TW576755B - Improved rhodium electrocatalyst and method of preparation - Google Patents

Abstract

An improved novel rhodium sulphide catalyst for reduction of oxygen in industrial electrolyzers which is highly resistant towards corrosion and poisoning by organic species, thus making it particularly suitable for use in aqueous hydrochloric acid electrolysis, also when technical grade acid containing organic contaminants is employed. By modifying the method of preparation, the activity and consistency of the catalyst is substantially improved.

Description

576755 案號 91132842 年 月 曰 修正 五、發明說明（1) 先前技術 HC 1水溶液電解是高值氯氣的公知回收方法。塩酸水 溶液係豐富的化學副產品，尤其是以氯為反應物之化學工 廠，在此情況下，電解池陽極室釋出的氣，可作為進料再 循環至化學工廠。由於耗能大降，標準釋氫陰極改用耗氧 氣體擴散電極時，電極很引人注目。氣體擴散電極在此文 脈中成功操作的能力決定性視觸媒的性能和績效而定，亦 視氣體擴散電極的結構而定。 鉑一般認定為在廣泛條件下，氧利用電化學反應還原 (按：在酸性環境下產生水）最有效的觸媒。氣體擴散電極 以鉑質觸媒活化，已屬公知，在燃料電池和許多種電解池 方面有廣大用途。然而，HC 1水溶液電解使用鉑為陰極觸 媒有些嚴重的缺點，因為氣體擴散陰極不免至少部份會與 含有氣化物離子和溶解氣的液體電解質接觸。尤其是鉑易 受氣化物離子中毒，對氧的還原活性有負面影響。中毒的 第二來源是污染物所構成，尤其是有機物，大多數情況下 溶於進行電解的副產品塩酸内。 更重要的是，塩酸和溶解氣離子之合併複合作用，會 改變鉑金屬成為可溶性塩，溶解掉，使此材料不適用作氣 體'擴散電極。此外，在電解池定期停工時必須極其小心注 意，否則陰極電位突然轉變，加上高度侵蝕性的化學環境 ，造成大量觸媒溶解，以及其餘部份的部份失落。為電解 池有計劃停工修改程序會增加成本，但由於輸電網路上缺 電等意外原因，在突然無法控制的停工情況下，則很少或 根本無法應付。576755 Case No. 91132842 Modification 5. Description of the invention (1) Prior art HC 1 aqueous solution electrolysis is a well-known method for recovering high-value chlorine gas. The osmotic acid solution is a rich chemical by-product, especially in chemical plants using chlorine as a reactant. In this case, the gas released from the anode chamber of the electrolytic cell can be recycled to the chemical plant as feed. Due to the large reduction in energy consumption, the standard hydrogen-releasing cathode was noticeable when it was switched to an oxygen-consuming gas diffusion electrode. The ability of a gas diffusion electrode to successfully operate in this context depends critically on the performance and performance of the catalyst, and also on the structure of the gas diffusion electrode. Platinum is generally recognized as the most effective catalyst for reducing oxygen using electrochemical reactions under a wide range of conditions (by: producing water in an acidic environment). Gas diffusion electrodes are known to be activated with platinum catalysts, and have a wide range of uses in fuel cells and many types of electrolytic cells. However, the use of platinum as a cathode catalyst for HC 1 aqueous solution electrolysis has some serious disadvantages, because the gas diffusion cathode will inevitably come into contact with a liquid electrolyte containing gaseous ion and dissolved gas at least in part. In particular, platinum is susceptible to gaseous ion poisoning and has a negative effect on the reducing activity of oxygen. The second source of poisoning is the composition of pollutants, especially organic matter, which is mostly dissolved in the by-product of electrolysis, acetic acid. More importantly, the combined compounding effect of osmic acid and dissolved gas ions will change the platinum metal into soluble plutonium and dissolve it, making this material unsuitable for use as a gas' diffusion electrode. In addition, extreme care must be taken when the electrolytic cell is shut down periodically, otherwise sudden changes in the cathode potential, coupled with a highly aggressive chemical environment, will cause a large number of catalysts to dissolve and the rest to be lost. Modifying the procedures for planned shutdown of the electrolytic cell will increase costs, but due to unexpected reasons such as power shortages on the transmission grid road, in the case of sudden uncontrollable shutdowns, there will be little or no coping.

