1286490 九、發明說明 【發明所屬之技術領域】 本發明係有關於一種中空氧化矽粒子之製作方法，特別 是有關於一種在室溫下藉由酸鹼值的調整來形成中空氧化 矽粒子之製作方法。 【先前技術】 抗反射薄膜對於光電顯示器的應用上有著非常重要的 ^ 地位，尤其是大面積的顯示器薄膜。一般而言要達到抗反射 的目的，不外乎調整薄膜的折射率，如在基材上先鍍以高折 射率的薄膜，再鍍以低折射率的薄膜，即可藉由折射率的改 變來使反射率降低，達到抗反射的目的。中空粒子為顆粒内 存在著一個大的孔洞，此孔洞的存在可以使顆粒的折射率因 為空氣層的存在而降低，就可以應用於抗反射塗層的最外 層，也就是可以藉由中空粒子的添加來降低薄膜的折射率。 中空粒子在合成上是以模板的方式居多，例如： # 美國專利第4764498號揭露一種以喷霧乾燥方式形成 - 之中空粒子，是將矽溶膠或水玻璃與模板物質喷入加熱爐中 乾燥後，去除模板而得微米級多孔或中空粒子。 η 2003 年 Prak 等人於 Journal of Colloid and Interface Science第266期第107-114頁中揭露一種以微乳化的方 式，使用聚合物、四乙基石夕氧、介面活性劑在油水混合相中 製造氧化矽之中空粒子。 2004 年 Chen 等人於 Biomaterials 第 25 期第 723-727 1286490 頁中揭露種以奈米碳酸鈣為模板的方法，並將四乙基矽氧 披覆於此碳酸鈣模板上，最後將碳酸鈣模板以煅燒的方式移 除。 2003 年 Zhang 等人於 Journal 〇f c〇11()id — 第263期第467_472頁中揭露一種以奈米聚合物顆 粒為模板的方法，經過改質後在水熱的環境下，披覆一層氧 化石夕’再利用锻燒的方式將中間的模板移除而形成中空粒 子。 另外，在2005年Prak等人於迦〜山^眞匕 ㈣偷第40期第271_頁中揭露一種以石夕形顆粒為模 板的方法’在其表面吸附銀粒子後，以氫氟酸將矽形顆粒移 除’而留下具有奈米銀結構的中空粒子。 练S之，上述習知技術所採用的各種模板方式中，有的 是以有機顆粒為模板’有的是以奈米碳_為模板，有的是 以石^顆粒為模板，不論㈣何種材料當作模板，所需的製 =不疋水熱法就是加熱製程’都需要以高温锻燒或是以氮氣 酸腐钱的方式來去除模板，製繁 表程繁瑣而且成本鬲，導致習知 技術不適於應用在產業上來大量生產中空粒子。 因此，非常需要一種改進的中空粒子之製作方法，來解 =上述習知技術的製程繁璃、成本高，且無法大量生產的問 以達到簡化製程、降低成本以及大量生產的目的。 【發明内容】 本發明之一目的係在於提供一 種中空氧化矽粒 子的製 1286490 作方法’藉以經由常溫陳化階段來得到核殼結構，並且採用 鋁奈米粒子為模板，以在低劑量的化學腐敍條件（阳4 下’去除模板而得到中空粒子’因而解決製程繁璃的問題。 本發明的另-目的是在提供一種中空氧化梦粒子之製 作方法’藉以在室溫之下進行’且不需要以任何高溫加熱處 理的方式去除模板，因而大幅降低製造的能源及成本。 根據本發明之上述目的，提出—種中空氧化梦粒子之製 作方法。首先’提供—含銘離子之溶液，接著，加入沉激劑 至含鋁離子之溶液中’以形成含鋁粒子’將含鋁粒子過濾及 水洗後’加人酸驗值調整劑至含峰子，以調整含銘粒子之 酸驗值大約在4至5之間，接著，加入梦酸膠顆粒以形成一 核殼結構包覆含鋁粒子，以及調整核殼結構之酸鹼值大約至 1左右，以溶解含鋁粒子而製得中空氧化矽粒子。 依”、、本發明較佳實施例，上述之含銘離子之溶液可例 如是將硝酸銘或是氫氧化銘加入去離子水中所製得。 依”、、本發明一較佳實施例，上述之沉殿劑可例如是氨水 或碳酸銨。 依照本發明一較佳實施例，上述之酸鹼值調整劑可例如 疋硝酸、鹽酸、硫酸、磷酸、碳酸或醋酸。 應用上述中空氧化矽粒子之製作方法，由於是在室溫下 藉由酸驗值的調整’使含鋁粒子細化至奈米級後，加入矽酸 膠顆粒披覆於含銘粒子的表面，以形成一核殼結構包覆含鋁 粒子’再將溶液的酸鹼值調整到約1左右，使中間核心的含 銘不米粒子溶解’而形成奈米中空粒子。所以本發明的優點 1286490 係在於室溫之下，藉由酸鹼值的調整之製程即可獲得奈米中 空粒子，與其它習知製程相比，本發明所用的方法不僅相對 簡單化，更大幅降低製造時間、能源及成本。 【實施方式】1286490 IX. Description of the Invention [Technical Field] The present invention relates to a method for producing hollow cerium oxide particles, and more particularly to a method for forming hollow cerium oxide particles by adjusting pH value at room temperature. method. [Prior Art] The antireflection film has a very important position for the application of the photoelectric display, especially a large-area display film. In general, to achieve the purpose of anti-reflection, it is necessary to adjust the refractive index of the film, such as a film with a high refractive index on the substrate, and then a film with a low refractive index, which can be changed by the refractive index. To reduce the reflectivity and achieve anti-reflection. The hollow particles have a large hole in the particle. The existence of the hole can reduce the refractive index of the particle due to the presence of the air layer, and can be applied to the outermost layer of the anti-reflective coating, that is, by hollow particles. Add to reduce the refractive index of the film. The hollow particles are mostly in the form of a template, for example: # US Pat. No. 4,764,498 discloses a hollow particle formed by spray drying, which is obtained by spraying a cerium sol or water glass and a template material into a heating furnace. The template is removed to obtain micron-sized porous or hollow particles. η 2003, Prak et al., Journal of Colloid and Interface Science, 266, pp. 107-114, discloses a microemulsification method for the production of oxidation in a mixed phase of oil and water using a polymer, tetraethyl oxalate, or an surfactant. Hollow particles of 矽. In 2004, Chen