200924840 九、發明說明： 【發明所屬之技術領域】 本發明係麵定分散之奈綠雜子/無餘土複合物及其製法 係利用片狀無機黏土作為紐’以分散球狀結構的金屬材料，製備無有機物之 奈米金屬粒子之穩定液，並進-步乾燥臟粉體；產品可應驗化學催化及生 物抗菌方面，包括生物、醫藥、化學、化工、材料等。 【先前技術】 0 奈米銀粒子具有公認的抗菌效果，可殺死6⑽多種細g，比起自來水殺菌 用的氯多出數十倍的殺菌功能。奈米銀在多倍稀釋的情況下，對於大腸桿菌、 金黃色葡萄_ ’沙門氏桿g及綠膿桿龄，均有99 9_抑制功效。當細菌 被銀離子殺贿，雜子又會觀去的_上游離出來，再持續對活細菌做重 複的動作，直至所有_被消^由此可知，奈米銀的姐是屬於長效型抗菌 劑。銀是不具毒性的物質，純奈米銀也可食用，因此對人體無害。美國藥物食 品檢驗局也強調此種產品可以運用於商品並繼續被量產。目前己經發表的文獻 ❹中，有關奈米銀治療的報導’最有名的有痤瘡、娜、抗過敏、盲腸炎、關節 炎、抗癌、糖尿病等等。透過奈米技術，可使銀粒子的活性變大，表面積增加， 其殺菌功能增強至銀的2〇〇倍左右。 目前製備奈綠子的方法’有以高能量的詩，紅麟（_細e) 固態物質裂解成奈米尺度大小的粒子。有的是將金属固態物質，氣化成氣態金 屬蒸氣、,再以冷凝聚域金屬奈雜子^或者是以有機雜_氧化還原法來 製備奈米銀。在製備過程中，操作複雜，所需的設備也大幅增加生產成本，而 且在操作賴造的雌巾H顾在ppm的賴下柯断，絲高銀離子 濃度’還原時易造成銀粒子聚集，降低產品功效，因此操作範圍有限，加上低 濃度下所製備出的奈米銀，總量不高，反應面積小，使得催化及抗菌效果有限。 Ο ❹ 200924840 在製備時，所使用的有機溶劑與有機界面活性劑對於環境亦是一種負擔，能否 應用在醫療或其他材料上，達到抗菌、殺菌的目的，仍是一個未知數。 為使奈来金屬粒子穩定，並防止粒子產生凝集現象，在製備金屬奈米粒子 過程中’通常需添加分細或保制。保赫的作时式包&⑴藉由靜電 排斥力’使粒子表面吸附電荷，形成電雙層，粒子表面帶有相同電荷，則當兩 個粒子相互接近，縣排斥力會增加，防錄子凝t若表面吸賴陰離子被 中性吸附練代，麻面電荷顧少，凡得關力將錄子難。另外在高濃 度粒子下或溶_子強度增加時，由於介電強度的，電雙層被壓縮，而不 利粒子的穩定；⑵藉由立體阻礙，粒子表面若有吸附保護劑，藉由有機分子 在金屬粒子表卿祕護綱，樣雜子的凝聚稱為立體歡。常用的保護 劑種類包括：水溶性高分子類（如PVP、PVA、p〇lymethy ) viny ie齡、舰等）、 界面活性劑、配位基或螫合劑e 【發明内容】 本發月之目的在於提供-種敎分散之奈米 及其製法，謂魅物聽學_穌 齡土複合物200924840 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a disperse nano-heteron/non-remaining composite and a method for producing the same, which utilizes flaky inorganic clay as a metal material for dispersing a spherical structure, The preparation of the solid solution of the organic metal-free nano metal particles and the stepwise drying of the dirty powder; the product can be subjected to chemical catalysis and biological antibacterial aspects, including biology, medicine, chemistry, chemicals, materials and the like. [Prior Art] 0 Nano silver particles have a recognized antibacterial effect and can kill 6 (10) kinds of fine g, which is dozens of times more bactericidal than chlorine used for sterilization of tap water. In the case of multiple dilutions, nano silver has a 99 9_ inhibitory effect on E. coli, golden yellow grapes _'s Salmonella g and green pus age. When the bacteria are killed by silver ions, the miscellaneous will be released from the _, and then continue to repeat the action on the living bacteria until all _ is eliminated. It can be seen that the silver silver sister is a long-acting type. Antibacterial agents. Silver is a non-toxic substance, and pure nano-silver is also edible, so it is harmless to the human body. The US Food and Drug Administration also emphasized that such products can be used in commodities and continue to be mass-produced. Currently published literature, reports on nano-silver treatments are most famous for acne, na, anti-allergy, appendicitis, arthritis, anti-cancer, diabetes and so on. Through the nanotechnology, the activity of the silver particles is increased, the surface area is increased, and the bactericidal function is enhanced to about 2 times that of silver. At present, the method for preparing nematic greens has a high-energy poem, and the red lining (_fine e) solid matter is cleaved into nanoparticles of a nanometer size. Some are to vaporize a solid metal material into a gaseous metal vapor, and then to prepare a nanosilver by