201029775 六、發明說明： 【發明所屬之技術領域】 奈米技術 【先前技術】 無 【發明内容】 本發明係有關於合成可調粒徑奈米金屬、雙金屬、多金屬或合金之核殼材料之方 法’按，奈米粒子具小尺寸、表面與量子效應產生之特異性質，廣泛應用於觸媒電子、 光學、磁性與超導體、及醫藥等，但奈米材料之更精緻化應用之關鍵處，則是合成可調 粒徑與形狀、大小均一、及高分散性之奈米粒子，傳統合成奈米粒子之方法例如··化學 還原法、金屬蒸鑛及雷射照射等都無法合成大小均一及可調粒徑與形狀之奈米金屬粒 子。 另外，奈米金屬表面活性高，易在操作或應用環境中進行物理、化學反應例如氧化 或團聚而增加顆粒尺寸大小或改變形狀，而減少其實際應用效率。 又’傳統合成奈米粒子之方法除無法產生大小均一及可調粒徑與形狀之奈米金属粒 子’也無法調控雙金屬、多金屬或合金之比例，更無法大量生產。 緣是，發明人有鑑於此，秉持多年之學術研究及實務經驗，以非常簡單之方法，合 ❹ 成之-種可調粒控奈米金屬、雙金屬、多金屬或合金之核殼材料，成為一種新型奈米材 料也兼具能源、環保、生醫、觸媒及光電應用價值 【實施方式】 本發明係有關於合成一種可調粒徑奈米金屬、雙金屬、多金屬或合金之核殼材料， 並利用其可調粒徑、大小均一、不易被氧化或團聚之特殊結構與物化特性，可有效應用 於光熱獵殺惡性腫瘤、藥物調控傳遞、奈米反應器、高效散熱管、高效散熱膏添加劑、 高效奈米熱流體(thermal fluid)添加劑、高速噴注熱觸媒、奈米核能、及富集廢水中重金 屬等’為使本發明使用之技術手段、發明特徵，達成目的與功效易於了解，茲配合圖式 及圖號詳細說明如下： 本發明之實施例一：光熱獵殺惡性腫瘤 201029775 奈米核殼材料例如：⑽c、Ni@c、Ag@c、CuAg(合金)@C、CuNi(雙 應用於光熱獵殺惡性腫瘤，利用近紅外光雷射师聰⑶編2))照射奈米核殼材料約 10〜15分鐘’使其魏総震動產生触’可使奈雜殼材制遭之紐腫瘤溫度提升 至41〜5(TC，致使惡性腫瘤細胞死亡。 本發明之實施例二：藥物調控傳遞 奈米核殼材料之金屬核可析出，生成一種新型可調祕中空碳球(H@C)材料，透過 控制藥物在中空球核與外界液體之交換及傳輸，可雛加入中空球核之藥物傳遞，藥物 釋出之時間，可控制在1〇~ 180分鐘之間。 φ 本發明之實施例三：奈米反應器 可調粒徑中空碳球材料，可另添加所需、可調粒徑銅、辞觸媒於中空球核中，在 30〜80°C進行催甲醇部分氧化反應，生成h2。 本發明之實施例四：高效散熱管 將奈米Cu@C塗佈於CPU或LED散熱管内壁，左管外部加熱至3〇〇〜7〇此，使散 熱管内部工作流體(水)進行蒸氣重組’剝除奈米碳殼(C + 士〇 + c〇+抑，隨後抽真空 至10〜15毫米汞柱壓力’直接封裝熱導管，形成具奈米銅毛細結構之燒結式散熱管，該 散熱管之最大熱傳量至少增加60%，而且程序操作簡單、成本低廉。 Φ 本發明之實施例五：高效散熱膏添加劑 添加1〜20%之奈米鋼賊材料如Cu@c添加於cpu或LED散熱膏中可增加軌導 係數⑽n-K)至少篤。所添加之Cu@c，成本非常錄，另外，由於長期處於高溫 之CPU S LED散熱膏’事實上更加有利，因為散熱膏中之殘餘氧易被Cu@c之碳殼消 耗’形成奈米金屬銅，可大幅增加熱導係數，也降低散齡中有機物劣化反應速率，提 升散熱膏之效率及使用期限。 本發明之實施例六：高效奈米流體(Najjofluid)添加劑 添加0.2〜3%不同粒徑之奈米核殼材料例如Cu@c於水中，可有效提升奈米流體之 熱導係數20〜30%。此外，外層碳殼也具降低奈細粉被流體氧化之速率騎止奈米鋼 聚集沉澱之樣。可制於散熱用之鮮f喊體及替倾環水散熱之流體。 5 201029775 本發明之實施例七：高速喷注熱觸媒 奈米核殼材料例如1〜5〇/<Fe2〇3@C混合於超臨界C〇2流體中，可將Fe203@C之 碳層氧化’提升Fe203觸溫度至·可极高速姐、催化麟油頁岩、油砂 或高分子塑橡膠廢棄物中之重質碳氫化合物，再以超臨界c〇2萃取回收較輕質碳氣化合 物油類’其效率可提升至少20〜25%。 本發明之實施例八：奈米核能 如第4圖說明合成之可調粒徑奈米金屬、雙金屬、多金屬或合金之核殼材料之相依 曲線’估算可合成奈米U235@c (U之粒徑約為M nm)，尤其其外殼之碳層（以類鑽石 及石墨碳為主）可減緩奈米U之輻射污染之問題，若奈米u@c分散於f溫離子炼液 • (iGnieliqUid)巾，可在微魏電漿帽溫度提升至5_1壯，啟動可錄量之核裂 解連鎖反應’產生可微調之奈米核能，有利於發展奈米級核能發電系統。 本發明之實施例九：富集廢水中有價重金屬 以醣類化合物例如：環湖精(cyclodextrin)、葡萄糖(gluc〇se)、殿粉(St·)或其他多 醣物等萃取、富集廢水(尤其是電鑛或化學機械研磨廢水)中之重金屬，除可降低廢水中 金屬量至少90%，也可製成奈米核殼材料，提升其附加價值。 综上所述，本發明實施例確能達到所_之功效，又其展示之具體功能不僅未曾 見諸同類產品中，亦未曾公開於巾請前’誠已完全符合專利法之規定與要求，爰依法提 〇 出發明專利之申請’懇請惠予審査，並賜准專利，則實感德便。 【圖式簡單說明】 如第1圖說明本發日月可調粒徑奈米金屬、雙金屬、多金屬或合金之核殼材料之合成 方法’醣類化合物(例如：環糊精(cycl〇dextrin)、葡萄糖(glu_)、澱粉咖⑻、或其他 多聽物（pdysacch^ride)等)螯合萃取金属離子成為錯合物，在⑽貌乾燥12〜36、小 a夺’另在150〜650C粉體碳化2〜12小時’生成可調粒徑奈米金屬、雙金屬、多金屬或 合金之核殼材料。第2圖之xrd圖顯示所合成之奈翻、奈練、奈綠、奈米銅銀 雙金屬、奈米舰合金化學結構，各自之繞射波峰具寬胖特性顯示其奈米尺寸，且無金 屬氧化態存在。第3 _補合成之可雕徑奈米金屬(M@C)、雙金屬、多金屬或合金 之核殼材料之_結構示意圖，所合成之奈雜子具減結構，⑽金屬縣外層碳所 6 201029775 包夾，尤其，奈米粒子均勻分散，顆粒大小均一。第4圖顯示所合成之奈米核殼材料之 粒徑大小，可以調控醣化合物之〇H基與金屬離子之莫耳比例(OH/M)，合成可調、所 需奈米金屬粒徑範圍為4~80 nm。第4圖(a)顯示奈米Cu@C、Ag@C、Rh@C及Pd@C 核殼之金屬粒徑大小與OH/M莫爾比例之關係，OH/M比例大於7時’合成最小尺寸之 Cu (7 nm)、Ag (15 nm)、Rh (4 nm)及 Pd (7 nm);當 OH/M 比例減少，金屬粒徑增加， OH/M小於1.2時，金屬粒徑大於1〇〇nm，其他金屬也表現類似結果。尤其，所建置之 相依曲線(correlative curve)(如第4圖(b)) ’其中粒徑大小(particle size (dp))、金屬離子價 數(valence of metal (Z))及原子半徑(atomic radius (r))，可以據以合成其他可調粒徑金 屬、雙金屬、多金屬或合金之核殼材料。 Φ 藉由以上說明’本發明合成之可調粒徑奈米金屬、雙金屬、多金屬或合金之核殼材 料至少具下列優點： 1.具可調粒徑、大小均一，不易被氧化或團聚之特殊結構與物化特性，成為一種新型奈 米材料也兼具能源、環保、生醫、觸媒及光電應用價值。 2·合成方法簡單、成本低廉’又可依據已建置完成之相依曲線(如第4圖⑽，可以調控 醣化合物之OH基與金屬離子之莫耳比例(〇H/M)，合成可調所需奈米金屬粒程範圍 為4~8〇nm之大部分金屬、雙金屬、多金屬或合金之核殼材料。 