et al., Biomaterials, No. 25, pp. 723-727 1286490, discloses a method using nano-calcium carbonate as a template, and tetraethyl cerium oxide is coated on the calcium carbonate template, and finally the calcium carbonate template is applied. Remove by calcination. In 2003, Zhang et al., Journal 〇fc〇11() id - p. 263, pp. 467_472, discloses a method using nano-polymer particles as a template. After modification, it is coated with a layer of oxidation in a hydrothermal environment. Shi Xi' removes the intermediate template by means of calcination to form hollow particles. In addition, in 2005, Prak et al. revealed the method of using Shishi-shaped particles as a template in the case of Shijia~shan^(4) stealing the 40th issue of 271_, after the adsorption of silver particles on the surface, hydrofluoric acid will be The scorpion-shaped particles are removed to leave hollow particles having a nano-silver structure. In the above-mentioned conventional techniques, some of the various template methods used are organic particles as templates. Some use nano carbon as a template, and some use stone particles as a template, regardless of (4) which materials are used as templates. The required system = not the hydrothermal method is the heating process 'all need to be calcined at high temperature or the method of removing the template by means of nitrogen acid rot, making the complicated process and costly, resulting in the unsuitable application of the conventional technology in the industry. Come up to mass production of hollow particles. Therefore, there is a great need for an improved method for producing hollow particles to solve the above-mentioned conventional techniques of manufacturing process, high cost, and incapable of mass production to achieve a simplified process, reduced cost, and mass production. SUMMARY OF THE INVENTION One object of the present invention is to provide a method for making a hollow cerium oxide particle 1286490 as a method for obtaining a core-shell structure through a normal temperature aging stage, and using aluminum nanoparticle as a template for low-dose chemistry. The problem of rot-forming conditions (removing the template to obtain hollow particles under yang 4) thus solving the problem of process glass. Another object of the present invention is to provide a method for producing hollow oxidized dream particles 'by performing at room temperature' and It is not necessary to remove the template by any high-temperature heat treatment, thereby greatly reducing the energy and cost of manufacturing. According to the above object of the present invention, a method for producing hollow oxidation dream particles is proposed. First, 'provide a solution containing a precursor ion, and then Adding a stimulant to the solution containing aluminum ions to form aluminum-containing particles. After filtering and washing the aluminum-containing particles, add a human acid value adjuster to the peak to adjust the acid value of the containing particles. Between 4 and 5, then, adding the smear particles to form a core-shell structure to coat the aluminum-containing particles, and adjusting the pH value of the core-shell structure About to about 1 to dissolve the aluminum-containing particles to obtain hollow cerium oxide particles. According to a preferred embodiment of the present invention, the above-mentioned solution containing the ionic ions can be added, for example, to nitric acid or hydrazine. According to a preferred