condensing a poly-molecular metal or by an organic hetero-oxidation method. In the preparation process, the operation is complicated, the required equipment also greatly increases the production cost, and in the operation of the female towel H, in the case of ppm, the silver high ion concentration tends to cause silver particles to aggregate. The product efficiency is limited, so the operation range is limited, and the nano silver prepared at a low concentration is not high in total amount, and the reaction area is small, so that the catalytic and antibacterial effects are limited. Ο ❹ 200924840 At the time of preparation, the organic solvent and organic surfactant used are also a burden on the environment. Whether it can be applied to medical or other materials for antibacterial and sterilization purposes is still unknown. In order to stabilize the nematic metal particles and prevent the particles from agglomerating, it is usually necessary to add fineness or protection during the preparation of the metal nanoparticles. Baohe's time-based package & (1) causes the surface of the particle to adsorb electric charge by electrostatic repulsion force to form an electric double layer with the same charge on the surface of the particle. When the two particles are close to each other, the county repulsive force will increase, and the anti-recording will be prevented. If the surface is absorbed by the neutral adsorption, the surface charge is less, and it is difficult to record the matter. In addition, under high concentration particles or when the strength of the solution increases, the electric double layer is compressed due to the dielectric strength, which is unsatisfactory for the stability of the particles; (2) by the steric hindrance, if there is an adsorption protectant on the surface of the particle, the organic molecule In the metal particle celebrity secrets, the aggregation of the miscellaneous is called stereo. Commonly used types of protective agents include: water-soluble polymers (such as PVP, PVA, p〇lymethy) viny ie age, ship, etc.), surfactants, ligands or chelating agents e [Summary of the matter] It is to provide a kind of nano-dispersed nanometer and its preparation method, which is called enchantment
Uspect rati0)為⑽〜〗，_的奈米片狀^^力效。本發明利用長徑比 (aspect ratio)為1的球狀奈米銀粒子，避免其聚隼立H礙’以分散長徑比 黏土所具有之娜娜質咖，㈣另外， 200924840 【實施方式】 本發明之較佳實施例係叫四面體及獻面縣2:1的層狀雜 物為载體。利用Ag+交換層間他種陽離子，藉由負電荷吸附在黏土膠體上，經由 化學還原法’ V蚊在黏土表面，黏土對銀的麵力很強，粒子間不易互相吸 引，並且利用黏土立體結構障礙避免聚集，達到均句分散的效果。 本發明較佳實施例使用的材料包括： 1.人工合成的層狀矽酸鹽黏土礦物：讓，陽離子交換容量（cec卜Ο』？ mequiv/g，CO-OP Chemical Co.製造。 Ο 2.硝酸銀：^Ν〇3，交換取代黏土層間此+，還原後形成奈米銀粒子。 3. 硼氫化鈉：NaBH4，強還原劑。 4. 曱醇：CH3〇H，95%，弱還原劑。 以下詳細說明較佳實施例的操作步驟，其中實施例卜16係以甲醇還原法製 備奈米銀’其中實施例16係於還原過程加入氙燈的照射；實施例17〜19係以NaBH4 還原法製備奈米銀’其中實施例19係於還原過程加入氙燈的照射。 實施例1 先配製SWN溶液（1. 〇 wt%)及AgN〇3溶液（1. 〇 wt%)，然後取AgN〇3⑽（1. 〇 wt% ’ 0. 68g)緩慢加入SWN溶液（30g，1. 〇 wt%)中，使AgVCEC的比例為0. 