576755 _案號91132842_年月 曰 修正_ 五、發明說明（2) 其他始族金屬呈現類似命運。例如按照P 〇 u r b a i X的 《水溶液電化學平衡總覽》，微粉化铑金屬可溶於熱濃硫 酸、王水和充氧塩酸内。同理，（水合）Rh203 · 5H20易溶於 HC 1和其他酸内。在美國專利第5，9 5 8，1 9 7號所載铑/氧化 铑質觸媒内容中，此等問題已部份緩和。尤其是铑/氧化 铑系統雖然活性稍遜於鉑之對氧還原，卻不會因氣化物離 子而中毒。鉑對含有少量溶解氯的塩酸水溶液之化學抵抗 性有明顯增進。然而，需要有活化步驟來獲得此觸媒的充 分活性和穩定型式，而如此觸媒必須包含在氣體擴散電極 内時，會引起某些限制。例如，觸媒的化學和電子狀態因 在空氣中燒結而變化，這是技藝中已知氣體擴散電極製法 中很常用的步驟。如美國專利第5，9 5 8，1 9 7號所述，要更 換此步驟或隨後要恢復觸媒的活性和穩定型式，必須進行 繁雜和/或昂貴的操作。前述铑/氧化铑固有之限制，由 美國專利第6，1 4 9，7 8 2號所揭示新穎硫化铑觸媒加以克服 。茲發現在製法内引進某些變化，使績效和一貫性可獲得 超越美國專利第6，1 4 9，7 8 2所揭示的意外增益。 發明目的 本發明之目的，在於提供一種氧還原用改進觸媒，對 高度腐蝕性媒質具有所需而意'外之化學安定性，因而透過 出發物料的預處理，可以實現此等改進。 本發明另一目的，在於提供氧還原用改進觸媒，在有 機污染物存在下具有所需而意外之電觸媒活性。 本發明又一目的，在於提供帶有改進觸媒之新穎氣體 擴散電極，具有所需而意外的電觸媒性能，以及較低和更576755 _ Case No. 91132842_ Year Month Revision _ 5. Description of the invention (2) Other founding metals show similar fate. For example, in accordance with the "Overview of the Electrochemical Equilibrium of Aqueous Solutions" of Po ur b a i X, micronized rhodium metal is soluble in hot concentrated sulfuric acid, aqua regia, and oxygenated osmic acid. Similarly, (hydrated) Rh203 · 5H20 is easily soluble in HC 1 and other acids. These problems have been partially alleviated in the rhodium / rhodium oxide catalyst content contained in U.S. Patent Nos. 5,9 5,8,197. In particular, the rhodium / rhodium oxide system, although slightly less active than platinum for oxygen reduction, is not poisoned by gaseous ions. The chemical resistance of platinum to aqueous solutions of gallic acid containing a small amount of dissolved chlorine has been significantly improved. However, an activation step is required to obtain a fully active and stable version of this catalyst, and such a limitation will be caused when the catalyst must be contained in a gas diffusion electrode. For example, the chemical and electronic state of the catalyst changes due to sintering in air, which is a very common step in gas diffusion electrode manufacturing methods known in the art. As described in U.S. Patent Nos. 5,9,58,197, complicated and / or expensive operations must be performed to change this step or to subsequently restore the activity and stability of the catalyst. The aforementioned inherent limitations of rhodium / rhodium oxide are overcome by the novel rhodium sulfide catalyst disclosed in U.S. Patent No. 6,1,49,7,82. It is found that the introduction of certain changes in the manufacturing method allows performance and consistency to be surpassed by the unexpected gains disclosed in U.S. Patent Nos. 6,14,7,82. OBJECTS OF THE INVENTION The object of the present invention is to provide an improved catalyst for oxygen reduction, which has the required chemical stability for highly corrosive media. Therefore, these improvements can be achieved through the pretreatment of starting materials. Another object of the present invention is to provide an improved catalyst for oxygen reduction, which has the required and unexpected electrical catalyst activity in the presence of organic pollutants. Another object of the present invention is to provide a novel gas diffusion electrode with improved catalyst, which has the required and unexpected electrical catalyst performance, and lower and more