embodiment of the present invention, the above-mentioned sinking agent may be, for example, ammonia water or ammonium carbonate. According to a preferred embodiment of the present invention, the above-mentioned pH adjusting agent may be, for example, nitric acid. , hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid or acetic acid. The application method of the above hollow cerium oxide particles is carried out by adjusting the acid value at room temperature to refine the aluminum-containing particles to the nanometer level, and then adding citric acid. The rubber particles are coated on the surface containing the inscription particles to form a core-shell structure coated with the aluminum-containing particles, and then the pH value of the solution is adjusted to about 1 to dissolve the intermediate core containing the insoluble particles. The hollow particles of rice. Therefore, the advantage of the present invention 1286490 is that the hollow particles can be obtained by the process of adjusting the acid-base value at room temperature, and the method used in the present invention is not only relative to other conventional processes. Of a single, more significantly reduce manufacturing time, energy and costs. [Embodiment
鋁是一種兩性化合物，在極酸（pH < 1 )或極鹼（pH > 10)的環境，鋁都會溶解。本發明利用鋁之此種特性，將 其形成顆粒之後，藉由酸鹼值的調整使之細化成奈米粒子， 並以此奈米粒子為基核，加入矽酸膠顆粒，使其披覆於鋁奈 米粒子的表面上形成核殼結構，最後再將酸鹼值調整到約^ 左右，使鋁奈米粒子溶解，而形成奈米中空粒子。本發明藉 由酸鹼值的調整即可獲得奈米中空粒子，與其它習知製程才曰目 比，本發明所用的方法不但製程相對簡單，而且成本花費也 較低。 在此實施例中，揭露一種中空氧化矽粒子之製作方法， 其步驟包含提供-含銘離子之溶液，接著，加人沉殿劑至含 銘離子之溶液中’以形成含銘粒子，將含銘粒子過濾及水洗 後，加入酸驗值調整劑至含鋁粒子，以調整含鋁粒子之酸鹼 值大約在4至5之間’接著，加人發酸膝顆粒以形成一核殼 結構包覆含銘粒子，以及調整核殼結構之酸驗值大約至！ 左右，以溶解含鋁粒子而得到中空奈米粒子。 請參照第1圖，其係飨示根據本發明之一較佳實施例之 中空：化隸子之製作流程圓。首先，如步㈣所示提 ，=銘離子之溶液’其中含铭離子之溶液係將可溶性的 銘化5物例如硝酸銘或氫氧化料，加人水性溶劑例如去離 8 1286490 銘離:，如步驟12所示’加入-沉殿劑至含 驗值中沉殿劑係調整該含_子之溶液之酸 人10之間’使銘離子從溶液中沉殿析出成為 二=子’在本實施例中，此沉殿劑的成分例如是氨 兔酸錢。之後，如步驟14所示，將所 \j 濾以及水洗製程。接著，如，驟16所-粒子進仃過 ^M^Λ,^者如步驟16所不，加入第一酸鹼值 一酸性分散液’此第一酸驗值調整劑係藉由酸 值來調整3銘粒子的大小，使含銘粒子的大小範圍變化可 從微米級到奈米級，在本實施财，為得到奈米級的含銘粒 子，酸性分散液的酸鹼值會被調整到大約4至5之間，其中 第-酸鹼值調整劑的成分例如是硝酸’然不限於此，其它的 無機酸例如鹽酸、硫酸、磷酸與碳酸以及有機酸例如醋酸也 可以使用，熟習此技蓺者举钎7^ ^ 议贫者田可了解，由於酸鹼值調整劑係用 來調整上述酸性分散液之酸驗值，而f知其他種類之酸類亦 可作為酸驗值調整劑，因此本發明之酸驗值調整劑並不限於 上述所舉。接著，如步驟18所示，加入矽酸膠顆粒，此矽 酸膠顆粒會披覆在含IS粒子的表面上以形成—核殼結構，此 核殼結構會包覆整個含㈣子，在本實施例中，除了使用石夕 酸膠顆粒外’丨―種選擇是使❹酸或四乙氧基石夕烧 (TEOS)等切材料。接著，如步驟2()所示，加入第二酸 鹼值調整劑以調整此酸性分散液的酸鹼值至大約丨左右，此 步驟會使中間核心的含銘粒子溶解，只留下包覆在含銘粒子 外面的核殼結構而形成奈米中空粒子，在本實施例中，此第 二酸鹼值調整劑的成分例如是硝酸，然不限於此，其它的盈 機酸例如鹽酸、硫酸、磷酸與碳酸以及有機酸例如醋酸也可 9 1286490 以使用，熟習此技藝者當可了解，由於酸鹼值調整劑係用來 調整上述酸性分散液之酸鹼值，而習知其他種類之酸類亦可 作為酸鹼值調整劑，因此本發明之酸鹼值調整劑並不限於上 述所舉。 本發明是將鋁沉澱粒子藉由酸鹼值的調整，使之細化 後，另一方面以矽酸膠顆粒加入陳化，在陳化期間矽酸膠顆 粒會披覆於鋁沉澱粒子的表面，最後再將溶液的酸鹼值調整 到約1左右，使中間的銘沉殿粒子溶解，而形成奈米中空粒 子，本發明藉由酸鹼值的調整即可獲得中空粒子，所以簡化 了習知中空粒子之製作方法。 以下列舉一較佳實施例以更詳盡闡述本發明之中空氧 化石夕粒子之製作方法的應用，然其並非用以限定本發明，因 =本發明之保護範圍#視後專利範圍所界定者為 實施例一 中後首：知取重量約18g之硝酸鋁均勻溶於25ml去離子水 中後，再加入稀釋5倍之氨水 8^1〇 Τ以調整溶液之酸鹼值至 ⑶之間’但以酸鹼值在9〜9 5夕m 著，將m π μ ·5之間所侍的效果較好。接 考將所侍的沉澱物經過過瀘、Aluminum is an amphoteric compound in which aluminum is dissolved in a very acidic (pH < 1 ) or polar base (pH > 10) environment. The present invention utilizes the characteristic of aluminum, and after forming the particles, it is refined into nano particles by adjusting the acid-base value, and the nano particles are used as the core, and the citrate rubber particles are added to be coated on the particles. A core-shell structure is formed on the surface of the aluminum nanoparticle, and finally the pH value is adjusted to about φ, so that the aluminum nanoparticle is dissolved to form a nano hollow particle. In the present