201041968 六、發明說明： 【發明所屬之技術領域】 本發明疋有關於一種本半柳不选人 一 _不含有害;::::::=:子:別 殼素之複合物及其製法。 /、、’、甲 【先前技術】 近年來，奈米科技已廣泛被應用至各領 目1 極受褐目的科技產業，尤其是 為目别 Ο Ο 粒子應用至曰常製品上，更=二金屬材質的奈米 更成為目則最熱門的趨勢。例如， 奈米等級的金奈米粒子’能㈣穿過人體皮膚約2微米大小 =細孔，進人人體的表皮組織，並能藉由其所具備的高含 特性，促進血液循環與新陳代謝，進而產生活化細胞的作 =，所以當與衣服布料或面膜結合時，可製成機能性服錦或 保養㈣。此外，由於銀本身具有抗@效果，且不具毒 性’因此將其製成奈米粒子時’能表現顯著的脫臭殺菌效果 ’因此’可制在各種生活衛生製品上，並提供更佳的安全 衛生品質。 目前製造奈米粒子的方法主要分為化學與物理二種製 造方法’其中，以化學法製造奈米粒子時多在溶液中進行， 為了防止所製出的奈米粒子相聚集’及維持穩定分散狀態， 通常會在溶液中添加穩定劑（stabil㈣或保護劑，但這些試 劑多為有機化學物質’具有容易成為污染源及危害人體健康 的缺點，導致以此種方式所製出的貴金屬奈米粒子不適於應 用 在會與生物體發生接觸的產 口口或日常用品上，而使奈米粒 201041968 子的應用受到侷限。 此外，鑑於貴金屬奈米粒子具有極佳的活化細胞、抗 菌、除臭及過滤％•功能，並具有特殊的熱學與光學性質，因 此，可藉由將不同的貴金屬材質的奈米粒子結合到特定的基 材上，使該基材具有更多的附加功能，而能提升其實用價值 由於奈米材料（nan〇materials)在應用上可使產品具有輕 薄短小、省能源、高容量密度、高精細、高性能與低公害等 特性’並能帶給傳統產業昇級、高科技產業持續發展和永續 發展的推動力，使奈米材料成為奈米科技發展的基石，因此 ’發展以安全無毒方式製造責金屬奈米粒子的方法並利用 貴金屬奈米粒子的特性提升特定基材的使用性能，以開發出 具有較佳實用價值且可供日t應用的產品，仍存在有持續開 發研究的需求。 ' 【發明内容】 。。因此，本發明的目的，是在提供一種以製程相對較簡 早’且所製出的成品不含有害人體的化學成分的貴金 米粒子與甲殼素之複合物的製法。 不 、於是，本發明貴金屬奈米粒子與甲殼素之複合物的製 法’包含下列步驟： ⑴配製一含有預定濃度 度之甲设素的第一溶液，該 、翻及此荨的組合，部分貴 表面；及 之貴金屬離子錯合物與預定濃 等貴金屬離子是選自於金、銀 金屬離子是吸附於該等甲殼素 201041968 (ii)藉由提供一能量作用於步驟⑴中的第一溶液或將該 第一溶液靜置一段時間的方式，使吸附於甲殼素表面的貴 金屬離子及懸浮於該第一溶液中的貴金屬離子被還原為貴 金屬奈米粒子，進而在該第一溶液中分別形成貴金屬奈米 粒子與甲殼素之複合物，及貴金屬奈米粒子。 本發明貴金屬奈米粒子與曱殼素之複合物的製法的有 益效果在於：藉由形成貴金屬離子錯合物，使貴金屬離子 能分散於該第一溶液中，再透過甲殼素中的氮與貴金屬離 〇 子間的吸引力使貴金屬離子附著於曱殼素表面，再配合施 加特定的能量作用，就能使金屬離子被還原成金屬奈米粒 子並附著在曱殼素上，進而製得貴金屬奈米粒子與甲殼素 ' 之複合物，由於本發明在製程中未使用對人體有害的化學 成分，所製得的製品不需再進行複雜的化學成分分離程序 ，就能供直接使用，使本發明能以較簡化、環保，且符合 安全衛生標準的製程製得複合物產品，而極具應用價值。 進一步地，本發明還提供一種製程相對較簡單，且最 Ο 終產品中不含有害人體之化學成分的貴金屬奈米粒子與曱 殼素之複合物。 於是，本發明貴金屬奈米粒子與曱殼素之複合物包含 一曱殼素基材，及多數個吸附在該曱殼素基材上的貴金屬 奈米粒子。 該等貴金屬奈米粒子的材質是選自於金、銀、鉑及其等的組合 〇 本發明貴金屬奈米粒子與曱殼素之複合物的有益效果 5 201041968 在於：結合甲殼素與貴金屬奈米粒子製成複合物，可透過 曱殼素容易吸附乙醛的特性’及貴金屬奈米粒子的催化特 性，使吸附在該甲殼素上的乙醛被快速分解並使—氧化碳 氧化為無毒的二氧化碳，而能提供較佳的空氣淨化與過濾 效果’使本發明具有可發展為具有較佳過濾效率之過濾產 品的實用價值。 【實施方式】 有關本發明之前述及其他技術内容、特點與功效，在 以下配合參考圊式之一個較佳實施例的詳細說明中，將可 清楚的呈現。 參閱圖1與圖2,本發明貴金屬奈米粒子與曱殼素之複 合物的製法的較佳實施例包含下列步驟： 步驟101是配製一含有預定濃度之貴金屬離子錯合物 與預定濃度之甲殼素（chit〇san，分子式為（C6Hn〇4N)n，也被 稱為幾丁聚醣）的第一溶液，該等貴金屬離子是選自於金、 銀、鉑及此等的組合，部分貴金屬離子是吸附於該等曱殼 素表面。 其中，β亥曱设素的 >辰度較佳是大於等於〇1公克/公升 ，最佳則是大於等於1公克/公升，及該貴金屬離子錯合物 在。亥第一溶液中的濃度較佳為〇 〇〇〇lppm〜3〇〇〇〇ppm。且該 貴金屬離子錯合物可以直接藉由使用市售已含有預定貴金 屬鹽類的液體產品取得’此時，可直接在該液體產品或稀 釋的液體產品中加入甲殼素即可，不需另外添加電解質。 該貴金屬離子錯合物也可以使用一選自下列群組中的方法 201041968 製得：化學法、電化學法 含有金離子的第二溶 皮電化子法。下列以製備- 式： 液為例，說明前述三種方法的製備方 ⑴化學法：先將金溶於 得到黃色針狀的四水合物曰… 再進仃热發冷卻’可 . ⑽劑中，就能得到有;二將該晶體粉末溶於預 .將該晶體粉末溶於水中“金錯合物的溶液，在此，是 (2) 電化學法：在含右 〇 …、定電流密度電解質的溶液中， 方式，可將黃金由電極溶二:=、線性掃描等電化學 . 離子（在料㈣子）錯合物的第二減。 有貝金屬 (3) 聲波電化學法：在含 、*以定電位、定電流密度、循的溶液中， 化學方式，實驗時溶液輔以超描、線性掃描等電 溶出為僧“、 盪，可將黃金由電極 人版 ’’進而製得有貴金層離子（在此為金離子）的錯 〇 ，可.、電化予作用的過程中輔以超音波振盪 屬太/於，錢中的貴金屬離子的量提升，使最終貴金 不、未粒子的產量也能獲得提升。 β、需要說明的是，在該實施例中，該貴金屬離子錯合物 =電化學法將貴金屬片氧化溶解於—含有賤量電解f =二溶液中而製得，該電解質是選自於氣化納、氯化鉀 ^酸^與溶解的金離子形成氯金酸根離子而吸附於 么、表面田使用氯化納或氣化鉀作為電解質時，除了 n食持命液的電中性外，由於此類物質不會對人體造成傷 201041968 害，相對較符合安全衛生的標準，但也可以使用人 物的鹽類、驗類或酸類物質作為該電解質，例如了: 用氯化氫為電解質，但由於氯化氯為強酸，使用時須^ 以符合安全標準…，對銀片或白金片的貴金屬片= 在電化學法中則需使用硝酸或硫酸作為電解質較佳。在 本只施例中’是將該第二溶液中的電解質濃度配製為〇·1Ν ，但該電解質的濃度不應受限，根據實驗，通常電解新，曲 度過低_水溶液導電性降低，可能㈣無㈣行電2 實驗或電化學效率不佳，當濃度高於〇1N日寺，因水溶液= 電性=高，理論上有利於進行電化學實驗’但使用過多之 電解質，則使原料成本增加，並可能影響最終所製得的主 金屬奈米粒子的純度。 ，貝 此外，可以在製備貴金屬離子錯合物前，將預定量的 甲殼素溶於該水溶液中，再以如前所述的方式在該溶液令 製備貴金屬離子錯合物以形成該第一溶液，也可以先在該 含有電解質的溶液中製造貴金屬離子錯合物以形成該第2 溶液，再將甲殼素溶於已含有貴金屬離子錯合物的第二溶 液中而形成該第一溶液，同樣能製得含有預定濃度之責2 屬離子錯合物與預定濃度之曱殼素的第一溶液，在本二施 例中，該等貴金屬離子為金離子，並以電化學法製備含有 金離子錯合物的第二溶液，該金離子錯合物是金離子與氣 離子形成氯金酸根離子的型態，由於該第二溶液為弱酸環 衩，曱设素在此環境下易形成帶正電的陽離子形態，氣金 酸根離子則為帶負電的離子形態，藉此，使甲殼素與氣金 201041968 酸根離子容易相靠近’並能透過氯金酸根離子中的金離子 與該甲殼素中的氮元素形成穩定吸附，因此，金離子是以 氣金酸根離子的狀態吸附於甲殼素表面。在該實施例中， 該第二溶液的pH值並無限制，但對製備金奈米粒子與甲殼 素之複合物而言’在中性時可製得較高的金奈米粒子濃度 ’酸性溶液（尤其是pH值小於3)時產量則較差。因此，該 第二溶液的pH值較佳為設定在6〜8。 其中’甲殼素是幾丁質（chitin)溶於酸性溶液中時，以 〇 將其乙醯基（CH3C〇-)被移除，只剩下以葡萄糖胺（c6h13no5) 為組成單位所構成的多醣類（Polysaccharide)天然聚合物，在 酸性溶液中，由於胺基被質子化（pr〇t〇nati〇n)使甲殼素形成 . 正電的基團，並具有生物特徵與物理化學性質，加上來源 -天然無毒，在食品、醫藥、化妝品業與生物工程都具有極 高的應用潛力。此外’已有研究指出甲殼素在常溫下可與 乙搭反應形成Sdiiff氏驗（Sehiff base)形式，藉此，可吸附 #在空氣中或液體中的乙駿，而有開發作為淨化與過遽材 ^ 質的應用價值。 步驟102是提供一能量作用於步驟101中的第一溶液 乂使吸附於該甲设素表面的貴金屬離子及懸浮於該第一 溶液中的貴金屬離子被還原為貴金屬奈米粒子，進而在該 第々液中形成貴金屬奈米粒子與甲殼素之複合物，及貴 粒子。但即使未提供能量，直接將該第—溶液在 。曰 2〜3天，由於甲殼素中的氮原子未共用之電子對 了將其電子轉移至帶正電荷之貴金屬離子，使其還原為責 9 201041968 金屬奈米粒子，囡，士 . 屬離子及懸浮二:：：吸附於該甲殼素表面的貴金 的貴金屬奈米粒子的濃度較低、產量也相對較:开 量作提供一種選自下列群組中的方式提供能 、f 令的第一溶液：加熱至沸騰並持續一# Π，照射紫外光、照射雷射光：： =磁波、超音波、電化學及加入化學還原劑，藉此，使 該第一溶液中的貴金屬離子被還原為貴金屬奈米粒子。盆 中’该紫外光的波長範圍較佳為2〇〇nm〜铜⑽，及該可見 ，的波長範圍較料侧nm〜7〇〇nm。在本實施例中主要 是藉由電化學作用或加熱至滞騰的方式使吸附於甲殼素上 :貴金屬離子被還原為貴金屬奈米粒子。其中，所形成的 貴金屬奈米粒子的粒徑可控制在Glnm〜5GGnm的範圍内， 進一步地，若該貴金屬奈米粒子為金時，則其粒徑較佳為 5nm〜30nm。 步驟103是離心’以分別形成一含有貴金屬奈米粒子 與甲殼素之複合物的沉澱物，及一含有貴金屬奈米粒子的 澄清液。藉此，能分別獲得金奈米粒子，及由金奈米粒子 與甲榖素所形成的複合物二種產品。 較佳地’所製出的複合物各具有一個甲殼素基材及多 數個吸附在該曱殼素基材上的貴金屬奈米粒子。所製出的 複合物產品可利用甲殼素容易吸附負電物質的特性，與貴 金屬奈米粒子優良的化學催化活性、淨化及分解空氣或液 10 201041968 體中的雜質的特性，而能進一步應用於一選自下列群組中 的產叩.面膜、保養品、化妝品、酒類飲品、裝酒容器、 保健食⑽防煙口罩、防毒面具、氣體感測器、空氣清淨 香煙與夺加之内容物、濾嘴產品、癌症治療標耙藥物 與士醫投藥系統藥物之添加劑、生化感測器、食品添加劑 、抗菌功能產品、廢水處理產品及傷口敷料。 . 丨女可利用金奈米粒子抗老化與可活化細胞的特性 & u粒子的抗菌性，及甲殼素可保濕與良好生物相容 Ο .故的特性，增進面膜、保養品與化妝品的效果。利用金太 米粒子可去除酒中乙盤，及甲殼素可去除重金屬及捕捉: . +的特险改善酒.類飲品的風味，也可以與裝酒容器的材料 相尨合，用於改善其所盛裝酒類的風味。此外，利用金奈 二，子=老化與甲殼素去油月旨、降膽固醇的特性作為保健 ^〇〇或作為一般食品添加劑並應用於糕點麵包等食品的 ^作°利用金奈米粒子與銀奈米粒子可去除乙盤、—氧化 ⑯與甲搭的特性，及甲殼素可補捉-氧化碳、乙酸與甲臨 、用而此去除空氣中有害物質，使該複合物適於應用作 :=口罩、防毒面具、氣體感測器、空氣清淨劑及香煙 ^ *之内谷物等產品◦當將該複合物應用於製造香煙與 .之濾嘴產品時，可利用曱殼素吸附煙霧中主流煙 (mStream sm〇ke)内的乙醛與一氧化碳，再透過金奈米粒 化7催化特性，使乙醛被分解為二氧化碳與水，及使一氧 被虱化為二氧化碳，藉此將煙霧.中有害人體健康的物 質刀解為無害的物質，達到淨化空氣的效果該濾嘴產品 11 201041968 可以是香煙與雪莊底部本身的遽嘴，也可以 煙與雪莊上另外外加的遽嘴產品。利 太=於 素之複合物中，夺乎们1 u …卡粒子與甲殼 質的功的特性與甲殼素吸附雜 質的功-製成抗菌功能產品。利用金奈米粒子 複合物中，甲殼素可吸附捕捉污染物與奈米金;;分解污毕 物的特性而能應用於廢水處理中以改善處理效率。利用甲 殼素可修護傷口與金奈米粒子 子=ΓΤ快速癒合。另外，還能藉由金奈米粒 f J瑪帶藥物、其輿甲匈_去丨， 丹興Τ ^•又素良好的生物相容性、盔， =1易於生物代謝的特性作為癌症治療標_物與生 ^又樂系統藥物之添加劑。而金奈米粒子物於與蛋白質、 與:主與亀配對、甲殼素與金奈米粒子良好的生物相容性 生化Γ特14 ’及甲殼性易於生物代謝的特性則可供應用於 的化二器：由於f實施例製造過程中未使用對人體有害 冑'^甲㊅素原本就為天然無毒的原料，因此， 得的責金屬奈米粒子與甲殼素之複合物，及貴金屬 y、、’子—種產α°，不需再進行複雜的分離程序或清洗過 二移除有害物質’就能供直接使用，使本發明的製造方 的^對具有較精簡、環保’且所製出的產品也較安全衛生 勒性。但為了避免製造過程中所用的原料中含有雜質而 屬：、、製°〇的功效受影響的，也可以在該曱殼素的貴金 支主還原為貝金屬奈米粒子後，再進行水洗、浸泡等 著、、程序以移除雜質並進一步純化金屬奈米粒子，接 者再w自然風乾或烘乾的方式乾燥該複合物產品。 12 201041968 <具體例一-以加熱法製備貴金屬奈米粒子與甲殼素之複 合物> 分別配製0.1N氯化鈉溶液40ml作為al溶液’及含有 濃度lg/L甲殼素的0.1N氯化鈉溶液40ml作為bl溶液，再 分別以電化學法在al、bl溶液中製備金離子，分別以一金 基材片為工作電極（working electrode)、一白金片為輔助電 極（counter electrode)及銀/氯化銀電極管為參考電極 (reference electrode)進行氧化-還原循還（oxidation-reduction 〇 cycle，施加的電位為-0.28V~~l-1.22V(vs. Ag/AgCl) ’ 以 500mV/s掃描500次），藉此對金基材進行電解以分別在al 、b 1溶液中形成金離子，在電解過程中同時對al、b 1溶液 -施以攪拌，其中al、bl溶液的pH值皆為ρΗ6·5，接著，利 . 用一加熱器以6°C /min的加熱速率將al、b 1溶液加熱至沸 騰，以在bl溶液中形成金奈米粒子與曱殼素之複合物，及 在al溶液中形成金奈米粒子。並分別進行如下的檢驗分析 及說明其結果： 〇 (1)分別量測a 1、b 1溶液電解後加熱前及加熱後二種狀 態下的紫外光-可見光吸收光譜（使用儀器：Perkin-Elmer Lambda 35 spectrophotometer)。另外配製一僅含有 0.1g/L 曱殼素的0.IN氯化鈉溶液為cl溶液作為空白比對。 電解後加熱處理前，a 1溶液的顏色為黃色，加熱後， al溶液顏色仍維持黃色，顯示al溶液可能未發生明顯的還 原反應，反觀b 1溶液，加熱後其顏色由黃色逐漸轉變為紅 色，金奈米粒子的顏色即為紅色，顯示bl溶液有明顯的還 13 201041968 原反應發生。 如圖2與圖3所示，分別為加熱前及加熱後的分析圖 表，圖2顯示al、bl溶液分別在31311111及3Unm出現最大 吸收帶訊號’ c 1溶液則未出現明顯吸收帶訊號，顯示a j、 bl溶液中出現的吸收峰應為金電解後在溶液中出現的 AuC14其中’ AuC14通常是以自組裝單層（seif_assembied monolayers ’ SAMs)的模式吸附在甲殼素表面。