2，Uspect rati0) is (10) ~〗, _ nano-sheet ^ ^ force effect. The present invention utilizes spherical nano silver particles having an aspect ratio of 1, and avoids the aggregation of the N-type coffee which is dispersed in the aspect ratio clay. (4) In addition, 200924840 [Embodiment] The preferred embodiment of the present invention is a tetrahedron and a layered impurity of 2:1 in Xian County as a carrier. Using Ag+ exchange layer cations, adsorbed on the clay colloid by negative charge, through the chemical reduction method, 'V mosquitoes on the clay surface, the clay has strong surface power to silver, the particles are not easy to attract each other, and the clay is used for three-dimensional structural obstacles. Avoid aggregation and achieve the effect of uniform sentence dispersion. Materials used in preferred embodiments of the invention include: 1. Synthetic layered silicate clay mineral: cation exchange capacity (cec Ο ??? mequiv/g, manufactured by CO-OP Chemical Co.) Ο 2. Silver nitrate: ^Ν〇3, exchange between the clay layer to replace this +, after reduction to form nano silver particles. 3. Sodium borohydride: NaBH4, strong reducing agent 4. Sterol: CH3 〇 H, 95%, weak reducing agent. The operation steps of the preferred embodiment are described in detail below, wherein the embodiment 16 is to prepare nano silver by the methanol reduction method, wherein the embodiment 16 is irradiated with a xenon lamp during the reduction process; and the examples 17 to 19 are prepared by the NaBH4 reduction method. Nano silver 'Example 19 is the irradiation of xenon lamp during the reduction process. Example 1 First prepare SWN solution (1. 〇wt%) and AgN〇3 solution (1. 〇wt%), then take AgN〇3(10) ( I, 〇wt% ' 0. 68g) slowly added to the SWN solution (30g, 1. 〇wt%), so that the ratio of AgVCEC is 0.2.
Ag取代黏土層間的Na，溶液會呈現淡米黃色。接著，在溶液中加入足量的甲醇 (MeOH，約6〜8mL)，此時溶液無明顯變化。經隔水加熱至70〜80°C，溶液顏色 慢慢產生變化，進行甲醇還原層間銀離子之反應。當反應2〜3小時後，溶液就 會呈現深酒紅色，振盡後即為產物。 實施例2〜15 操作步驟同實施例1，但增加AgN〇3(aq) (1 wt%)的劑量，使AgVCEC的比例 200924840 分別為 0.4、0· 6、0. 8、1. 〇、1. 5、2. 0、3.0、5. 0、8. 0、10、20、30、35、200 ; 曱醇（MeOH)亦根據比例適度增加。 實施例16 操作步驟同實施例5，但在以隔水加熱進行還原反應同時，並以氙燈照射溶 液。 實施例17 先配製 SWN 溶液（1. 〇 wt°/〇 及 AgN〇3溶液（1. 〇 wt%)，然後取 AgN〇3(aq) (L 〇 〇 wt% ’ 0. 68g)，緩慢加入 SWN 溶液（30g，1. 0 wt%)中’使 AgVCEC 的比例為 〇. 2， Ag+取代黏土層間之Na+，溶液會呈現淡米黃色。接著，將粉末狀NaBH4 (〇. 〇〇75g) 分次加入溶液，溶液會立即呈現深的黃綠色，攪拌均勻並振盪後，此溶液即為 產品。 實施例18 操作步驟同實施例17，但AgVCEC的比例改為1. 〇。 φ實施例19 操作步驟同實施例18，但在添加NaBH4進行還原反應同時，並以氙燈照射溶 液。 產物分析 取上述實施例所得的產物Ag-SWN溶液1 ml，滴在cm2破璃基材上，放 置烘箱以80X：乾燥2小時後，將此玻璃基材鑛碳觀察，以進行下列分析。 1·均勻分散性 以SEM觀察實施例5及18的粉狀產物，結果分別如第2圖及第3圖所示。 圖中明顯看出，以甲醇及Ν·為還原劑所製成的奈来銀/無機點土複合物不皆 •B· 200924840 具有良好的分散性及均勻度；其中甲醇還原法所得的奈米銀/無機黏土複合物， 其均勻度更優於NaBH4還原法。 第4圖及第5圖則為實施例16及19的產物，相較於第2圖及第3圖，氙 燈照射所得的奈米銀粒子的粒徑明顯變小；這是由於能量增加，使分子彼此間 產生較大的干擾行為，而形成粒徑較小的粒子。 相較於傳統製程使用有機溶劑為反應媒介，其產物烘乾後不易分散，粒子 容易聚集，僅能用TEM觀察。若應用於材料表面的塗抹’經過烘乾或風乾後， 會出現相同的聚集問題’在材料應用方面較困難。 此外’在製作SEM樣本時發現，產物可緊密吸附在載玻片上，這是由於黏 〇 土本身的吸附力大，因此可讓溶液均勻分佈在玻片上。此一特性可讓產品廣泛 應用於各種材料，而且可依需要進行塗佈或喷霧。 2.粒徑分析 表1為實施例1〜19的粉狀產物的平均粒徑；其中甲醇還原法所得的奈米銀 /無機黏土複合物，其平均粒麵僅為麵4還原法的_半。本發明製成的奈米 銀粒子因為她極小’朗具有較大的表面積，抗菌及麟的侧也會因反應 總面積變大而提升。 * Ο 甲賴·生成的奈米錄觀法小，這是由於ψ醇為弱還原 劑必須藉由隔水加熱才能進行銀離子還原反應，因此奈絲生成速度緩慢， 形成的顆粒小。相反地，議是強還原劑，還原速度快，所形成奈米銀的粒徑 …:而-還原過程1疋在黏土層間進行，因此奈米銀的粒徑大小會受到限 制，產生的顆粒將比傳統方法微小。 200924840 表1 實施 AgVCEC 還原劑 氙燈 層間距離 平均粒徑（nm) 例 照射 (A) Dn Dw D*/Dn 1 0. 2 甲醇 無 13. 8 15. 0 17. 7 1. 18 2 0.4 甲醇 無 13. 8 14. 9 16. 9 1. 13 3 0· 6 甲醇 無 13. 9 20. 1 24. 1 1. 20 4 0. 8 甲醇 無 13. 8 22. 4 27. 1 1. 21 5 1. 0 甲醇 無 13. 9 25. 9 30. 1 1. 16 6 1.5 甲醇 無 13. 7 29. 6 37. 6 1. 