576755 五、發明說明（3) 為一致之操作 本發明再 之電解池，並 本發明上 白。 發明内容 本發明新 性惰性載體上 步驟，且出乎 可保持全盤對 地不被塩酸水 塩酸電解池内 觸媒最好 黏合劑、混拌 上並合併黏合 可塗在織物的 碳布、碳紙， 屬網所製成。 高表面積 其他微細化載 如此塗佈 常操作條件下 諸如在塩酸副 電壓、電流密 在觸媒製 Ά 91132842 電壓576755 V. Description of the invention (3) Consistent operation The present invention is an electrolytic cell, and the present invention is white. SUMMARY OF THE INVENTION The novel inert carrier step of the present invention is better than the catalyst that can keep the entire surface from being touched by the acid in the electrolytic cell. The best binder is to mix and mix and combine the carbon cloth and carbon paper that can be coated on the fabric. Made of nets. High surface area, other fine-grained coatings, such coatings, under normal operating conditions, such as osmium acid secondary voltage, current density, and catalyst production Ά 91132842 voltage

二^在於提供含有本發明氣體擴 ^供塩酸電解成氯之改進方法。-述和其他目的及優點，由如下詳述即 散電極 可明 穎電 與否 意外 氧還 溶液 使用 塗佈 導電 化學 均可 地， 原之 一氣 時， 在基 性載 黏合 或双 或對腐蝕 劑。 一側 觸媒 。此 在氣 電觸 混合 遇停 材的 體和 劑可 側。 性電 ，由 觸媒 化物 媒活 物之 工不 至少 黏合 為疏 基材 解液 硫化 在使 離子 性。 複合 需特 一側 劑， 水性 可為 有抵 铑構 用之 和有 此外 作用 別小 ，亦 或承 或親 編織 抗性 成，承載 前不需任 機分子存 ，觸媒出 所溶解， 心 〇 可單獨使 載在導電 水性，而 或不織物 的任何導 載體之例，包 體’但以碳黑 觸媒之基材可 ’尤其在高度 產品電解情況 度和使用壽命 含石墨、各種形式的碳 為佳。 用作氣體擴散電極，顯 € 環境和低純度反 下使用時，以前得不到 於導電 何活化 在下， 乎意外 因而在 用、加 性載體 混合物 ’或由 電性金 ，以及 示在通 應物， 的電池 先質在The second aspect is to provide an improved method for the electrolysis of gallic acid to chlorine containing the gas expansion of the present invention. -Reference and other purposes and advantages, as detailed below, the scattered electrode can be used to indicate whether the electricity is accidental or not. The redox solution is used to coat the conductive chemistry. In the same way, the basic carrier is bonded or double or anti-corrosive. Catalyst on one side. This is the side of the gas and electric contact mixing materials and agents can be side. Sexual electricity is not at least adhered to the sparse substrate by the catalyst and the catalyst, and the solution is vulcanized to make it ionic. The compound requires a special agent, and the water can be a combination of anti-rhodium structure, but also has a small effect, or it can be made or resistant to weaving. It does not require any molecular molecules to be stored before loading, and the catalyst is dissolved. Examples of any conductive carrier that is contained in a conductive water-based or non-woven fabric, the package body 'but the substrate with a carbon black catalyst may', especially at a high degree of product electrolysis and a service life containing graphite, various forms of carbon are good. When used as a gas diffusion electrode, when it is used under the environment and low purity, it cannot be used to conduct electricity. It is unexpectedly used, additive carrier mixture, or made of electrical gold, and it is shown in the product. The battery precursor is