另外，由於 二者的基線一致，顯示甲殼素的存在與否不會干擾電解反 應的進行’據此可合理推測甲殼素可在電解前加入亦可在 電解後再加入氯化鈉溶液中。圖3顯示加熱處理後，bl溶 液在520nm出現明顯的吸收帶，原來3丨丨nm的吸收帶則消 失，此結果顯示在bl溶液中有金奈米粒子生成，al溶液則 仍只有在313nm出現明顯吸收帶訊號，對應實驗過程中所 觀察到的a 1 /谷液與b 1溶液的顏色變化情形，顯示當以加熱 法進行還原時，溶液中有甲殼素時則有利於金離子還原為 金不米粒子。當將b 1溶液以超音波震盡後再離心以去除曱 设素後進一步以 inductively coupled plasmo-mass spectrometer(ICP-MS)分析bl溶液離心後的澄清液部分，顯 不所合成的金奈米粒子的濃度約為 70ppm ° (2)於bl溶液中取一滴液體試樣，經真空乾燥後以穿透 電子顯微鏡（transmjssi〇n eiectr〇n mjcrosc〇py，簡稱為 TEM，型號：Philips Tecnai G2 F2〇)觀察。 ,如圖4所示’當針對特定區域計算該等金奈米粒子的 粒徑時’顯示其平均粒徑約為1 5nm，同時也顯示該等金奈 14 201041968 米粒子並未聚集，而是呈均勻分散。 (3) 對bl溶液進行X射線繞射（X-ray diffraction，簡稱 為XRD)量測，所用的儀器型號為ARL X’TRA Thermo，並 配備有可供分析液體樣品用的毛細管。 結果如圖5所示，對照XRD標準手冊，可由出現在 38.20、44.40、64.60 及 77.50 分別表示（111)、（200)、（220)及 (311)的波峰，表示bl溶液中有金元素存在，另外，出現在 23 °的呈較寬廣平緩的波峰則為非晶形的甲殼素存在的證明 〇 ，顯示在a 1溶液中具有金奈米粒子/曱殼素之複合物存在。 (4) 將加熱處理後的bl溶液以15000rpm離心3分鐘， 並以去離子水清洗，重複前述過程3次，收集粉末狀的產 ' 物樣品，再以高解析X射線光電子光譜（high resolution X- . ray photoelectron spectroscopy，簡稱為 HRXPS)進行檢測， 所使用的XPS量測儀器型號為ULVAC PHI Quantera SXM spectrometer ° 如圖6所示，顯示所收集到的粉末樣品中經分析後出 〇 現金與氮二種元素的訊號，由於所用的原料中只有甲殼素 含有氮元素，據此可推測該產物樣品中確實含有金與曱殼 素。 (5) 以HRXPS分別檢測bl溶液電解後加熱處理前，及 加熱處理後所獲得的產物，並針對Au 4f7/2-5/2 核-階層的光 譜作進一步的分析比對，分別以I、II表示加熱處理前、後 的結果。· 如圖7所示，顯示曲線II在84eV與87.7eV處有成對 15 201041968 電子光譜標準手册可知所測得的物 雙峰，顯示所測得物Τ二在正與88.leV處有成對之 =不本發明的製造方法確實能使吸附於甲殼素上的全 離子還原為金奈米粒子而製得金奈米粒子/f殼素之複合物 0 际分以上 的檢驗分析 禾201041968 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a compound that does not contain harmful ones;::::::=: sub-shell compound and its preparation method . /,, ', A [previous technology] In recent years, nanotechnology has been widely applied to the science and technology industry in which each of the leaders is extremely affected by browning, especially for the application of particles to the common products, more = two Nano-materials are the hottest trend in the world. For example, the nano-grade gold nanoparticle 'can (4) pass through the human skin about 2 micrometers in size = pores, enter the epidermal tissue of the human body, and can promote blood circulation and metabolism by virtue of its high content. In turn, the act of activating cells is produced, so when combined with clothing cloth or mask, it can be made into functional clothing or maintenance (4). In addition, since silver itself has an anti-effect and is not toxic, it can be used as a nano-particle to perform a deodorizing and sterilizing effect. Therefore, it can be made on various sanitary products and provide better safety. Hygienic quality. At present, the method for producing nano particles is mainly divided into two methods of chemical and physical production. Among them, when the nano particles are chemically produced, the solution is mostly carried out in solution, in order to prevent the formed nanoparticle particles from agglomerating and maintaining stable dispersion. In the state, stabilizers (stabs or protective agents are usually added to the solution, but these are mostly organic chemicals), which have the disadvantage of being easily a source of pollution and endangering human health, resulting in discomfort of precious metal nanoparticles produced in this way. It is applied to the mouth or daily necessities that come into contact with organisms, and the application of nanoparticle 201041968 is limited. In addition, since precious metal nanoparticles have excellent activated cells, antibacterial, deodorizing and filtration% • Functional, and has special thermal and optical properties, so it can be improved by combining different precious metal nanoparticles onto a specific substrate to give the substrate more additional functions. Value Because nano materials (nan〇materials) can make products light, thin, energy-saving, high-capacity The characteristics of degree, high precision, high performance and low pollution, and can promote the upgrading of traditional industries, the sustainable development of high-tech industries and the sustainable development, make nanomaterials become the cornerstone of the development of nanotechnology, so Safe and non-toxic method to manufacture metal nanoparticles and use the characteristics of precious metal nanoparticles to improve the performance of specific substrates, to develop products with better practical value and available for daily applications, there is still continuous development research The demand of the invention. Therefore, the object of the present invention is to provide a precious gold rice particle and chitin which are relatively simple in the process and which are manufactured without the harmful chemical components of the finished product. The method for preparing a composite. The method for preparing a composite of precious metal nanoparticles and chitin of the present invention comprises the following steps: (1) preparing a first solution containing a predetermined concentration of a sulphate, and turning the 溶液a combination of a noble surface ion; and a noble metal ion complex and a predetermined rich metal ion selected from the group consisting of gold and silver metal ions are adsorbed thereto Chitin 201041968 (ii) suspending precious metal ions adsorbed on the surface of chitin in the first solution by providing an energy to the first solution in step (1) or by allowing the first solution to stand for a period of time The precious metal ions are reduced to noble metal nanoparticles, and then a composite of noble metal nanoparticles and chitin is formed in the first solution, and noble metal nanoparticles. The complex of noble metal nanoparticles and chitin in the present invention The beneficial effect of the method is that by forming a noble metal ion complex, the noble metal ions can be dispersed in the first solution, and the noble metal ions are attached to the ruthenium through the attraction between the nitrogen in the chitin and the noble metal from the scorpion. The surface of the shell, combined with the application of specific energy, can reduce the metal ions to metal nanoparticles and attach to the chitin, thereby producing a complex of precious metal nanoparticles and chitin, due to the present invention. In the process, the chemical components harmful to the human body are not used, and the prepared products do not need to be subjected to complicated chemical separation procedures. Direct use of the present invention can be in a more simplified, environmental protection, and health and safety standards in line with the process to prepare a complex product, and great value. Further, the present invention also provides a composite of precious metal nanoparticles and chitin which are relatively