041800 organic matter such as bacteria, bacteria and viruses to kill mold g, fine g and virus. According to the above, both the silver nanoparticle and the zinc oxide naphtha have long-lasting anti-g, and (4) 'does not cause drug resistance, no toxicity, no irritating allergy and no influence on pH value. In the present invention, the properties of the silver nanoparticles and the oxidized nanoparticles are utilized, and materials such as oxidized nano particles and silver nanoparticles are applied to the production process of the porous carbon material, so that the carbon material of the present invention is made. The finished wire is made of a net mesh, a mask or other filter material. 'When it is installed in a dark installation position in an air conditioning ventilation system or a water purification system, it can absorb air and water suspended particles and microorganisms. It is also possible to achieve antibacterial and sterilizing effects on organic substances such as bacteria, viruses and molds by using zinc oxide nanoparticles and silver nanoparticles in the presence or absence of light. In the present invention, in order to produce a long-acting antibacterial and sterilizing effect of the porous carbon material, it is necessary to sufficiently infiltrate the zinc oxide nanoparticles and the silver nanoparticles into the porous structure of the porous carbon material, and the present invention The preparation method comprises the following steps, as shown in FIG. 1 : (101) oxidizing the nano-particles and silver salt powder (eg, silver nitrate (AgN〇3) and silver acetate (CHsCOOAg), etc.) by a predetermined weight percentage, Adding to an aqueous solution, uniformly mixing the two in the aqueous solution, and maintaining the aqueous solution at a first temperature, the aqueous solution being water, a test solution (such as KOH or NaOH aqueous solution), ammonia water (or ammonia gas), The water-soluble acrylic powder and the water-based adhesive are uniformly mixed according to a predetermined weight percentage. The alkali liquid is converted into silver hydroxide (AgOH) according to the following chemical formula:
AgN03(aq) + KOH^aq) 4 AgOH(ppt) + K+ + NCV ’由於氫氧化銀會在該水溶液中形成棕色沉澱，無法均勻地分散 在水溶液中，故尚必須在水溶液中添加氨水(或氨氣），以依下列化 11 201041800 學式，將氫氧化銀的沉殿’離子化成為氨化銀錯離子(Ag_3)+2): Ag〇H(pPt) + Ag(NH3)2+㈣ + 〇H· + 2H2〇 該水溶性壓克力粉末係-水雜分散劑，其侧係在溶解於水中 後，能使氧化鋅奈米粒子及氨化銀錯離子均勻且分散地懸浮在水 溶液中’該核_賴__錄化鋅絲奸及氨化銀錯 離子被混合人該水溶液時’能均皱覆在氧鱗奈錄子及氨化 銀錯離子的表面上； ❹（1〇2)將多孔性碳材(如：活性碳、竹碳或備長碳等)置入一烘箱供烤至 第二溫度，其中該第二溫度必需小於攝氏400度，且需大於該第 一溫度，且溫差範圍係在攝氏20〜80度間； (103)將該多孔性碳材浸入該水溶液中，進行一預定時間的勝使 知該夕孔性碳材及水溶賴能目溫差個，而產生渗透效應，令 該水溶液得以順利地滲透入該多孔性碳材的表面及内部密集分 佈的孔洞’使得氧化鋅奈綠子及氨驗錯軒能縣該水溶液 滲入該等孔洞； ❾（104)在該水，谷液中添加一預定重量百分比的甲搭邮册)或葡萄 糖’ 2繼續攪拌-預定時間，使得甲搭(HCH0)或葡萄糖能依下 歹J化予式，將滲入該多孔性碳材孔洞内的氨化銀錯離子，還原成 銀奈米粒子： 2Ag(NH3)2 (aq) + HCHO(1) + 20H' -> 2Ag(ppt) + HCOO' + NH4+ + 3NH3(g) + H20 ~夕孔f生碳材自該水溶液中取出’進行高溫乾燥處理，參閱 圖所示’以在該多孔性碳材2〇完全乾燥後，使該等孔洞21 12 201041800 中^軋化鋅奈綠子31及縣錄子32麟絲面所披覆的該 水冷性黏著劑33 ’穩定地附著在該多孔性碳材2㈣表面及内部 的孔洞21内壁’在該多孔性碳材表面及内部的孔洞21内壁形成 一氧化鋅及銀的奈米粒子複合膜。 —由於’在本發_製財財，氧靖絲好及銀奈米粒子係 猎其表_顧的該水雜黏麵，穩定_著顧糾性碳材的表 面及細義雜的制㈣，使得氧化鋅奈雜子及銀奈米粒子能 〇與-亥夕孔性石反材水久結合在一起’而令該多孔性碳材具備長效型抗 =防腐及觸媒效果。