麵IIFace II

576755 _案號91132842_年月曰 修正_ 五、發明說明（4) 回流溫度加熱，直至獲得異構物的穩定分配。氯化铑的異 構物分配是按照UV/V I S吸收光譜（按：意即光的波長是在紫 外線（U V )至可見光（V I S)區域内之光譜），以確保獲得穩定 狀態。所得硫化铑具有改進績效，由增加半波電位結果可 知。 無論硫化铑是否回流，在已經高度耗用的碳黑上澱積 電觸媒時，會在硫化铑的電觸媒内發生另一項改進。 在與氯化铑塩混合之前，碳黑以高能混合器分散。一 種方法是經由微流體化器完成，此係壓力驅動系統，如 Microfluidics(美國麻州牛頓市）等公司有售。 其他方法使用轉子/靜子法，將一組刀片固定，另一 組以高速繞固定組旋轉。如此作用對樣本產生較高剪力。 轉子/靜子操作常以分批模式進行。另一裝置是磨機，有 板之旋筒對溶液進行輸送剪力能量的功用。Kady公司（美 國、纟面因州S c a r b 〇 r o u g h市）提供此等機器範圍。凡此和類似 裝置稱為「勻化器」，以均勻而一致的方式，進行把固體 分散入溶劑内之重大功能。在以下實施例内將說明藉簡單 混合以形成碳黑分散的硫化铑觸媒前所未見的製造，並列 出結果。 合併兩種特點可得'最佳結果，即氣化铑的單一異構物 澱積在高度分散的碳黑上，得實質上提高半波電位之電觸 媒。 回流氣化铑溶液的混合物，與分散碳黑混合，並經超 音波步驟。再將硫化氳氣體噴入水溶性铑塩之水溶液内， 即製成硫化铑錯合物。氮氣可用作硫化氫的載體，而在反576755 _ Case No. 91132842_ Year Month Amendment _ V. Description of the invention (4) Heating at reflux temperature until stable distribution of isomers is obtained. The isomer distribution of rhodium chloride is based on the UV / V I S absorption spectrum (in terms: the wavelength of light is the spectrum in the ultraviolet (U V) to visible light (V I S) region) to ensure a stable state. The obtained rhodium sulfide has improved performance, which can be seen from the result of increasing the half-wave potential. Regardless of whether the rhodium sulfide is reflowed or not, another improvement occurs in the rhodium sulfide electrocatalyst when the electrocatalyst is deposited on the carbon black that has been highly consumed. The carbon black is dispersed in a high-energy mixer before mixing with rhodium rhenium chloride. One method is done via a microfluidizer, which is a pressure-driven system such as that available from companies such as Microfluidics (Newton, Mass.). Other methods use the rotor / static method to fix one set of blades and the other set to rotate around the fixed set at high speed. This action produces a higher shear force on the sample. Rotor / quiet operation is often performed in batch mode. The other device is a mill, which has the function of transmitting shear energy to the solution by a plate spinner. Kady, Inc. (Sca, rb, rog, uhh, U.S.A., USA) provides these machine ranges. These and similar devices are called "homogenizers" and perform a significant function of dispersing solids into solvents in a uniform and consistent manner. In the following examples, the production of a carbon black-dispersed rhodium sulfide catalyst by simple mixing to form a carbon black-dispersed rhodium sulfide catalyst will be explained, and the results will be listed. Combining the two features yields the 'best result', namely that a single isomer of vaporized rhodium is deposited on highly dispersed carbon black, and an electrical catalyst that substantially increases the half-wave potential is obtained. The mixture of vaporized rhodium solution was refluxed, mixed with dispersed carbon black, and subjected to an ultrasonic step. The rhenium sulfide gas is sprayed into an aqueous solution of water-soluble rhodium rhenium to prepare a rhodium sulfide complex. Nitrogen can be used as a carrier for hydrogen sulfide.