【主要元件符號說明】201029775 VI. Description of the invention: [Technical field of invention] Nanotechnology [Prior Art] No [Abstract] The present invention relates to synthesis of core-shell materials of tunable particle size nano metal, bimetal, polymetal or alloy The method is based on the small size, surface and quantum effect of nano particles, widely used in catalytic electronics, optics, magnetism and superconductors, and medicine, but the key to the more refined application of nanomaterials It is a synthetic nanoparticle with a uniform particle size, shape, size, and high dispersibility. Traditional methods for synthesizing nanoparticle, such as chemical reduction, metal distillation, and laser irradiation, cannot be uniform in size. And nano metal particles with adjustable particle size and shape. In addition, nano-metals have high surface activity and are susceptible to physical or chemical reactions such as oxidation or agglomeration in an operating or application environment to increase particle size or shape, thereby reducing their practical application efficiency. Moreover, the conventional method of synthesizing nano-particles cannot produce a ratio of bimetallic, polymetallic or alloy in addition to the inability to produce nano-sized metal particles of uniform size and shape and shape, and is not capable of mass production. The reason is that, in view of this, the inventors have been adhering to many years of academic research and practical experience, and in a very simple way, they have become a kind of core-shell material with adjustable grain-controlled nano-metal, bimetal, multi-metal or alloy. It is a new type of nano-material that also has the value of energy, environmental protection, biomedical, catalytic and optoelectronic applications. [Integrated mode] The present invention relates to the synthesis of a core of a tunable particle size nano metal, bimetal, polymetal or alloy. The shell material, and its special structure and physicochemical properties, which can be oxidized or agglomerated, can be effectively applied to photothermal hunting of malignant tumors, drug regulation and transfer, nano reactor, high efficiency heat pipe, and high efficiency. Thermal grease additive, high-efficiency thermal fluid additive, high-speed injection thermal catalyst, nano-nuclear energy, and heavy metal in wastewater, etc., to achieve the purpose and efficacy of the technical means and invention features used in the present invention It is easy to understand, and the drawings and figure numbers are described in detail as follows: Embodiment 1 of the present invention: photothermal hunting of malignant tumors 201029775 Nano core shell materials such as: c, Ni@c, Ag@c, CuAg (alloy) @C, CuNi (double applied to photothermal hunting of malignant tumors, using near-infrared light laser Shi Cong (3) 2)) Irradiation of nano-core material about 10~ 15 minutes 'to make Wei Wei vibration to produce a touch' can increase the temperature of the tumor of the navel shell material to 41~5 (TC, causing the death of malignant tumor cells. Example 2 of the present invention: drug regulation and delivery of nanonuclei The metal core of the shell material can be precipitated to form a new type of adjustable hollow carbon sphere (H@C) material. By controlling the exchange and transmission of the drug in the hollow core and the external liquid, the drug can be transferred to the hollow core. The release time can be controlled between 1 〇 and 180 minutes. φ The third embodiment of the invention: the nanometer reactor adjustable particle size hollow carbon sphere material, can be added with the required, adjustable particle size copper, The catalyst is subjected to partial methanol oxidation reaction at 30 to 80 ° C to form h2 in a hollow core. Embodiment 4 of the present invention: a high-efficiency heat-dissipating tube is coated with a nano-Cu@C on the