simple in process and which do not contain chemical components harmful to the human body in the final product. Thus, the composite of the noble metal nanoparticles and the chitin of the present invention comprises a chitin substrate, and a plurality of precious metal nanoparticles adsorbed on the chitin substrate. The material of the noble metal nanoparticles is selected from the group consisting of gold, silver, platinum and the like. The beneficial effect of the combination of the noble metal nanoparticles of the present invention and the chitin is 5 201041968: combining chitin with precious metal nano The particles are made into a composite, which can easily adsorb the characteristics of acetaldehyde through the chitin and the catalytic properties of the noble metal nanoparticles, so that the acetaldehyde adsorbed on the chitin is rapidly decomposed and the carbon oxide is oxidized to non-toxic carbon dioxide. , and can provide better air purification and filtration effect 'to make the invention have the practical value that can be developed into a filtration product with better filtration efficiency. The above and other technical contents, features and effects of the present invention will be apparent from the following detailed description of the preferred embodiments. Referring to FIG. 1 and FIG. 2, a preferred embodiment of the method for preparing a composite of precious metal nanoparticles and chitin of the present invention comprises the following steps: Step 101: preparing a shell containing a predetermined concentration of a noble metal ion complex and a predetermined concentration. a first solution of chit〇san, a molecular formula of (C6Hn〇4N)n, also known as chitosan, which is selected from the group consisting of gold, silver, platinum, and combinations of these, precious metals The ions are adsorbed on the surface of the chitin. Wherein, the > Chen of the 曱 曱 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳The concentration in the first solution of hai is preferably 〇1 ppm to 3 〇〇〇〇 ppm. And the noble metal ion complex can be obtained directly by using a liquid product which is commercially available and contains a predetermined precious metal salt. In this case, chitin can be directly added to the liquid product or the diluted liquid product without additional addition. Electrolyte. The noble metal ion complex can also be obtained by a method selected from the group consisting of: chemical method, electrochemical method, second solution electrowinning method containing gold ions. The following is a preparation - formula: liquid, for example, to explain the preparation of the above three methods (1) chemical method: first dissolve the gold to obtain a yellow needle-like tetrahydrate 再 ... and then heat the hair to cool ' can. (10) agent, The crystal powder can be dissolved in the pre-solution. The crystal powder is dissolved in water. The solution of the gold complex, here (2) electrochemical method: in the right enthalpy..., constant current density electrolyte In solution, the way to gold can be dissolved by the electrode two: =, linear scanning, etc. Electrochemical. The second subtraction of the ion (in the material (four) sub) complex. There is a shell metal (3) sonic electrochemical method: in the * In the solution of constant potential, constant current density, and circulation, the chemical method, the solution is supplemented by ultra-drawing, linear scanning, etc., and the electric solution is 僧", sway, and the gold can be made from the electrode version" The gold layer ions (here, gold ions) are faulty, and the process of electrification is supplemented by ultrasonic oscillations. The amount of precious metal ions in the money is increased, so that the final precious gold is not, no particles. The output can also be improved. β, it should be noted that, in this embodiment, the noble metal ion complex=electrochemical method is obtained by oxidatively dissolving a precious metal piece in a solution containing a quantity of electrolysis f=two, which is selected from the group consisting of gas. When sodium hydride, potassium chloride, acid and dissolved gold ions form chloroaurate ions and are adsorbed on them, and surface fields use sodium chloride or potassium hydride as electrolytes, in addition to the neutrality of n-feeding liquid, Since such substances do not cause harm to the human body in 201041968, they are relatively safe and hygienic, but they can also use the salt, test or acid substances of the person as the electrolyte, for example: using hydrogen chloride as the electrolyte, but due to chlorine Chlorine is a strong acid, which must be used in accordance with safety standards..., precious metal sheets for silver or white gold sheets = nitric acid or sulfuric acid is preferred as the electrolyte in electrochemical methods. In the present example, 'the electrolyte concentration in the second solution is formulated as 〇·1Ν, but the concentration of the electrolyte should not be limited. According to the experiment, the electrolysis is usually new, the curvature is too low _ the conductivity of the aqueous solution is lowered, Possible (4) No (4) Rowing 2 Experimental or electrochemical efficiency is poor, when the concentration is higher than 〇1N 日寺, because the aqueous solution = electrical = high, theoretically beneficial for electrochemical experiments 'but using too much electrolyte, the raw materials The cost increases and may affect the purity of the final master metal nanoparticles produced. In addition, a predetermined amount of chitin may be dissolved in the aqueous solution before preparing the noble metal ion complex, and the noble metal ion complex is prepared in the solution as described above to form the first solution. Alternatively, the noble metal ion complex may be firstly formed in the electrolyte-containing solution to form the second solution, and then the chitin is dissolved in the second solution containing the noble metal ion complex to form the first solution. A first solution containing a predetermined concentration of a genus ion complex and a predetermined concentration of quercetin can be obtained. In the second embodiment, the noble metal ions are gold ions and are electrochemically prepared to contain gold ions. a second solution of the complex compound, the gold ion complex is a form in which gold ions and gas ions form a chloride acid ion, and since the second solution is a weak acid ring, the element is easily formed in this environment. The cation form of electricity, the gas metalate ion is a negatively charged ion form, whereby chitin and the gas gold 201041968 acid ion