576755 __案號 91132842__月_g_ 修正 五、發明說明（5) 應完成時，且用純氮流來排淨過量硫化氫。所得固體利用 過濾、洗濯、在例如1 2 5 C乾燥至常量，加以回收。所得 硫化姥。形式必須在5 5 0。 - 6 5 0 °c的惰性氛圍内加熱，最好 在6 0 0 C以上，以形成硫化铑觸媒之良好界定結晶型。加 熱可歷數小時，視批料大小而定，而溫度的選擇對形成充 分安定而活性的觸媒具有關鍵性。 若溫度太低，諸如3 〇 〇 t，所得微晶不充分界定，而 觸媒女疋性不足。若溫度太高，即725 °c，未受承載的觸 媒有優異的酸安定性，但未擁有充分的電化學活性。 圖式簡單 第1圖為硫化铑觸媒樣品承載於轉盤電極（RDE)尖端， 並經電壓掃描所得典型流體動力電壓圖。三電極組成採用 飽和甘汞參，電極（SCE)，和鉑絲抗衡電極。溶液為5%HC1 ，在飽和空氣的室溫測試。在半平台高度之半波位置用作 分析電壓。 第2圖為使用氧去極化氣體擴散電極，從HC1產生c 採用氣體擴散電極測試系統簡單流程圖。 第3圖為使用實施例1或比較例1之方法製成的一系列 觸媒，並添加於實施例2 (b)氣體擴散電極内衍生之曲線 圖。各觸媒使用RDE評估，再於第2圖組成中測試的、氣體擴 散電極内評估。曲線圖把來自RDE(£ 1/2)的分析電壓與同 樣觸媒用的實驗電池内所得加以比較。 第4圖表示比較例丨觸媒，以只有原料塩回流製成的觸 媒，以只有奴黑分散和混合物的聲波降解法製成的觸媒， 以及兼具回流和分散/聲波降解法製成的觸媒之半波位置576755 __Case No. 91132842__ 月 _g_ Amendment V. Description of the invention (5) When it should be completed, pure hydrogen flow should be used to remove excess hydrogen sulfide. The obtained solid is filtered, washed, dried to a constant at 1 2 5 C, and recovered. The resulting rhenium sulfide. The form must be 5 5 0. -Heating in an inert atmosphere at 650 ° C, preferably above 600 C, to form a well-defined crystal form of rhodium sulfide catalyst. Heating can take several hours, depending on the batch size, and the choice of temperature is critical to the formation of a sufficiently stable and active catalyst. If the temperature is too low, such as 300 t, the microcrystals obtained are insufficiently defined, and the catalyst is not sufficiently sexual. If the temperature is too high, ie, 725 ° C, the unsupported catalyst has excellent acid stability, but does not have sufficient electrochemical activity. The diagram is simple. Figure 1 is a typical hydrodynamic voltage diagram obtained by scanning the voltage of a rhodium sulfide catalyst sample at the tip of a turntable electrode (RDE). The three-electrode composition uses a saturated calomel ginseng, electrode (SCE), and a platinum wire counter electrode. The solution is 5% HC1 and tested at room temperature in saturated air. The half-wave position at the half-platform height is used as the analysis voltage. Figure 2 is a simple flow chart of a gas diffusion electrode test system using oxygen depolarized gas diffusion electrodes to generate c from HC1. Figure 3 is a graph of a series of catalysts made using the method of Example 1 or Comparative Example 1 and added to the gas diffusion electrode of Example 2 (b). Each catalyst was evaluated using RDE, and then evaluated in the gas diffusion electrode tested in the composition of Figure 2. The graph compares the analytical voltage from RDE (£ 1/2) with that obtained in an experimental battery for the same catalyst. Figure 4 shows a comparative example. The catalyst is a catalyst made of only the raw material 塩 reflow, a catalyst made of the sonic degradation method with only slave black dispersion and mixture, and a combination of reflow and dispersion / sonic degradation Half-wave position of the catalyst