耻，當該纽性雜被絲製作淨水遽芯、 1氣/慮網σ罩或其它濾、材時，該多孔性碳材本身的多孔性結構特徵， 除了能遽除水衫氣巾_f及污垢外，該多紐碳材表面及孔洞内 土的氧化鋅及銀的奈米粒子複合膜，亦能在有光或無光的狀態下，實 現對細菌、黴菌和病毒等有機物的抗菌及殺菌效果，由於，該多孔性 碳材具有不會產生抗、無雜、無舰職性、無縣照活化及 ◎不受酸驗值影響等諸多優點，且具有長效型抗菌、殺菌、防霉及除臭 等效果’故能在被製作成各式遽材後，僅需被定期清洗，即能反覆使 用，符合綠色環保的要求。 “在本發明之一最佳實施例中，該水溶液係由水、氧化辞奈米粒子、 俩銀及/或醋酸銀、水溶性壓克力粉末、水性黏著劑、氨水(或氨氣） 及鹼液(如KOH或NaOH水溶液)等成份，依下列的重量百分比，均勻 處合而成： (1) 水：如：去離子水或純水等，其重量百分比為80%〜99% ; (2) 氧化鋅的奈米粒子··其重量百分比為〇·2%〜1〇%，在該實施例中， 13 201041800 係先將氧化辞研磨成奈米(nanometer)大小的粒子，^奈米等於十億 分之1米(10-9meter) ’或奈米級大小的粒子，即約為1〜1〇〇奈米: 介於分子和次微米間的奈米粒子； (3)水溶性的銀鹽粉末(如：硝酸銀(AgN〇3)及醋酸銀仰3C〇〇Ag) 等）·其重篁百分比為〇.〇〇1〇/0〜5〇/0，水溶性銀鹽粉末 解於水溶液，並在水溶液中釋放出氨化銀錯離子的特性； 心 ⑷鹼液：係氫氧化鉀或氫氧化鈉的水溶液，其重量百分比為 〇 〇.〇〇1%〜5% ’能在對水溶液進行攪拌的過程中，將銀鹽轉化成為氫 氧化銀’由於，氫氧化銀會在該水溶液中形成棕色沉殿，故無法均 勻地分散在水溶液中； ⑶氨水(或氨氣）：其重量百分比為_5%〜2S%，能在對水溶液進行 授拌的過程巾，將絲純的沉澱離子化成為氨化銀錯離子 (AgCNH^2)，由於，氨化銀錯離子又具有親氧的特性，故極易與氧 化鋅奈米粒子上的氧鍵結，而在該水溶液的調製過程中，均勾地附 著在氧化辞奈米粒子的表面； ©⑹水溶性壓克力粉末：其重量百分比為2%〜3〇%，其中該水溶性壓 克力粉末係-水溶性分散劑’其作用係在溶解於水中後，能使氧化 鋅奈米粒子及氨化銀錯離子均勻且分散地懸浮在水溶液中在該實 施例中，該水溶性壓克力粉末係一制稀酸衍生物(p〇lyaciyiic_ demative)，能使氧化鋅奈米粒子及氨化銀錯離子均勻分散在水溶 液中，而不致發生沉澱或齡積結塊的現象，如此，該等氧化鋅奈米 粒子及氨化銀錯離子始能隨水溶液順利地滲入該多孔性碳材表面 及其内密集分佈的該等孔洞；及 14 201041800 ⑺水溶絲賴··其重量她# α2%〜ω%，___係用 以包覆在水*液巾均勾且分散的氧化辞奈米粒子及氨化銀錯離子 的表面在該只知例中’該水溶性黏著劑係包含聚尿醋樹脂 (Umhane P〇lymer)、N_甲基比調⑼他吻恤驗㈣及三乙 胺(Tnethylamine)等成份，以在氧化鋅奈米粒子及氨化銀錯離子隨 賴水溶_魏渗透域多紐碳材的表面及内膽集分佈的 孔洞後，能在該多孔性碳材、經高溫乾燥處理而完全乾燥時，使氧化 ❸辞奈米奸及錄化侧形摘銀奈麵销其表面所披覆的該 水/合性黏著劑’穩定地附著在該多孔性碳材的表面及孔洞内壁，形 成-氧化鋅及銀的奈錄子複麵，使縣化鋅奈綠子及銀奈求 粒子能與該纽性碳材永久結合在—起’產生長效型抗菌、防腐及 觸媒的效果。 在該最佳實施财’該水溶液的第—溫度可為常溫或低溫，即攝 氏1 〇〜25度間’該多孔性碳材顆粒的第二溫度，則為攝氏3〇〜i〇5度間， 二者g差細縣持在觀2〇，賴，如此，#够級碳材被 ❾傾倒人該水溶液中，進行至少十分鐘的攪拌過程時，該纽性碳材及 水溶液間能因溫差作用’而產生渗透效應，使得該水溶液能順利地滲 入該多孔性碳材的表面及内部密集分佈的孔洞，將該等孔洞中的空氣 擠出，故，在攪拌過程中’會在該水溶液中冒出數量龐大的微小氣泡， 進而使得氧化鋅奈米粒子及氨化銀錯離子能隨著該水溶液滲入該等孔 洞，嗣，在該水溶液中添加重量百分比為〇 OOP/oM 〇5%的甲醛(HCH〇) 或0.002%〜G.1%顏糖(〇η12〇6 · h20)，且繼續·至少3G分鐘，使 得甲藤或葡萄糖能滲入該多孔性碳材的孔洞，而與其内的氨化銀錯離 15 201041800 子發生化學反應，使得氨化銀錯離子被還原成銀奈米粒子，且穩固地 附著在氧化辞奈米粒子的表面上，最後，將該多孔性碳材自該水溶液 中取出，在攝氏80〜200度的高溫下，進行乾燥處理，俟該多孔性碳材 完全乾燥後，該等孔洞中的氧化鋅奈米粒子及銀奈米粒子即能藉其表 面所披覆的該水溶性黏著劑，穩定地附著在該多孔性碳材的表面及内 部的孔洞内壁’形成-氧化辞及銀的奈米粒子複合膜。在本發明之前 述最佳實施例中，經反覆實驗證明，復參閱第2圖所示，該奈米粒子 〇複合膜中的氧化鋅奈米粒子31及銀奈米粒子32間的重量百分比，以 5.1〜60.1能對細g、病毒及黴龄有機物產生最佳的抗菌及滅菌效果。 按’以上所述，僅為本發明的一最佳具體實施例，惟本發明的特 徵並不侷限於此，任何熟悉該項技藝者在本發明領域内，可輕易思及 的、又化或修飾，皆應涵盍在以下本發明的申請專利範圍中6 【圖式簡單說明】 第1圖係本發明的製程示意圖；及 第=圖係利用本發明製程所製作的一多孔性碳材結構的局部剖面 不意圖。 20 21 31 32 【主要元件符號說明】 多孔性碳材 孔洞 氧化鋅奈米粒子 銀奈米粒子 16 201041800 水溶性黏著劑 ..............33 〇AgN03(aq) + KOH^aq) 4 AgOH(ppt) + K+ + NCV 'Because silver hydroxide forms a brown precipitate in the aqueous solution and cannot be uniformly dispersed in the aqueous solution, it is necessary to add ammonia to the aqueous solution (or Ammonia gas, according to the following formula 11 201041800, the ionization of silver hydroxide is ionized into silver silicide (Ag_3)+2): Ag〇H(pPt) + Ag(NH3)2+(4) + 〇H· + 2H2〇 The water-soluble acrylic powder-water dispersing agent, the side of which is dissolved in water, enables the zinc oxide nanoparticles and the silver hydride silver ions to be uniformly and dispersedly suspended in the aqueous solution. When the 'nuclear _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 2) placing a porous carbon material (such as activated carbon, bamboo carbon or long carbon, etc.) into an oven for baking to a second temperature, wherein the second temperature must be less than 400 degrees Celsius and greater than the first temperature, And the temperature