are easily close to each other and can transmit gold ions in the chloride ion and Nitrogen adsorption chitin forming a stable, and therefore, the gold ions are gold ions state gas adsorbed on the surface of chitin. In this embodiment, the pH of the second solution is not limited, but for the preparation of the composite of gold nanoparticles and chitin, 'higher gold nanoparticle concentration' can be obtained when neutral. The yield is poor when the solution (especially at a pH of less than 3). Therefore, the pH of the second solution is preferably set to 6 to 8. Where 'chitin is chitin dissolved in an acidic solution, the oxime group (CH3C〇-) is removed by hydrazine, leaving only the glucosamine (c6h13no5) as the constituent unit. Polysaccharide natural polymer, in acidic solution, because the amine group is protonated (pr〇t〇nati〇n) to form chitin. Positively charged group, and has biological characteristics and physicochemical properties, plus The source - natural non-toxic, has high application potential in food, medicine, cosmetics and bioengineering. In addition, 'research has pointed out that chitin can react with ethylene at room temperature to form a Sdiiff base form, whereby it can adsorb #B in air or in liquid, and it is developed as purification and sputum. The application value of the material. Step 102 is to provide an energy to the first solution in step 101, so that the noble metal ions adsorbed on the surface of the substrate and the noble metal ions suspended in the first solution are reduced to noble metal nanoparticles, and then A complex of precious metal nanoparticles and chitin is formed in the mash, and noble particles are formed. But even if no energy is supplied, the first solution is directly placed.曰 2~3 days, due to the electrons in the chitin that are not shared by the electrons, the electrons are transferred to the positively charged noble metal ions, which are reduced to the blame. 9 201041968 Metal nanoparticles, 囡, 士. 属 ions and Suspension 2::: The concentration of precious metal nanoparticles adsorbed on the surface of the chitin is lower and the yield is relatively higher: the amount of opening provides a first choice from the following group to provide energy, f Solution: heated to boiling and continued for one Π, irradiated with ultraviolet light, irradiated with laser light:: = magnetic wave, ultrasonic, electrochemical and chemical reducing agent, whereby the precious metal ions in the first solution are reduced to precious metals Nano particles. The wavelength of the ultraviolet light in the basin is preferably from 2 〇〇 nm to copper (10), and the visible wavelength range is from nm to 7 〇〇 nm on the material side. In this embodiment, adsorption to chitin is mainly carried out by electrochemical action or heating to stagnation: precious metal ions are reduced to noble metal nanoparticles. Here, the particle diameter of the formed noble metal nanoparticles can be controlled within the range of G1 nm to 5 GGnm, and further, when the noble metal nanoparticles are gold, the particle diameter thereof is preferably 5 nm to 30 nm. Step 103 is performed by centrifugation to form a precipitate containing a complex of noble metal nanoparticles and chitin, and a clear liquid containing noble metal nanoparticles. Thereby, it is possible to obtain two kinds of products, namely, a gold nanoparticle and a composite formed of a gold nanoparticle and a quinone. Preferably, the composites produced each have a chitin substrate and a plurality of precious metal nanoparticles adsorbed on the chitin substrate. The prepared composite product can be further applied to the characteristics of the negatively adsorbing negatively charged substance by chitin, the excellent chemical catalytic activity with the noble metal nanoparticle, the purification and decomposition of the impurity in the air or the liquid. Choose from the following groups: masks, skin care products, cosmetics, alcoholic beverages, wine containers, health foods (10) smoke masks, gas masks, gas sensors, air-clean cigarettes and content, filters Products, cancer treatment standard drugs and medical medicine system drug additives, biochemical sensors, food additives, antibacterial functional products, wastewater treatment products and wound dressings. Prostitutes can take advantage of the anti-aging and activatable cell characteristics of the gold nanoparticles and the antibacterial properties of the u particles, and the moisturizing and good biocompatibility of the chitin, so that the properties of the mask, skin care and cosmetics are enhanced. . The use of Jintai rice particles can remove the alcohol in the plate, and the chitin can remove heavy metals and capture: + The special insurance improves the flavor of the wine. It can also be combined with the materials of the wine container to improve its environment. Contains the flavor of alcohol. In addition, the use of Jinnai, sub = aging and chitin degreasing, cholesterol-lowering characteristics as a health care or as a general food additive and used in cakes and other foods, the use of gold nanoparticles and silver The nano particles can remove the characteristics of the E disk, the oxidation 16 and the Methyl, and the chitin can make up - the carbon oxide, the acetic acid and the methyl, and the harmful substances in the air are removed, so that the composite is suitable for application: = masks, gas masks, gas sensors, air cleaners, and cigarettes. * Grains and other products. When this compound is used in the manufacture of cigarettes and filter products, it can be used in the mainstream of smoke adsorption. The acetaldehyde and carbon monoxide in the smoke (mStream sm〇ke), and then through the catalysis characteristics of the gold granulation, the acetaldehyde is decomposed into carbon dioxide and water, and the oxygen is decomposed into carbon dioxide, thereby smog. The substance that is harmful to human health is solved as a harmless substance, and the effect of purifying the air is achieved. The filter product 11 201041968 can be the mouth of the cigarette and the bottom of the snow house itself, or the additional mouthpiece of the smoke and snow. In the composite of Litai = Yu, the properties of the card particles and chitin are captured and the work of chitin adsorbing impurities is made into an antibacterial functional product. In the gold nanoparticle composite, chitin can adsorb and capture pollutants and nano gold; and can decompose the characteristics of the waste material and can be applied to wastewater treatment to improve the treatment efficiency. The use of chitin can repair wounds and gold