invention, nano hollow particles can be obtained by adjusting the pH value, and the method used in the present invention is not only relatively simple in process but also low in cost, compared with other conventional processes. In this embodiment, a method for fabricating a hollow cerium oxide particle is disclosed, the method comprising the steps of: providing a solution containing a precursor ion, and then adding a sinking agent to a solution containing a metal ion to form a particle containing a After the particle filtration and water washing, add the acid value adjuster to the aluminum-containing particles to adjust the acid-base value of the aluminum-containing particles to be between 4 and 5. 'Next, add the acid-knee particles to form a core-shell structure coating. Containing the Ming particles, and adjusting the acid shell of the core-shell structure is about! Left and right, to dissolve the aluminum-containing particles to obtain hollow nanoparticles. Referring to Fig. 1, there is shown a process flow circle according to a preferred embodiment of the present invention. First, as shown in step (4), = solution of the imide ion, which contains the solution of the imide ion, which is a soluble enriched substance such as nitric acid or hydroxide, added with an aqueous solvent, for example, to remove 8 1286490: As shown in step 12, 'add------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------ In the embodiment, the component of the sinking agent is, for example, ammonia rabbit acid. Then, as shown in step 14, the \j filter and the water wash process. Then, for example, the particles in step 16 are passed through ^M^Λ, and if not in step 16, the first acid-base value-acid dispersion is added. This first acid value adjusting agent is based on the acid value. Adjust the size of the 3 Ming particles so that the size range of the containing particles can be changed from micron to nanometer. In this implementation, in order to obtain the nanometer-containing particles, the acidity and alkalinity of the acidic dispersion will be adjusted to Between about 4 and 5, wherein the component of the pH-adjusting agent is, for example, nitric acid is not limited thereto, and other inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and carbonic acid, and organic acids such as acetic acid may also be used.蓺 举 7 7 ^ ^ The poor people can understand that because the pH adjuster is used to adjust the acid value of the above acid dispersion, and know that other types of acids can also be used as acid test regulator The acid value adjusting agent of the present invention is not limited to the above. Next, as shown in step 18, phthalic acid granules are added, and the phthalic acid granules are coated on the surface of the IS-containing particles to form a core-shell structure, which covers the entire (tetra)-containing sub- In the examples, in addition to the use of the lyoside gum particles, the 丨-species selection is a tantalum or tetraethoxy zebra (TEOS) or the like. Next, as shown in step 2 (), a second acid-base adjusting agent is added to adjust the acid-base value of the acidic dispersion to about 丨. This step dissolves the containing core particles of the intermediate core, leaving only the coating. The nano hollow particles are formed in the core-shell structure outside the inner particles. In the present embodiment, the composition of the second acid-base adjusting agent is, for example, nitric acid, but is not limited thereto, and other