14 7 2. 0 甲醇 無 13. 2 41. 6 49. 9 1. 20 8 3. 0 甲醇 無 14. 6 49. 1 70. 1 1.43 9 5. 0 甲醇 無 15. 8 55. 7 83.2 1.49 10 8. 0 甲醇 無 15. 9 56. 3 88.4 1. 57 11 10 甲醇 無 脫層 60. 7 92. 1 1. 54 12 20 甲醇 無 脫層 65. 2 101 1. 55 13 30 曱醇 無 脫層 71. 6 115 1. 61 14 35 甲醇 無 脫層 83.4 125 1. 51 15 200 甲醇 無 脫層 16 1. 0 甲醇 有 13. 2 9. 8 10. 7 1. 09 17 0. 2 NaBH4 無 13. 8 26 39 1. 5 18 1.0 NaBH4 無 13. 7 45. 7 59. 3 1.3 19 1.0 NaBH4 有 13. 8 17. 7 42. 5 2.40 -to· 200924840 ，Ag replaces Na between clay layers, and the solution will appear pale beige. Next, a sufficient amount of methanol (MeOH, about 6 to 8 mL) was added to the solution, at which time the solution did not change significantly. After heating to 70-80 ° C by water, the color of the solution slowly changes, and the reaction of silver ions between the layers of methanol reduction is performed. After 2 to 3 hours of reaction, the solution will show a deep burgundy color and will be the product after it has been shaken. Example 2~15 The operation procedure is the same as in Example 1, except that the dose of AgN〇3(aq) (1 wt%) is increased so that the ratio of AgVCEC is 2009,4840 is 0.4, 0.6, 0.8, 1. 〇, 1 5, 2. 0, 3.0, 5.0, 8. 0, 10, 20, 30, 35, 200; sterol (MeOH) also increased moderately according to the proportion. Example 16 The procedure was the same as in Example 5 except that the reduction reaction was carried out while heating with water, and the solution was irradiated with a xenon lamp. Example 17 First prepare a SWN solution (1. 〇wt ° / 〇 and AgN 〇 3 solution (1. 〇 wt%), then take AgN 〇 3 (aq) (L 〇〇 wt% ' 0. 68g), slowly added In the SWN solution (30g, 1.0% wt%), the ratio of AgVCEC is 〇. 2, Ag+ replaces Na+ between the clay layers, and the solution will be pale beige. Then, the powdered NaBH4 (〇. 〇〇75g) is divided. After the solution was added, the solution immediately showed a deep yellow-green color. After stirring and shaking, the solution was the product. Example 18 The procedure was the same as in Example 17, but the ratio of AgVCEC was changed to 1. 〇 Example 19 Operation The procedure was the same as in Example 18, except that NaBH4 was added to carry out the reduction reaction, and the solution was irradiated with a xenon lamp. Product Analysis 1 ml of the product Ag-SWN solution obtained in the above example was dropped on a cm2 glass substrate, and placed in an oven at 80X. After drying for 2 hours, the glass substrate ore was observed for the following analysis: 1. Uniform Dispersibility The powdery products of Examples 5 and 18 were observed by SEM, and the results are shown in Figures 2 and 3, respectively. It is obvious in the figure that neramin/inorganic made of methanol and rhodium as a reducing agent Inconsistent soil composition • B· 200924840 has good dispersibility and uniformity; the nano-silver/inorganic clay composite obtained by methanol reduction method has better uniformity than NaBH4 reduction method. Figure 4 and Figure 5 The products of Examples 16 and 19, compared with Figures 2 and 3, the particle size of the nano-silver particles obtained by the xenon lamp irradiation is significantly smaller; this is due to the increase in energy, which causes the molecules to