inner wall of a CPU or an LED heat-dissipating tube. The outside of the left tube is heated to 3 〇〇 to 7 〇, so that the working fluid (water) inside the heat pipe is vaporized. The group 'stripping the nanocarbon shell (C + gentry + c〇 + suppress, then vacuuming to 10~15 mm Hg pressure) directly encapsulates the heat pipe to form a sintered heat pipe with a nano copper capillary structure, The maximum heat transfer capacity of the heat pipe is increased by at least 60%, and the program operation is simple and the cost is low. Φ Embodiment 5 of the present invention: high-efficiency heat-dissipating paste additive is added with 1~20% of nano steel thief material such as Cu@c added to cpu Or LED thermal grease can increase the rail conductivity coefficient (10)n-K) at least 笃. The added Cu@c, the cost is very recorded, in addition, due to the long-term high temperature CPU S LED thermal grease 'is actually more advantageous, because the thermal grease The residual oxygen is easily consumed by the carbon shell of Cu@c to form nano-metal copper, which can greatly increase the thermal conductivity coefficient, reduce the degradation rate of organic matter in the age of the dispersion, and improve the efficiency and service life of the thermal grease. Embodiment 6 of the present invention: a high-efficiency nano fluid (Najjofluid) additive is added with 0.2 to 3% of a nano-core shell material of different particle diameters such as Cu@c in water, which can effectively improve the thermal conductivity of the nano-fluid by 20 to 30%. . In addition, the outer carbon shell also has a sample that reduces the rate at which the nanopowder is oxidized by the fluid and rides on the nano steel. It can be used for the heat-dissipating body and the fluid for heat dissipation. 5 201029775 Embodiment 7 of the present invention: high-speed injection of a thermal catalyst nano core shell material such as 1~5〇/<Fe2〇3@C mixed in a supercritical C〇2 fluid, which can carbonize Fe203@C Layer oxidation 'improves the Fe203 touch temperature to the extremely high-speed sister, catalyzed the heavy hydrocarbon in the oil shale, oil sands or polymer plastic rubber waste, and then extracts the lighter carbon gas with supercritical c〇2 Compound oils' efficiency can be increased by at least 20 to 25%. Embodiment 8 of the present invention: Nano nuclear energy as shown in Fig. 4 illustrates the dependence curve of the synthesized core-shell material of a tunable particle size nano metal, bimetal, polymetal or alloy 'estimally synthesizes nano U235@c (U The particle size is about M nm), especially the carbon layer of the outer shell (mainly diamond-like and graphite carbon) can slow down the radiation pollution of nano U, if the nano-u@c is dispersed in the f-temperature refining liquid• iGnieliqUid) towel can raise the temperature of micro-Wei plasma cap to 5_1 strong, and start the recordable nuclear cracking chain reaction' to produce fine-tunable nano-nuclear energy, which is conducive to the development of nano-scale nuclear power generation system. Embodiment 9 of the present invention: the valuable heavy metal in the enriched wastewater is extracted and enriched with a saccharide compound such as cyclodextrin, glucose (gluc〇se), temple powder (St·) or other polysaccharides ( Especially in the heavy metal of electro-mine or chemical mechanical grinding wastewater, in addition to reducing the amount of metal in the wastewater by at least 90%, it can also be made into nano-core shell material to enhance its added value. In summary, the embodiments of the present invention can achieve the functions of the present invention, and the specific functions of the present invention have not only been seen in similar products, nor have they been disclosed before the towel. The company has fully complied with the requirements and requirements of the Patent Law.