nanoparticles. In addition, it can also be used as a cancer treatment target by means of Jinnai granules, f Jemao drugs, its armor, arsenic, sputum, and sputum, and good biocompatibility, helmet, and =1. _ things and raw ^ and music system additives. The gold nanoparticles are compatible with proteins, with: primary and quinone, chitin and gold nanoparticles, good biocompatibility, biochemical characteristics, and chitin-prone bio-metabolism. Second: Because the f example is not used in the manufacturing process, it is harmful to the human body. ^A hexacycline is originally a natural non-toxic raw material, therefore, the compound of the metal nanoparticles and chitin, and the precious metal y, 'Sub-production α°, no need to carry out complicated separation procedures or cleaning twice to remove harmful substances' can be used directly, so that the manufacturer of the invention has a relatively simple, environmentally friendly and produced The products are also safer and healthier. However, in order to avoid the impurities contained in the raw materials used in the manufacturing process, and the effect of the system is affected, the precious metal support of the chitin may be reduced to the shell metal nanoparticles, and then washed. Soaking, etc., to remove impurities and further purify the metal nanoparticles, and then dry the composite product by air drying or drying. 12 201041968 <Specific Example 1 - Preparation of composite of noble metal nanoparticles and chitin by heating method > 40 ml of 0.1 N sodium chloride solution was prepared as an al solution' and 0.1 N chlorination containing a concentration of lg/L of chitin 40ml of sodium solution was used as bl solution, and gold ions were prepared by electrochemical method in a1 and bl solutions, respectively. A gold substrate was used as a working electrode, a platinum plate was used as a counter electrode, and silver/chlorine was used. The silver electrode tube is used as a reference electrode for oxidation-reduction ( cycle (applied potential -0.28V~~l-1.22V (vs. Ag/AgCl)' is scanned at 500mV/s 500 times), thereby electrolyzing the gold substrate to form gold ions in the al and b 1 solutions respectively, and simultaneously stirring the al and b 1 solutions in the electrolysis process, wherein the pH values of the a and bl solutions are both ρΗ6 ·5, then, using a heater to heat the al, b 1 solution to boiling at a heating rate of 6 ° C / min to form a complex of gold nanoparticles and chitin in the bl solution, and The gold nanoparticles are formed in the al solution. The following inspections were carried out and the results were as follows: 〇(1) Measure the UV-Vis absorption spectra of the a1 and b1 solutions after electrolysis and before heating (using instruments: Perkin-Elmer) Lambda 35 spectrophotometer). In addition, a 0.1 N sodium chloride solution containing only 0.1 g/L of quercetin was prepared as a cl solution as a blank alignment. Before the heat treatment after electrolysis, the color of the a1 solution is yellow. After heating, the color of the al solution remains yellow, indicating that the al solution may not undergo a significant reduction reaction. In contrast, the b1 solution gradually changes from yellow to red after heating. The color of the gold nanoparticles is red, indicating that the bl solution is obviously still 13 201041968 the original reaction occurs. As shown in Fig. 2 and Fig. 3, respectively, the analysis charts before and after heating, Fig. 2 shows that the maximum absorption band signal 'c 1 solution appears in the 31311111 and 3Unm of the al and bl solutions respectively, and no obvious absorption band signal appears. The absorption peak appearing in the aj and bl solutions should be AuC14 which appears in the solution after gold electrolysis. ' AuC14 is usually adsorbed on the surface of chitin in the form of seif_assembied monolayers 'SAMs. In addition, since the baselines of the two are consistent, it is shown that the presence or absence of chitin does not interfere with the progress of the electrolysis reaction. It can be reasonably assumed that chitin can be added before electrolysis or added to the sodium chloride solution after electrolysis. Figure 3 shows that after heat treatment, the bl solution shows a distinct absorption band at 520 nm, and the original absorption band of 3 丨丨 nm disappears. This result shows that gold nanoparticles are formed in the bl solution, and the al solution still appears only at 313 nm. Significant absorption of the signal, corresponding to the color change of a 1 / gluten and b 1 solution observed during the experiment, showing that when the reduction is carried out by heating, the presence of chitin in the solution is beneficial to the reduction of gold ions to gold. Not rice particles. When the b 1 solution was shaken by ultrasonic waves and then centrifuged to remove the sputum, the clarified liquid portion after centrifugation of the bl solution was analyzed by inductively coupled plasmo-mass spectrometer (ICP-MS), and the synthesized gold nanoparticles were not synthesized. The concentration of the particles is about 70ppm ° (2) Take a drop of liquid sample in bl solution, and dry it under vacuum to penetrate electron microscope (transmjssi〇n eiectr〇n mjcrosc〇py, TEM for short, model: Philips Tecnai G2 F2 〇) Observe. As shown in Fig. 4, 'when the particle size of the gold nanoparticles is calculated for a specific region', the average particle diameter is about 15 nm, and it is also shown that the Jinnai 14 201041968 rice particles are not aggregated, but Dispersed evenly. (3) X-ray diffraction (XRD) is applied to the bl solution. The instrument model is ARL X'TRA Thermo and is equipped with a capillary for analysis of liquid samples. The results are shown in Fig. 5. In contrast to the XRD standard manual, peaks represented by (111), (200), (220), and (311) appearing at 38.20, 44.40, 64.60, and 77.50, respectively, indicate the presence of gold in the bl solution. In addition, the presence of a broad, gentle peak at 23 ° is evidence of the presence of amorphous chitin, indicating the presence of a complex of gold nanoparticles/chitin in the a 1 solution. (4) Centrifuge the heat-treated bl solution at 15,000 rpm for 3 minutes, rinse with deionized water, repeat the above procedure 3 times, collect a powdery sample, and then use high resolution X-ray photoelectron spectroscopy (high resolution X). - ray photoelectron spectroscopy (abbreviated as HRXPS) for testing, the model used for the XPS measuring instrument is ULVAC PHI Quantera SXM spectrometer ° as shown in Figure 6, showing the cash and nitrogen after analysis of the collected powder samples The signal of the two elements, since only chitin contained nitrogen in the raw materials used, it is speculated that the product sample does contain gold and chitin. (5) HRXPS was used to detect the product obtained after the heat treatment of the bl solution, and after the heat treatment, and further analyze and analyze the spectrum of Au 4f7/2-5/2 core-level, respectively, I. II shows the results before and after the heat treatment. · As shown in Figure 7, the display curve II is paired at 84eV and 87.7eV. 15 201041968 The electronic spectrum standard manual shows the measured doublet, indicating that the measured object is at the positive and 88.leV. For the production method of the present invention, it is possible to reduce the total ion adsorbed on chitin to the gold nanoparticle, and to obtain a composite analysis of the composition of the gold nanoparticle/f-shellin.