第10頁 576755 _SS_9U32842 曰 修正 五、發明說明（6) 比較。 第5圖RI1CI3 · nH2〇剛溶解之溶液和回流2· 5小時後所得 典型UV/VIS譜。 實施方^ 、在以實施例中記述若干較佳具體例，以說明本發明 。然而’須知本發明無意限制於特定具體例。 實施例1 ^ 按I述製備一批100克承載於碳上之硫化铑。把定量 氣化姥塩加。到脫離子水，調成Rh金屬濃度約60 i。此溶 ，（9 0 - 1 0 0 c )回流過夜，即約丨6小時。回流進度以uv/V! s 光譜追蹤。回流完成時，在47〇 —47 5nmi收與在374-38〇nm 吸收之比，應在〇 · 9 -1 · 1範圍，以1為佳。參見第5圖，為 回流2 · 5小時後所得的典型光譜。 另行在大型（約4公升）燒杯内，把64.00克Vulcan XC - 入2.0公升脫離子水内。混合物利用Silvers〇n(g)轉子 /靜子加以鬲剪力混合。混合物以Μ⑽—g 〇⑽r P m在水平和 直立方向激烈攪拌。經高剪力混合，分散的碳混合物移到 有大型授拌棒的容器，加4〇〇毫升69 g/1 RhO溶液（27· 6克 Rh金屬）。把溶液在磁力攪動板上混合至少5分鐘。 把容器放入超音波浴内2 〇分鐘，進一步處理金屬和碳 黑混合物。用氮以大約3〇 1/hl^淨容器3〇_6〇分鐘。令h2S 以所需流量冒泡通過容器，典型上約8 — 9公升/小時，同時 氣以3 0 1 /hr繼續。HJ開始冒泡後5小時，取少量溶液混合 物樣品。經過濾，以XRF*UV/VIS核對Rh濃度，以確認生 成物在碳載體上之吸收。確認生成物在碳上吸收完全後，Page 10 576755 _SS_9U32842 Revision V. Description of Invention (6) Comparison. Figure 5. Typical UV / VIS spectrum obtained after RI1CI3 · nH2O solution and 2.5 hours after reflux. The implementer ^ describes some preferred specific examples in the examples to illustrate the present invention. However, it should be noted that the present invention is not intended to be limited to specific examples. Example 1 ^ A batch of 100 grams of rhodium sulfide supported on carbon was prepared as described in I. Increase the amount of gasification. In deionized water, adjust the Rh metal concentration to about 60 i. This solvent, (90-100 c) refluxed overnight, that is, about 6 hours. The reflow progress is tracked in the uv / V! S spectrum. When the reflux is completed, the ratio of the 47nm to 47nm nm absorption to the 374nm to 380nm absorption ratio should be in the range of 0.9 to 1.1, preferably 1. See Figure 5 for a typical spectrum obtained after 2.5 hours at reflux. Separately, put 64.00 grams of Vulcan XC-in a large (about 4 liter) beaker into 2.0 liters of deionized water. The mixture was mixed using a Silverson (g) rotor / stator with shearing force. The mixture was stirred vigorously with Μ⑽—g〇⑽r P m in the horizontal and upright directions. After high shear mixing, the dispersed carbon mixture was transferred to a container with a large stir bar, and 400 ml of a 69 g / 1 RhO solution (27.6 g of Rh metal) was added. Mix the solution on a magnetic stir plate for at least 5 minutes. The container was placed in an ultrasonic bath for 20 minutes to further process the metal and carbon black mixture. The container was purged with nitrogen at about 31 / hl ^ for 30-60 minutes. H2S is bubbled through the container at the required flow rate, typically about 8-9 liters / hour, while gas continues at 30 1 / hr. Five hours after HJ started bubbling, take a small sample of the solution mixture. After filtration, the Rh concentration was checked with XRF * UV / VIS to confirm the absorption of the product on the carbon support. After confirming that the product is completely absorbed on the carbon,