difference is in the range of 20 to 80 degrees Celsius; (103) immersing the porous carbon material in the aqueous solution for a predetermined period of time The porous carbon material and the water-soluble lanthanum can have a temperature difference, and the osmotic effect is generated, so that the aqueous solution can smoothly penetrate into the surface of the porous carbon material and the densely-distributed pores in the interior, so that the zinc oxide nano green and the ammonia test The energy solution of the county can penetrate into the holes; ❾ (104) in the water, the valley liquid is added with a predetermined weight percentage of the mailing list) or the glucose '2 continues to stir - the predetermined time, so that the HCH (HCH0) or glucose can According to the formula of 歹J, the silver halide dissociated ions infiltrated into the pores of the porous carbon material are reduced to silver nanoparticles: 2Ag(NH3)2(aq) + HCHO(1) + 20H' -> 2Ag(ppt) + HCOO' + NH4+ + 3NH3(g) + H20 ~ 夕孔f raw carbon material is taken out from the aqueous solution 'for high-temperature drying treatment, as shown in the figure' to completely dry the porous carbon material 2〇 Thereafter, the water-cooling adhesive 33' covered by the holes 21 12 201041800 and the slabs of the slabs of the slabs are stably attached to the surface and interior of the porous carbon material 2 (4). The inner wall of the hole 21 forms a zinc oxide on the inner surface of the porous carbon material and the inner wall of the hole 21 The nanoparticle composite film. -Because of 'in this hair _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Therefore, the zinc oxide nano-hybrids and the silver nano-particles can be combined with the -Hay-porous stone anti-water for a long time, and the porous carbon material has a long-lasting anti-corrosion and catalytic effect. Shame, when the nucleus is made of pure water enamel core, 1 gas/care net σ hood or other filter material, the porous structural characteristics of the porous carbon material itself, in addition to the water hood wipes _ In addition to f and dirt, the zinc oxide and silver nanoparticle composite film on the surface of the multi-carbon material and the soil in the hole can also be used for antibacterial activities against bacteria, molds and viruses in the presence or absence of light. And the bactericidal effect, because the porous carbon material has many advantages such as no anti-wear, no impurity, no ship-bearing property, no county activation, and ◎ not affected by the acid value, and has long-acting antibacterial, sterilization, Anti-mildew and deodorization effects, so it can be used repeatedly after being made into various coffins, which can meet the requirements of green environmental protection. "In a preferred embodiment of the present invention, the aqueous solution is composed of water, oxidized nano particles, two silver and/or silver acetate, a water-soluble acrylic powder, an aqueous adhesive, ammonia (or ammonia), and The components such as lye (such as KOH or NaOH aqueous solution) are uniformly mixed according to the following weight percentages: (1) Water: such as deionized water or pure water, the weight percentage thereof is 80%~99%; 2) The nanoparticle of zinc oxide has a weight percentage of 〇·2%~1〇%. In this embodiment, 13 201041800 first oxidizes the oxidized word into a nanometer-sized particle, Equal to 1 meter of a billion (10-9meter) 'or nanometer-sized particles, ie about 1~1 nanometer: nanoparticle between the molecule and the submicron; (3) water-soluble Silver salt powder (such as: silver nitrate (AgN〇3) and silver acetate 3C〇〇Ag), etc.) The percentage of heavy bismuth is 〇.