have a larger relationship with each other. Interfering with the behavior, and forming particles with smaller particle size. Compared with the traditional process, the organic solvent is used as the reaction medium, the product is not easy to disperse after drying, the particles are easy to aggregate, and can only be observed by TEM. If applied to the surface of the material After drying or air drying, the same aggregation problem will occur, which is difficult in material application. In addition, when the SEM sample was produced, it was found that the product could be closely adsorbed on the glass slide because the adsorption of the clay itself was large. Therefore, the solution can be evenly distributed on the slide. This feature allows the product to be widely used in various materials, and can be coated or sprayed as needed. 2. Particle size analysis Table 1 is the embodiment 1~1 The average particle diameter of the powdery product of 9; wherein the nano silver/inorganic clay composite obtained by the methanol reduction method has an average grain size of only _half of the surface reduction method. The nano silver particles produced by the invention are because of her The extremely small 'Lang has a large surface area, and the side of the antibacterial and Lin will also increase due to the larger total area of the reaction. * Ο The nanometer image produced by Jia Lai is small, which is due to the fact that sterol is a weak reducing agent. The silver ion reduction reaction can be carried out by heating with water, so the formation speed of the nanofilament is slow, and the formed particles are small. Conversely, it is a strong reducing agent, the reduction speed is fast, the particle size of the formed nano silver is...: and the reduction process 1疋 is carried out between the clay layers, so the size of the nanosilver is limited, and the resulting particles will be smaller than the conventional method. 200924840 Table 1 Implementation of AgVCEC Reducing Agent Xenon Light Interlayer Distance Average Particle Size (nm) Example Irradiation (A) Dn Dw D*/Dn 1 0. 2 Methanol No 13. 8 15. 0 17. 7 1. 18 2 0.4 Methanol No 13 8 14. 9 16. 9 1. 13 3 0· 6 Methanol without 13. 9 20. 1 24. 1 1. 20 4 0. 8 Methanol without 13. 8 22. 4 27. 1 1. 21 5 1. 0 Methanol without 13. 9 25. 9 30. 1 1. 16 6 1.5 Methanol without 13. 7 29. 6 37. 6 1. 14 7 2. 0 Methanol without 13. 2 41. 6 49. 9 1. 20 8 3. 0 methanol without 14. 6 49. 1 70. 1 1.43 9 5. 0 methanol without 15. 8 55. 7 83.2 1.49 10 8. 0 methanol without 15. 9 56. 3 88.4 1. 57 11 10 methanol without off Layer 60. 7 92. 1 1. 54 12 20 Methanol free delamination 65. 2 101 1. 55 13 30 decyl alcohol without delamination 71. 6 115 1. 61 14 35 Methanol without delamination 83.4 125 1. 51 15 200 Methanol without delamination 16 1. 0 Methanol has 13. 2 9. 8 10. 7 1. 09 17 0. 2 NaBH4 No 13. 8 26 39 1. 5 18 1.0 NaBH4 No 13. 7 45. 7 59. 3 1.3 19 1.0 NaBH4 has 13. 8 17. 7 42. 5 2.40 -to· 200924840 ,