____

第11頁 576755 ‘年月 曰 修正 案號 91132842 五、發明說明（7) 停止硫化氫流動。繼續以氮棑淨過夜。翌日，使用真命果 經Buchner漏斗過濾觸媒，不洗濯，只稍微淋洗容器〃（二⑽ ，升）。過滤後的中間物在〜120。(：溫度的烘箱内放置過 夜。乾燥後，準備烘箱，以氬在室溫排淨丨小時。繼續惰 性排淨，烘箱溫度在1小時内從室溫上升产 6 5 0 °C保持2小時，加熱器關閉後，令烘爐在氬内冷卻^室 f $夜。觸媒從供爐除去後，經分析，製成氣體擴散電極 或溽膜電極總成。 比較例1 按下述程序製備100克受承載的硫化铑：取57.3克 RhCl3 · nH20(算成鍺金屬為39· 88%)溶入2公升脫離子（D· j) 水内，不調節pH。加53· 4克Vulcan XC-72活性炭，混合物 利用磁力攪拌器打漿。 再使用氮為載氣，將硫化氩喷入周圍溫度的漿液内。 讓混合物按所述反應7小時。反應完成時，以氮排經系統 ’除去殘餘HsS。剩餘溶液經真空過濾，把固體孤離，再用 脫離子水洗淨，在125 °c乾燥至常量。 所得觸媒餅最後磨成細粉，在流動氬内經6 5 (TC歷2小 時。得碳上觸媒負荷2 7 - 2 8 %，以铑金屬計算。 實施例2 、 上列實施例全部觸媒，連同商業化Vulcan XC-72上之 麵（例如E-TEK， Inc製品），可以了列若干不同形態利用。 本备明觸媒不受氣體擴散電極結構的限制。 (a)ELAT®電極：從市售產品選用碳布基材，經紗對緯 紗比為1 ’每吋約2 5 - 5 0支紗，厚度1 0 - 1 5密耳。厚5 - 5 0密Page 11 576755 ‘Year and Month Amendment No. 91132842 V. Description of Invention (7) Stop the flow of hydrogen sulfide. Continue purifying with azazone overnight. On the following day, the catalyst was filtered through a Buchner funnel using a real fruit. Rinse the container a little (2 ，, l) without washing. The filtered intermediate was at ~ 120. (: The temperature is left in the oven overnight. After drying, prepare the oven, and argon purge at room temperature for 丨 hours. Continue inert purge, the oven temperature rises from room temperature within 1 hour to produce 650 ° C for 2 hours, After the heater was turned off, the oven was allowed to cool in the argon chamber. The catalyst was removed from the furnace and analyzed to make a gas diffusion electrode or tritium membrane electrode assembly. Comparative Example 1 Prepare 100 according to the following procedure. Gram supported rhodium sulfide: Take 57.3 grams of RhCl3 · nH20 (calculated as germanium metal 39. 88%) and dissolve it in 2 liters of deionized (D · j) water without adjusting the pH. Add 53.4 grams of Vulcan XC- 72 activated carbon, the mixture was beaten with a magnetic stirrer. Then nitrogen was used as a carrier gas, and argon sulfide was sprayed into the slurry at ambient temperature. The mixture was allowed to react for 7 hours as described. When the reaction was completed, nitrogen was passed through the system to remove residual HsS. The remaining solution was vacuum filtered, the solid was isolated, washed with deionized water, and dried to a constant temperature at 125 ° C. The obtained catalyst cake was finally ground into a fine powder, and was passed through flowing argon for 6 5 (TC for 2 hours). The catalyst load on carbon is 27-28%, calculated based on rhodium metal. Example 2 All the catalysts in the above examples, together with the surface of the commercial Vulcan XC-72 (such as E-TEK, Inc products), can be used in a number of different forms. The catalysts are not limited by the structure of the gas diffusion electrode. (a) ELAT® electrode: a carbon cloth substrate is selected from commercially available products. The warp-to-weft ratio is 1 'about 2 5-50 counts per inch, and the thickness is 10-15 mils. The thickness is 5-5 0 mils.