fermenting acids such as hydrochloric acid and sulfuric acid are used. Phosphoric acid and carbonic acid and organic acids such as acetic acid can also be used in the use of 9 1286490. It is understood by those skilled in the art that since the pH adjusting agent is used to adjust the acidity and alkalinity of the above acidic dispersion, other kinds of acids are known. It can also be used as a pH adjuster, and therefore the pH adjuster of the present invention is not limited to the above. In the invention, the aluminum precipitated particles are refined by the adjustment of the acid-base value, and on the other hand, the citrate rubber particles are added to the aging, and the citrate rubber particles are coated on the surface of the aluminum precipitated particles during the aging. Finally, the pH value of the solution is adjusted to about 1, so that the middle Mingshen particles are dissolved to form nano hollow particles, and the present invention can obtain hollow particles by adjusting the acid-base value, thus simplifying the habit Know how to make hollow particles. The following is a list of preferred embodiments to illustrate in more detail the application of the method for producing the hollow oxidized oxide particles of the present invention, which is not intended to limit the invention, since the scope of protection of the present invention is defined by the scope of the patent. In the first part of the first embodiment, it is known that about 18 g of aluminum nitrate is uniformly dissolved in 25 ml of deionized water, and then diluted with 5 times of ammonia water 8^1 〇Τ to adjust the pH value of the solution to between (3) The pH value is between 9 and 9 pm, and the effect between m π μ ·5 is better. After taking the test, the sediment that has been served has passed through
的硝酸，調零^ n "夂冼。之後，利用0.47M 在4〜4.5之間所得的效果較佳。所得漿心广裡：：驗, 3.24Wt%之石夕酸膠3mi ^ 口入固含篁大約 鹼值至1左太，將所侍懸洋液以硝酸調整酸 圖所示。 、人超音波處理後，所得的結果如第2 請參閲第2圖，係利用本 之實施例一的方法所製得 10 1286490 之中空氧化梦粒子之TEM照片。從昭Η 、 製得的粒子為粒徑小於1〇〇nm之夺；、"：得知本發明所 不木級中空氧化矽粒子。 簡言之，本發明之中空氧切粒子之製作方法，立特徵 在於將含銘的沉㈣藉由酸驗值的調整，使其顆粒細：成夺 米級後，再加人錢膠顆粒陳化，之㈣溶液㈣驗值調整 到約1左右，使核心的鋁沉澱物溶解，而形成奈米中空顆 粒。因此，本發明克服習知技術之水熱法以及加熱製程需要 以高溫鍛燒的方式或是用氫氟酸腐餘的方式才能將中間模 ，移除的缺點’直接藉由酸驗值的調整就可以移除模板而獲 得奈米中空粒子’所以與其它製程相比，本發明所用的方法 相對簡單。再者’應用本發明之方法不僅簡化習知中空氧化 矽粒子之製作方法，而且大幅降低製造的能源及成本，更可 快速量產中空氧化石夕粒子。 由上述本發明較佳實施例可知，本發明為一種以含鋁粒 子為模板來製作中空氧化矽粒子之方法，有別於一般以其它 粒子為模板所製成的中空粒子，本發明的優點在於不需要高 /里與咼壓的反應製程，只需在室温下藉由酸鹼值的調整，即 了達到製作中空氧化石夕粒子的目的。如此一來，本發明之中 工氧化石夕粒子之製作方法不僅簡化習知中空氧化石夕粒子之 製程，更大幅降低製造時間、能源及成本，進而可快速量產 中空氧化石夕粒子。藉由本發明所製作的中空氧化矽粒子，由 於具有製作速度快且成本低的優勢，將更可廣泛地應用於抗 反射薄膜之使用上。 雖然本發明已以數個較佳實施例揭露如上，然其並非用 以限定本發明’任何熟習此技藝者，在不脫離本發明之精神 11 1286490 和棘圍内，當可作各種之更動盥 ®合遇切“種之更勳與潤飾，因此本發明之保護範 圍田視後附之申請專利範圍所界定者為準。 【圖式簡單說明] 為讓本發明之上述和其他目的、特徵、和優點能更明顯 易懂，下文特舉一較佳實施例，並配合所附圖式，作詳細說 明如下： ’ 第1圖係繪示根據本發明一較佳實施例之中空氧化矽 粒子之製作流程圖；以及 第2圖係根據本發明之另一較佳實施例所形成之务米 級中空氧化矽粒子之TEM照片。 ,、 【主要元件符號說明】 10 : 提供含有鋁離子之溶液 12 : 加入沉澱劑 14 : 進行過濾以及水洗 16 : 加入第一酸驗值調整劑 18 : 加入矽酸膠顆粒 20 : 加入第二酸鹼值調整劑 12Nitric acid, zeroing ^ n "夂冼. Thereafter, the effect obtained by using 0.47 M between 4 and 4.5 is preferred. The obtained pulp heart is wide:: test, 3.24Wt% of the stone acid gel 3mi ^ mouth into the solid content 篁 about the base value to 1 left too, the desired suspension of the liquid is adjusted with acid by nitric acid. After the human ultrasonic treatment, the results obtained are as shown in Fig. 2, and a TEM photograph of the hollow oxidized dream particles of 10 1286490 was obtained by the method of the first embodiment. The particles obtained from