〇〇1〇/0~5〇/0, and the water-soluble silver salt powder is dissolved. An aqueous solution, and the characteristics of releasing silver chloride stionic ions in an aqueous solution; heart (4) lye: an aqueous solution of potassium hydroxide or sodium hydroxide, the weight percentage of which is 〇〇.〇 〇1%~5% 'In the process of stirring the aqueous solution, the silver salt is converted into silver hydroxide'. Because silver hydroxide forms a brown sink in the aqueous solution, it cannot be uniformly dispersed in the aqueous solution; (3) Ammonia water (or ammonia gas): the weight percentage is _5%~2S%, and the pure precipitate can be ionized into silver ammonia mis-ion (AgCNH^2) in the process towel for mixing the aqueous solution. The silver amide silver ion has an oxophilic property, so it is easily bonded to the oxygen on the zinc oxide nanoparticle, and in the preparation process of the aqueous solution, it is attached to the surface of the oxidized nanoparticle; © (6) Water-soluble acrylic powder: 2% to 3% by weight of the water-soluble acrylic powder-water-soluble dispersing agent, which acts to dissolve zinc oxide and dissolve zinc in zinc oxide. The particles and the silver amide silver ion are uniformly and dispersedly suspended in the aqueous solution. In this embodiment, the water-soluble acrylic powder is a dilute acid derivative (p〇lyaciyiic_demative) capable of causing zinc oxide nanoparticles and The silver amide silver mision is uniformly dispersed in the aqueous solution, No precipitation or ageing agglomeration occurs, so that the zinc oxide nanoparticles and the silver hydride silver ions can smoothly penetrate into the pores of the porous carbon material and the pores densely distributed therein with the aqueous solution; 14 201041800 (7) Water-soluble silk Lai · · Its weight her # α2% ~ ω%, ___ is used to coat the surface of the water * liquid towel and the dispersed oxidized nano particles and silver amide silver ions In the case of only known, the water-soluble adhesive contains Umhane P〇lymer, N-methyl ratio (9), his cheek test (4) and triethylamine (Tnethylamine), etc. After the rice particles and the silver hydride silver ion are dissolved in the surface of the surface of the multi-carbon material and the pores of the inner layer of the permeable layer, the porous carbon material can be dried under high temperature and dried completely. The water/adhesive adhesive that is coated on the surface of the surface of the porous carbon material is stably attached to the surface of the porous carbon material and the inner wall of the hole to form zinc oxide and silver. Naizizi complex, so that the county zinc nucleus and Yinnai particles can be permanently associated with the new carbon