爰Improved the application for invention patents in accordance with the law's request for review and granting patents. [Simple description of the diagram] As shown in Figure 1, the synthesis method of the core-shell material of the adjustable particle size nano-metal, bimetal, polymetallic or alloy is described as 'saccharide compound (eg cyclodextrin). Dextrin), glucose (glu_), starch coffee (8), or other polyphonic material (pdysacch ^ride), etc.) chelate extraction of metal ions into a complex, in the (10) appearance dry 12~36, small a win 'other in 150~ The 650C powder is carbonized for 2 to 12 hours to form a core-shell material of a tunable particle size nano metal, bimetal, polymetal or alloy. The xrd diagram in Fig. 2 shows the chemical structure of the synthesized Nai, Nai, Nai green, nano-copper-silver bimetal, and nano-ship alloy. The diffraction peaks of each have a wide fat characteristic and show their nanometer size, and no The metal oxidation state is present. The structure of the 3rd _ complement synthetic can be carved metal nano-metal (M@C), bimetallic, multi-metal or alloy core-shell material, the synthesized naphtha with reduced structure, (10) metal county outer carbon 6 201029775 Bundle, in particular, the nanoparticles are evenly dispersed and the particle size is uniform. Figure 4 shows the particle size of the synthesized nano-core shell material, which can regulate the molar ratio (OH/M) of the 〇H group and the metal ion of the sugar compound, and the synthesis can be adjusted to the range of the desired nano metal particle size. It is 4~80 nm. Figure 4 (a) shows the relationship between the particle size of the nano-Cu@C, Ag@C, Rh@C and Pd@C core shells and the OH/M Mohr ratio. When the OH/M ratio is greater than 7, 'synthesis The smallest size of Cu (7 nm), Ag (15 nm), Rh (4 nm), and Pd (7 nm); when the OH/M ratio decreases, the metal particle size increases, and when the OH/M is less than 1.2, the metal particle size is larger than At 1 〇〇 nm, other metals also showed similar results. In particular, the established correlation curve (eg Figure 4 (b)) 'where particle size (dp)), metal ion valence (valence of metal (Z)) and atomic radius ( Atomic radius (r)), which can be used to synthesize other core materials of adjustable size metals, bimetals, polymetallics or alloys. Φ By the above description, the core-shell material of the tunable particle size nano metal, bimetal, polymetal or alloy synthesized by the invention has at least the following advantages: 1. It has adjustable particle size, uniform size, and is not easily oxidized or agglomerated. The special structure and physicochemical properties have become a new type of nanomaterials that also have the value of energy, environmental protection, biomedical, catalytic and optoelectronic applications. 2. The synthesis method is simple and the cost is low. According to the correlation curve that has been completed (such as Figure 4 (10), the molar ratio of OH group to metal ion of sugar compound (〇H/M) can be adjusted, and the synthesis can be adjusted. The required core metal range of 4~8〇nm is the core material of most metals, bimetals, polymetallics or alloys.