At 顯不本發明的製造方法確 實此在不另外使用其他有害人體健康的化學物質的情兄下 ’就能製出貴金屬奈米粒子與甲殼素之複合物，且所製出 的貴金屬奈米粒子能維持穩定分散而不聚集的狀態。 <具體例二-以含有不同濃度甲殼素之第一溶液。及以不 同加熱速率之加熱法製備責金屬奈米粒子與甲殼素之複合 物> 分別配製（MN氯化鈉溶液4〇ml作為a2溶液、含有濃 度〇.lg/L甲设素的〇.1N氣化鈉溶液4〇ml作為溶液及 含有lg/L曱殼素的〇.ιΝ氯化鈉溶液4〇mi作為c2溶液，另 外配製二個同樣含有lg/L甲殼素的㈣氣化納溶液偏 作為d2溶液與e2歸，以<具體到一>所述的相樣方式盘 條件在a2〜e2溶液中形成金離子，再利用一加熱器以 /mm的加熱速率將a2〜C2溶液加熱至沸騰，並以4Cic/min的 加熱速率將d2溶液加熱沸騰，及以1(rc/min將e2溶液加 熱至沸騰，以分別在a2〜e2溶液中形成金奈米粒子。並分別 進行如下的檢驗分析及說明其結果： (1)分別量測a2、b2及c2溶液電解後加熱前的紫外光· 16 201041968 可見光吸收光譜，並量測a2〜e2溶液加熱後的紫外光-可見 生吸收光譜。 廿…、4程顯不，a2、b2溶液加熱前後的溶液顏色都維 持只色，.，、頁TF a2、b2溶液可能未發生明顯的還原反應，反 觀c2 /奋液，加熱後其顏色由黃色逐漸轉變為紅色，金奈米 粒子的顏色即為紅色’顯示e2溶液有明顯的還原反應發生 〇 如圖8與圖9所示，分別為加熱前及加熱後的檢驗圖 〇 表圖8』不a2與b2溶液在313nm出現明顯訊號，c2在 11 nm出現吸收峰5fl號，此範圍出現的吸收峰訊號應為金電 解後分散在a2、b2及〇2溶液中的AuCl4·。另外，圖9顯示 加熱處理後，c2溶液在522nm出現明顯的吸收帶訊號，原 纟3Unm的吸收峰則消失，此結果顯示在C2溶液中有金奈 米粒子生成’ a2、b2溶液則在313nm #出現明顯吸收峰， 對應實驗過程中所觀察到的a2，c2溶液的顏色變化情 形，顯示當以加熱法進行還原時，溶液中有甲殼素時則有 〇 矛1J於金離子還原為金奈米粒子，b2溶液中雖含有甲殼素 (〇.lg/L) ’但在522nm附近也未出現明顯訊號，顯示甲殼素 濃度過低所形成的金奈米粒子的數量也#低而不易僧測到 ，因此曱殼素的濃度較佳為大於等於j g/L。當進一步以 inductively coupled plasmo_mass spectr〇meter(icp_Ms)分析 c2溶液顯示所合成的金奈米粒子的濃度約為6〇ppm。未含 有甲殼素的a2溶液以ICP_MS分析的結果則顯示溶液中= 金奈米粒子的濃度約3Ppm。顯示曱殼素的存在有助於增加 17 201041968 金奈米粒子的產量。 如圖9所示，C2、d2、e2溶液中的曱殼素濃度皆為J g/L，加熱速率分為 6〇c/min、4cc/mint：/min、i〇<t/min， 加熱後出現明顯訊號的波長位置顯示在c2、d2、e2溶液中 者有生成金奈米粒子，但因加熱速率不同，波長出現位置 也出現偏移，使C2、d2與e2溶液所偵測到的吸收帶波長分 別為522nm、519nm& 531nm，由於波長長短會受奈米粒徑 大小影響，暗示不同的加熱速率可能使所形成的金奈米粒 子的粒徑不同。 (2)於C2〜e2溶液中分別取一滴液體試樣，經真空乾燥 後以穿透式電子顯微鏡（TEM)觀察。 以TEM觀察的結果顯示d2、c2與e2溶液中的金奈米 粒子也疋呈無聚集而均勻分聚的狀態，選定特定範圍内的 奈米粒子分別量測粒徑與計算後，顯示d2、^與e2溶液中 的奈米粒子平均粒徑則分別為5nm、1〇11111與3〇nm’此與前 述紫外光-可見生吸收光譜的量測結果相呼應，顯示加熱速 率越慢可得到粒徑越小的金奈米粒子，因此可利用改變加 熱速率控制所製出奈米粒子的大小。 <具體例二-以電化學法製備貴金屬奈米粒子與曱殼素之 複合物> 分別配製0·1Ν氣化鈉溶液4〇ml作為a3溶液及含有 濃度lg/L曱殼素的0·1Ν氣化鈉溶液4〇ml作為b3溶液，再 以如 < 具體例 > 所述的方式在a3、b3溶液中製備金離子，接 著，再以白金片取代金基材片作為工作電極，並仍以該白 18 201041968 金片為輔助電極，及銀/氯化銀電極管為參考電極，再藉由 對陰極施加0.6V的過電位使金離子還原為金奈米粒子，以 在b3溶液甲形成金奈米粒子與曱殼素之複合物，及在a3溶 液中形成金奈米粒子。並分別進行如下的檢驗分析及說明 其結果： (1) 分別量測a3、b3溶液電解後及進行電化學還原後的 紫外光-可見光吸收光譜（使用儀器：Perkin-Elmer Lambda 35 spectrophotometer) ° 0 電解後進行電化學還原前，a3、b3溶液中因為AuC14_ 的存在而呈現為黃色，進行電化學還原後，a3溶液顏色仍 維持黃色，顯示a3溶液可能未發生明顯的還原反應，反觀 ' b3溶液，其顏色由黃色逐漸轉變為紅色，金奈米粒子的顏 .色即為紅色，顯示b3溶液有明顯的還原反應發生。 如圖10所示，經電化學還原後，b3溶液在522nm出 現明顯的吸收帶，a3溶液在該波長附近則無明顯的吸收峰 訊號，該吸收峰訊號出現的位置為金奈米粒子的特性，對 Ο 應實驗過程中所觀察到的a3溶液與b3溶液的顏色變化情形 ，顯示當溶液中有曱殼素存在時則有利於金離子還原為金 奈米粒子。當將b3溶液以超音波震盪後再離心以去除甲殼 素後， 進一步以 inductively coupled plasmo-mass spectrometer(ICP-MS)分析b3溶液離心後的澄清液部分，顯 示所合成的金奈米粒子的濃度約為60ppm。 (2) 於b3溶液中取一滴液體試樣，經真空乾燥後以穿透 式電子顯微鏡觀察。 19 201041968 如圖11所示，當針對特定區域計算該等金奈米粒子的 粒徑時，顯示其平均粒徑約為15nm，同時也顯示該等金奈 米奈米並未聚集，而是呈均勻分散。此外，如圖11所示， 亦顯示多個深色的金奈米粒子200吸附於灰色的曱殼素20 表面。 (3) 對b3溶液進行X射線繞射（X-ray diffraction，簡稱 為XRD)量測，所用的儀器型號為ARL X’TRA Thermo，並 配備有可供分析液體樣品用的毛細管。 結果與<具體例一>的量測結果類似，亦在38.2°、44.4° 、64.6°及77.5°出現分別可代表示金之特殊結晶面（111)、 (200)、（220)及（311)的波峰訊號，表示b3溶液中有金元素 存在，另外，出現在23 °的呈較寬廣平缓的波峰訊號顯示 有非晶形的甲殼素存在，由此可知b3溶液中亦形成有金奈 米粒子/甲殼素之複合物。 (4) 將電化學還原後的b3溶液以15000rpm離心3分鐘 ，並以去離子水清洗，重複前述過程3次，收集粉末狀的 產物樣品，再以高解析X射線光電子光譜（high resolution X-ray photoelectron spectroscopy，簡稱為 HRXPS)進行檢測 ，所使用的XPS量測儀器型號為ULVAC PHI Quantera SXM spectrometer ° 如圖12所示，顯示所收集到的粉末樣品中經分析後出 現金與氮二種元素的訊號，由於所用的原料中只有曱殼素 含有氮元素，據此可推測該產物樣品中確實含有金與曱殼 素0 20 201041968 本發明的製法除了能以不含有害化學It is obvious that the manufacturing method of the present invention can produce a complex of noble metal nanoparticles and chitin without using other chemicals harmful to human health, and the noble metal nanoparticles produced can be produced. It can maintain a state of stable dispersion without aggregation. <Specific Example 2 - A first solution containing different concentrations of chitin. And the heating method at different heating rates is used to prepare the composite of metal nanoparticles and chitin. > (MN sodium chloride solution 4 〇ml as a2 solution, containing 〇.lg / L 甲 素 〇. 1N gasified sodium solution 4〇ml as a solution and lg.ιΝ sodium chloride solution containing 4g of lg/L cinnamate as c2 solution, and two (4) gasification nano solution containing lg/L chitin As a d2 solution and e2, a gold ion is formed in the a2~e2 solution in a phase-like mode condition of <specific to one>, and a2~C2 solution is further heated by a heater at a heating rate of /mm. The mixture was heated to boiling, and the d2 solution was heated to boil at a heating rate of 4 Cic/min, and the e2 solution was heated to boiling at 1 (rc/min) to form gold nanoparticles in the a2~e2 solution, respectively. The test analysis and the results are as follows: (1) Measure the ultraviolet light before heating after the electrolysis of a2, b2 and c2 solutions respectively. 16 201041968 Visible light absorption spectrum, and measure the ultraviolet light-visible absorption after heating of a2~e2 solution Spectrum. 廿..., 4 steps are not visible, a2, b2 solution before and after heating solution All of them maintain color, ., and page TF a2, b2 solution may not have obvious reduction reaction, in contrast to c2 / Fen liquid, its color gradually changes from yellow to red after heating, the color of the gold nanoparticle is red 'display The e2 solution has obvious reduction reaction. As shown in Fig. 8 and Fig. 9, respectively, the test chart before and after heating, Fig. 8 shows that the a2 and b2 solutions show obvious signals at 313 nm, and c2 absorbs at 11 nm. Peak 5fl, the absorption peak signal appearing in this range should be AuCl4· dispersed in a2, b2 and 〇2 solution after gold electrolysis. In addition, Figure 9 shows that after heating treatment, c2 solution showed obvious absorption band signal at 522nm. The absorption peak of the original Un3Unm disappeared. The results showed that there were gold nanoparticles in the C2 solution. The a2 and b2 solutions showed obvious absorption peaks at 313 nm#, corresponding to the color of the a2, c2 solution observed during the experiment. The change shows that