第6圖進一步將實補卜15的粉狀產物的平均粒徑賴成圖，顯示AgVcEC 。制的是，即使Ag+/咖比例增加到 ’所得不核/無機黏土複合物的平均粒徑僅為l25nm。亦即，本發明 用少量的黏土即可達聽護_分散效果，可製備高濃度奈綠溶液，因此可 備規模，或是在相同反應條件下增加製備總量，達到濃縮的效果，提 升整個製程的效能。 本發明以水作域應介質，而非傳統的有機溶劑，同時原料是源於自然界 的黏土，所以不會對環境或人體造成負擔及危害。 ©本發·較佳實施例雖係仙·，但亦可以獨_土做域體’例如蒙 脫土、人工合成雲母、水滑石等，其CEC、片徑大小、比表面積、電荷密度及立 體結構皆會有所差異，但都可絲作為保護劑，生成奈米銀。至於層間電荷的 離子性質、價數、靜電吸㈣_、在層間分佈的均勻性、電荷密度及量的多 券’對於離子的交換過程’以致於後來的還原反應亦會造成影響。 本發明的還林祕N祕，不_獅然還原力強弱不 -，但健可以達到金祕子還原_效果，例如乙醇及其他醇類還原劑。 本發明實施·金屬離子不限於銀離子，可為金、銅、鐵或其他適當之金 ❹屬。銀離子來源亦不限於硝酸銀，只要能適當地提供銀離子即可，例如，域、Fig. 6 further shows the average particle diameter of the powdery product of Fig. 15 as a graph showing AgVcEC. It is found that even if the Ag+/coffee ratio is increased to 'the resulting non-nuclear/inorganic clay composite has an average particle diameter of only 15 nm. That is to say, the invention can achieve the listening and dispersing effect with a small amount of clay, and can prepare a high-concentration naphthalene solution, so that the scale can be prepared, or the total amount of preparation can be increased under the same reaction conditions to achieve the effect of concentration and enhance the whole. Process efficiency. The invention adopts water as a medium for medium, instead of a traditional organic solvent, and the raw material is derived from clay in nature, so it does not burden or harm the environment or the human body. ©本发· The preferred embodiment is a fairy, but it can also be used as a domain body such as montmorillonite, synthetic mica, hydrotalcite, etc., with CEC, chip size, specific surface area, charge density and stereo The structure will vary, but all can be used as a protective agent to produce nano silver. As for the ionic properties of the interlayer charge, the valence, the electrostatic absorption (four) _, the uniformity of distribution between layers, the charge density and the amount of the coupon 'for the exchange process of ions', the subsequent reduction reaction also has an effect. The secret of the invention is also N secret, not _ _ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ Implementation of the Invention The metal ion is not limited to silver ions and may be gold, copper, iron or other suitable metal genus. The source of silver ions is not limited to silver nitrate as long as it can properly supply silver ions, for example, domains,
AgBr、AgCl〇3、AgQ。 本發明比起-般的製備過程，其製程更為峡，因此可有效降低生產設備 及操作成本。此外，黏土是片狀的奈米材料，具有高比表面積⑽m2/g) 與南電荷密度（1 W2) ’朗於觸材料將有較高的機械性質、鲍定性以 及阻氣性，更可擴大其奈米金屬的應用範疇。 200924840 圖示簡單說明： 第1圖為本發明利用奈米片狀黏土分散球狀奈米銀粒子之示意圖； 第2~5圖為實施例5、18、16、19的粉狀產物的SEM圖； 第6圖為實施例1~15的粉狀產物的平均粒徑圖。 〇 ❹ -A·AgBr, AgCl〇3, AgQ. Compared with the general preparation process, the invention has a more process, which can effectively reduce production equipment and operating costs. In addition, clay is a sheet-like nanomaterial with a high specific surface area (10) m2/g) and a south charge density (1 W2). The material will have higher mechanical properties, ablation and gas barrier properties, and can be expanded. Its application of nano metal. 200924840 Brief description of the drawings: Fig. 1 is a schematic view showing the dispersion of spherical silver nanoparticles by nano-sheet clay according to the present invention; and Figs. 2 to 5 are SEM images of powder products of Examples 5, 18, 16, and 19. Fig. 6 is a graph showing the average particle diameter of the powdery products of Examples 1 to 15. 〇 ❹ -A·