Zhaoqi, the particle size is less than 1 〇〇 nm; and ": the non-wood-scale hollow cerium oxide particles of the present invention are known. Briefly, the method for producing the hollow oxygen-cut particles of the present invention is characterized in that the sedimentation of the inscription (4) containing the inscription is adjusted by the acid value to make the particles fine: after the rice level is reached, the human rubber particles are added. (4) The solution (4) is adjusted to about 1 to dissolve the core aluminum precipitate to form nano hollow particles. Therefore, the present invention overcomes the conventional art hydrothermal method and the heating process requires high-temperature calcination or hydrofluoric acid to reduce the disadvantage of the intermediate mold, which is directly adjusted by the acid value. The template can be removed to obtain nano hollow particles 'so the method used in the present invention is relatively simple compared to other processes. Further, the application of the method of the present invention not only simplifies the production method of the conventional hollow cerium oxide particles, but also greatly reduces the energy and cost of production, and enables the mass production of hollow oxidized oxide particles. According to the preferred embodiment of the present invention described above, the present invention is a method for producing hollow cerium oxide particles by using aluminum-containing particles as a template, which is different from hollow particles which are generally made of other particles as a template. The advantage of the present invention is that There is no need for a high/inverse and pressure-reacting reaction process, and it is only necessary to adjust the pH value at room temperature to achieve the purpose of producing hollow oxidized oxide particles. In this way, the method for producing the oxidized granules of the present invention not only simplifies the process of the conventional hollow oxidized oxide particles, but also greatly reduces the manufacturing time, energy, and cost, and further rapidly mass-produces the hollow oxidized oxide particles. The hollow cerium oxide particles produced by the present invention are more widely used for the use of the antireflection film because of their advantages of high production speed and low cost. While the present invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention to any of those skilled in the art, and various modifications may be made without departing from the spirit of the present invention, 11 1286490 and the spine. The combination of the above-mentioned and other objects and features of the present invention is subject to the definition of the patent application scope of the present invention. The advantages and advantages can be more clearly understood. The following is a detailed description of the preferred embodiment and the accompanying drawings, which are described in detail below: ' FIG. 1 is a diagram showing hollow cerium oxide particles according to a preferred embodiment of the present invention. Manufactured flow chart; and Fig. 2 is a TEM photograph of a hollow rice cerium oxide particle formed according to another preferred embodiment of the present invention. [, Main component symbol description] 10 : Providing a solution containing aluminum ions 12 : Add precipitant 14 : Filter and wash 16 : Add first acid test adjuster 18 : Add citric acid gel particles 20 : Add second acid base adjuster 12