when the reduction is carried out by the heating method, when there is chitin in the solution, the spear 1J is reduced to gold nanoparticles by the gold ion, and the b2 solution contains chitin (〇.lg/L) but Nothing appeared near 522nm The signal number indicates that the amount of gold nanoparticles formed by the too low chitin concentration is also low and not easy to detect, so the concentration of chitin is preferably greater than or equal to jg/L. When further inductively coupled with plasmo_mass spectr〇 The meter (icp_Ms) analysis of the c2 solution showed that the concentration of the synthesized gold nanoparticles was about 6 〇 ppm. The results of ICP-MS analysis of the a2 solution without chitin showed that the concentration of the gold nanoparticles in the solution was about 3 Ppm. It is shown that the presence of chitin contributes to the increase in the production of gold nanoparticles in 201041968. As shown in Fig. 9, the chitin concentrations in the C2, d2, and e2 solutions are all J g/L, and the heating rate is divided into 6〇c/min, 4cc/mint:/min, i〇<t/min, The wavelength position where the apparent signal appears after heating shows that the gold nanoparticles are generated in the c2, d2, and e2 solutions, but the wavelength appears in the position due to the different heating rate, so that the C2, d2, and e2 solutions are detected. The absorption band wavelengths are 522 nm, 519 nm & 531 nm, respectively, and the wavelength is affected by the size of the nanoparticle, suggesting that different heating rates may cause the particle size of the formed gold nanoparticles to be different. (2) A drop of the liquid sample was taken in the C2~e2 solution, dried under vacuum, and observed by a transmission electron microscope (TEM). The results of TEM observation showed that the gold nanoparticles in the d2, c2 and e2 solutions were also in a state of no aggregation and uniform aggregation. The particle size in the selected range was measured and the particle size was calculated. ^ The average particle size of the nanoparticles in the e2 solution is 5 nm, 1〇11111 and 3〇nm' respectively. This corresponds to the measurement results of the ultraviolet-visible absorption spectrum described above, indicating that the slower the heating rate is, the particles are obtained. The smaller the diameter of the gold nanoparticles, the change in heating rate can be used to control the size of the nanoparticles produced. <Specific Example 2 - Preparation of a composite of noble metal nanoparticles and chitin by electrochemical method> 4 〇ml of 0·1 Ν gasified sodium solution was prepared as a3 solution and 0 with a concentration of lg/L cin 1 Νml of a gasified sodium solution was used as the b3 solution, and gold ions were prepared in the a3, b3 solution in the manner as described in <Specific Example>, and then the gold substrate was replaced with a platinum substrate as a working electrode. And still use the white 18 201041968 gold plate as the auxiliary electrode, and the silver/silver chloride electrode tube as the reference electrode, and then reduce the gold ion to the gold nanoparticle by applying an overpotential of 0.6V to the cathode to b3 The solution A forms a complex of the gold nanoparticles and the chitin and forms the gold nanoparticles in the a3 solution. The following test analyses were carried out and the results were as follows: (1) The ultraviolet-visible absorption spectra of the a3 and b3 solutions after electrolysis and electrochemical reduction were respectively measured (using instrument: Perkin-Elmer Lambda 35 spectrophotometer) ° 0 Before electrochemical reduction after electrolysis, the a3 and b3 solutions appeared yellow due to the presence of AuC14_. After electrochemical reduction, the color of the a3 solution remained yellow, indicating that the a3 solution may not have a significant reduction reaction, and the 'b3 solution The color gradually changes from yellow to red, and the color of the gold nanoparticle is red, indicating that the b3 solution has a significant reduction reaction. As shown in Fig. 10, after electrochemical reduction, the b3 solution showed a distinct absorption band at 522 nm. The a3 solution had no obvious absorption peak signal near the wavelength, and the position of the absorption peak signal appeared as the characteristics of the gold nanoparticles. , Ο The color change of the a3 solution and the b3 solution observed during the experiment shows that when the chitin is present in the solution, it is beneficial to reduce the gold ions to the gold nanoparticles. After the b3 solution was vortexed by ultrasonic waves and then centrifuged to remove chitin, the clarified liquid portion after centrifugation of the b3 solution was further analyzed by inductively coupled plasmo-mass spectrometer (ICP-MS) to show the concentration of the synthesized gold nanoparticles. It is about 60ppm. (2) A drop of the liquid sample was taken in the b3 solution, dried under vacuum and observed under a transmission electron microscope. 19 201041968 As shown in FIG. 11, when the particle diameters of the gold nanoparticles are calculated for a specific region, the average particle diameter is about 15 nm, and it is also shown that the gold nanoparticles are not aggregated, but Disperse evenly. Further, as shown in FIG. 11, a plurality of dark gold nanoparticles 200 are also adsorbed on the surface of the gray chitin 20. (3) X-ray diffraction (XRD) is applied to the b3 solution. The instrument model is ARL X'TRA Thermo and is equipped with a capillary for analysis of liquid samples. The results are similar to the measurement results of <Specific Example 1>, and also appear at 38.2°, 44.4°, 64.6°, and 77.5°, respectively, which represent the special crystal faces (111), (200), (220) of gold and The peak signal of (311) indicates the presence of gold in the b3 solution. In addition, the broad and gentle peak signal appearing at 23 ° shows the presence of amorphous chitin, which indicates that Chennai is also formed in the b3 solution. A composite of rice particles/chitin. (4) The electrochemically reduced b3 solution was centrifuged at 15,000 rpm for 3 minutes, washed with deionized water, and the foregoing process was repeated 3 times to collect a powdery product sample, followed by high resolution X-ray photoelectron spectroscopy (high resolution X- Ray photoelectron spectroscopy (abbreviated as HRXPS) for detection, the model used for the XPS measurement instrument is ULVAC PHI Quantera SXM spectrometer ° As shown in Figure 12, it shows that the collected powder samples have two elements of gold and nitrogen after analysis. The signal, because only the chitin contains nitrogen element, it is speculated that the product sample does contain gold and chitin. 0 20 201041968 The process of the invention can be carried out in addition to no harmful chemicals.