material Together - since 'produce long-lasting antimicrobial effect, corrosion and catalyst. In the best implementation, the first temperature of the aqueous solution may be normal temperature or low temperature, that is, between 1 〇 and 25 degrees Celsius, and the second temperature of the porous carbon material particles is between 3 〇 and 5 deg. , the difference between the two counties in the county 2, Lai, so, # enough grade carbon material was dumped in the aqueous solution, for at least ten minutes of mixing process, the temperature difference between the carbon and the aqueous solution The action acts to create a osmotic effect, so that the aqueous solution can smoothly penetrate into the surface of the porous carbon material and the densely distributed pores therein, and the air in the holes is extruded, so that it will be in the aqueous solution during the stirring process. A large number of tiny bubbles are generated, so that the zinc oxide nanoparticles and the silver amide silver ions can penetrate into the pores with the aqueous solution, and a formaldehyde having a weight percentage of 〇OOP/oM 〇5% is added to the aqueous solution. (HCH〇) or 0.002%~G.1% saccharide (〇η12〇6 · h20), and continue for at least 3G minutes, so that the vine or glucose can penetrate into the pores of the porous carbon material, and the ammoniation therein Silver is wrong with 15 201041800 Sub-chemical reactions that make The silver amide silver ions are reduced to silver nanoparticles and firmly adhered to the surface of the oxidized nano particles. Finally, the porous carbon material is taken out from the aqueous solution at a high temperature of 80 to 200 degrees Celsius. After the porous carbon material is completely dried, the zinc oxide nanoparticles and the silver nanoparticles in the pores are stably adhered to the surface by the water-soluble adhesive coated on the surface. The surface of the porous carbon material and the inner wall of the pores of the porous carbon material form a composite film of oxide particles and silver nanoparticles. In the foregoing preferred embodiment of the present invention, the weight percentage of the zinc oxide nanoparticle 31 and the silver nanoparticle 32 in the nanoparticle composite membrane is as shown in the second experiment. With 5.1~60.1, it can produce the best antibacterial and sterilization effect on fine g, virus and mildew organic matter. The above description is only a preferred embodiment of the present invention, but the features of the present invention are not limited thereto, and any one skilled in the art can easily think about and reconcile or The modifications are all included in the following patent application scope of the present invention. 6 [Simple description of the drawings] Fig. 1 is a schematic view of the process of the present invention; and Fig. 1 is a porous carbon material produced by the process of the present invention. The partial section of the structure is not intended. 20 21 31 32 [Description of main component symbols] Porous carbon material Hole Zinc oxide nanoparticle Silver nanoparticle 16 201041800 Water-soluble adhesive ..............33 〇
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