Ο ’再透過離心方式， 值得說明的是，本發明的製 物質的方式製得貴金屬奈米粒與 樣可製得單純的貴金屬奈米粒子 該第一溶液φ枯喜人s _ ’及含有貴金屬奈米粒子的澄清液。 金屬奈米粒子時，也可以先利用超音 素上的貴金屬奈米粒子與甲殼素分離 为別收集含有甲殼素的沉殿物及含有 米粒子的量增加。 金不米粒子的澄清液，藉此，能使所收集至㈣$純的金奈 歸納上述，本發明貴金屬奈米粒子與甲殼素之複合物 ’、衣法可獲致下述的功效及優點，故能達到本發明的 一、 藉由甲殼素結合貴金屬奈米粒子形成複合物產品 ，可結合曱殼素與貴金屬奈米粒子的特性，增加產品的實 用效益，尤其是用於過濾器產品時，可利用曱殼素吸附雜 質的特性，及貴金屬奈米粒子分解與催化的特性，使吸附 在甲设素上的雜質快速分解為無害的物質，而能提供清淨 解毒或除污的使用效能。 二、 透過本發明的製造方法，由於製程中使用不易危 害人體的電解質溶液與天然來源的曱殼素作為原料，配合 施加不易造成污染的能源就能使貴金屬離子被還原為貴金 屬奈来粒子’並順利與甲殼素結合而形成責金屬奈米粒子 21 201041968 與甲殼素之複合物產品，由於製程較乾淨’在製出該複合 物產品後’可不需再進行分離程序或清洗處理’相對能減 少製程時間，使本發明具有製程較環保、有效率，且較符 合安全衛生標準的特性與優點。 三、在該製造方法中’透過在含有貴金屬離子錯合物 的第二溶液中添加曱殼素了作為複合物的原料外，由 於曱级素可供貴金屬離子與貴金屬奈米粒子吸附，當貴金 屬離子被還原為貴金屬奈米粒子時，仍能吸附在甲殼素上 ’可有效防止被還原的貴金屬奈米粒子沉積於電極基材上◎ 而減；產ΐ，使本發明的製法相對能製造較高產量的貴金 屬奈米粒子。 " 准以上所述者’僅為本發明之較佳實施例而已，當不 月b以此限疋本發明實施之範圍’即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1是一流程圖，說明本發明貴金屬奈米粒子與甲殼◎ 素之複合物的製法一較佳實施例； 圖2是一紫外光-可見光吸收光譜圖，說曰月al、Μ與 cl溶液在電解後加熱前所呈現的光譜； 、圖3是一紫外光-可見光吸收光譜圖，說明al與bl溶 液在電解後及加熱後所呈現的光譜； ,π圖是穿透式電子顯微鏡照像圖，說明b丨溶液中所 製侍的金奈米粒子的尺寸與分布情形； 22 201041968 圖5是一 X射線繞射圖，說明b 1溶液中的複合物的分 析結果； 圖6是一高解析X射線光電子光譜，說明b丨溶液中的 複合物的分析結果； 圖7是一高解析X射線光電子光譜，說明針對Au 4f7/2_ w核-階層的光譜分析bl溶液加熱處理前、後的結果； 圖8是一紫外光-可見光吸收光譜圖，說明a2與b2溶 液在電解後電化學還原前所呈現的光譜； 圖9是一紫外光·可見光吸收光譜圖，說明a2〜e2溶液 在電解後及電化學還原後所呈現的光譜； 圖10是一紫外光-可見光吸收光譜圖，說明a3、b3溶 液在電解後及電化學還原後所呈現的光譜； ,圖11疋一穿透式電子顯微鏡照像圖，說明b3溶液中所 裝仔的金奈米粒子的尺寸與分布，及吸附於甲殼素上的 形；及 圖12疋一尚解析X射線光電子光譜，說明b3溶液中 的複合物的分析結果。 23 201041968 【主要元件符號說明】 金奈米粒子 20.........曱殼素 200 24Ο 'Re-centrifugal method, it is worth noting that the method of preparing the material of the present invention produces precious metal nanoparticles and samples can be prepared from simple precious metal nanoparticles. The first solution φ 枯 人 s _ ' and contains precious metal nanoparticles A clear liquid of particles. In the case of metallic nanoparticles, the noble metal nanoparticles on the superphone can be separated from the chitin. The amount of the chitin containing the chitin and the amount of the rice particles is increased. The clear liquid of the gold non-rice particles, whereby the collected (four) $pure Chennai can be summarized as described above, and the complex of the precious metal nanoparticle of the present invention and chitin can be obtained, and the following effects and advantages can be obtained. Therefore, it is possible to achieve the first invention of the present invention, which can form a composite product by combining chitin with precious metal nanoparticles, and can combine the characteristics of the chitin and the precious metal nano particles to increase the practical benefit of the product, especially when used in a filter product. The characteristics of the adsorption of impurities by the chitin and the decomposition and catalysis of the noble metal nanoparticles can be utilized to rapidly decompose the impurities adsorbed on the substrate into harmless substances, and provide the use efficiency of detoxification or decontamination. 2. Through the manufacturing method of the present invention, since the electrolyte solution which is not harmful to the human body is used in the process and the natural source of chitin is used as a raw material, the precious metal ions can be reduced to the noble metal natrile particles by applying an energy source which is not easily polluted. Successfully combined with chitin to form a metal nanoparticle 21 201041968 Composite product with chitin, because the process is relatively clean 'after the preparation of the composite product' can be no longer need to separate the process or cleaning process 'relatively reduce the process Time, the invention has the characteristics and advantages that the process is more environmentally friendly, efficient, and more in line with safety and health standards. 3. In the manufacturing method, 'the addition of quercetin to the second solution containing the noble metal ion complex is used as a raw material of the composite, and the noble metal can be adsorbed to the noble metal ion and the noble metal nanoparticle. When the ions are reduced to the noble metal nanoparticles, they can still be adsorbed on the chitin, which can effectively prevent the reduced precious metal nanoparticles from being deposited on the electrode substrate, and can reduce the production of the present invention. High yield of precious metal nanoparticles. "The above is only a preferred embodiment of the present invention, and the scope of the present invention is limited to the scope of the present invention, i.e., the simple scope of the patent application scope and the description of the invention according to the present invention. Both effect changes and modifications are still within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a preferred embodiment of a process for preparing a composite of a noble metal nanoparticle and a carotenoid of the present invention; FIG. 2 is an ultraviolet-visible absorption spectrum diagram, The spectrum of the al, Μ and cl solutions before heating after electrolysis; Figure 3 is an ultraviolet-visible absorption spectrum, showing the spectrum of the a and bl solutions after electrolysis and after heating; A through-electron microscope photograph showing the size and distribution of the gold nanoparticles prepared in the b丨 solution; 22 201041968 Figure 5 is an X-ray diffraction diagram illustrating the results of the analysis of the complex in the b 1 solution Figure 6 is a high-resolution X-ray photoelectron spectroscopy showing the results of the analysis of the complex in the b丨 solution; Figure 7 is a high-resolution X-ray photoelectron spectroscopy showing the spectral analysis of the bl solution for the Au 4f7/2_ w core-hierarchy Figure 8 is an ultraviolet-visible absorption spectrum showing the spectrum of the a2 and b2 solutions before electrochemical reduction after electrolysis; Figure 9 is an ultraviolet/visible absorption spectrum, illustrating A2~e2 The spectrum of the liquid after electrolysis and after electrochemical reduction; Figure 10 is an ultraviolet-visible absorption spectrum showing the spectrum of the a3 and b3 solutions after electrolysis and electrochemical reduction; The size of the gold nanoparticles coated in the b3 solution and the shape adsorbed on the chitin; and the analytical X-ray photoelectron spectroscopy in the b3 solution The results of the analysis of the complex. 23 201041968 [Description of main component symbols] Golden nanoparticles 20.........Chitin 200 24