第12頁 576755 ^^ 91132842 五、發明說明（8) 耳的破布’可有利用於此目的。在碳布各側塗佈氟化聚人 物的混合物（聚四氟乙烯，PTFE，杜邦公司製品，商標。Page 12 576755 ^^ 91132842 V. Description of the invention (8) Ear rags can be used for this purpose. Coated with a mixture of fluorinated polymers (polytetrafluoroethylene, PTFE, DuPont products, trademarks) on each side of the carbon cloth.

Tef Ion®，和 Shawinigan 乙炔黑（SAD)碳，Cabot 公司產銷） ’每次塗後在室溫風乾，直到總負載為8 —10 mg/cm2。再在 碳基材一側多次塗佈粉末觸媒和Te f 1 on®之混合物，得一 層觸媒為0· 5-2 mg/cm2。最後塗佈後，碳布加熱到34〇 ， 經2 0分鐘。 (b) 單側ELAT®電極：重複上述ELAT®電極製造程序， 惟只在碳布一側施加S A B / T e f 1 ο η®混合物，負載為4 - 5 m g / cm2。在同側施加觸媒塗佈於SAB/Teflon®層頂面。 (c) 流動貫穿電極：選用和ELAT®電極同樣規格的碳布 ’於其一側施加觸媒粉末和T e f 1 ο η ®混合物，塗佈2 - 5次。 塗過的布再在340 °C加熱約20分鐘，得1·03 mg/cm2的姥金 屬。最後加熱步驟或燒結步驟咸信可熔化Teflon®，分佈 於碳觸媒全面。然而，為此電極可成功省略燒結步驟。 (d) 薄膜電極總成：配製油墨，包含大約3份觸媒和1 份（乾重）Nafio η®離聚物，諸如Solutions科技公司（美國 賓州Mendenhall市）所產銷，呈在水和甲醇、丙醇和/或 丁醇等低級脂族醇的混合物内之懸浮液。油墨經由噴或漆 ，施加於杜邦公司銷售的Na f i on® 3 2 4離子交換臈，以加 熱真空枱固定其位，亦可變通利用技藝上已知之其他離子 交換膜。施加接讀油墨層，直至澱積〇 · 0 5至1 m g的金屬/ mg/cm2觸媒。此總成又加熱以除去溶劑，並與適當電極背 面組合，如美國專利第6，1 0 3，0 77號所載。所述觸媒油墨 亦可變通施加於電極背面，隨後加熱，除去溶劑，與離子Tef Ion®, and Shawinigan acetylene black (SAD) carbon, produced and sold by Cabot) ’After each application, air-dry at room temperature until the total load is 8-10 mg / cm2. On the carbon substrate side, a mixture of powder catalyst and Te f 1 on® was applied multiple times to obtain a layer of catalyst of 0.5-2 mg / cm2. After the final coating, the carbon cloth was heated to 34 ° C for 20 minutes. (b) Single-sided ELAT® electrode: Repeat the above-mentioned ELAT® electrode manufacturing process, except that the S A B / T e f 1 ο η® mixture is applied to only one side of the carbon cloth with a load of 4-5 m g / cm2. Apply a catalyst on the same side to coat the top surface of the SAB / Teflon® layer. (c) Flow through electrode: Use a carbon cloth of the same size as the ELAT® electrode, and apply a mixture of catalyst powder and T e f 1 ο η ® on one side, and apply it 2 to 5 times. The coated cloth was heated at 340 ° C for about 20 minutes to obtain 1.03 mg / cm2 of rhenium. The last heating step or sintering step can melt Teflon® and distribute it throughout the carbon catalyst. However, the electrode can successfully omit the sintering step for this purpose. (d) Thin-film electrode assembly: formulated ink containing approximately 3 parts of catalyst and 1 part (dry weight) of Nafio η® ionomer, such as those produced by Solutions Technology Corporation (Mendenhall, PA, USA), in water and methanol Suspension in a mixture of lower aliphatic alcohols such as, propanol and / or butanol. The ink is applied by spraying or lacquering to Nafion® 3 2 4 ion-exchanging resin sold by DuPont, which is held in place by a heating vacuum table, and other ion-exchange membranes known in the art can also be used. A read-through ink layer is applied until 0.05 to 1 mg of metal / mg / cm2 catalyst is deposited. This assembly is heated again to remove the solvent and combined with a suitable electrode backside, as described in U.S. Patent No. 6,103,077. The catalyst ink can also be applied to the back of the electrode, and then heated to remove the solvent and ion.

第13頁 576755 卞 案號 9113284g_ 五、發明說明（9) 交換臈組合，形成相等i膜電極總成 實施例3 為證明按照實施例1所製成觸媒之一致性，並將使用 比較例1方法改進製成的多批觸媒加以比較，乃採用轉盤 電極（RDE )，獲得獨立於實驗電池測試的電化學資料。製 =硫化铑承載於碳之稀油墨，將33毫克受承載觸媒和25毫 升異丙醇及25毫升Μ水混合。總共！微升的此油墨，塗佈 於玻璃狀碳轉動電極（直徑6mm)的尖峰2_3次。一旦油墨乾 燥，施加另一層5% Nafion®離聚物溶液（1〇微升）了並蒸發 ^ ί電=(H放〜室溫的5% HC1。翻抗衡電極和標準甘汞 ^ ^電極（SCE)，連同轉盤，接至pAR 373電位計。在各種 二=:一=加電位掃描，由此記錄代表溶解氧還原的平 二二ΐ ^ 2 Ϊ二半之波型電位（見第1圖），用作觸媒氧還 ，反應之刀析扎標。正電位愈高，表示氧還原之方便性愈 大0 。 # / I二Ϊ t例L或比較例1之方法所製成觸媒，製作如實 K驗_ : ί 1 3氣體擴散電極。所得氣體擴散電極使 異冷μ ^/ 忒如下。按照實施例2配置電解實驗。 暴路的電極表面稽, 鈦網，以氧化釕觸ί活匕4隔^為Nafi〇n 324。陽極為 量，在〜5cm水私H 氣以化學計量過量的2. 5倍流 為知料5陽托4壓力加料至陰極，而1 3 一 1 5%氣化氫水溶 毫巴。除非另有i明ςϋ 0.372 ffl3/hr/cm2’反壓2〇。 kA/m2記錄。所有電I均壓是。在操作三天後，、於4 質溫度保持5 5 t ± 5 t =。，木流斋電阻校正。電池和電解P.13 576755 Case No. 9113284g_ V. Description of the invention (9) Exchange of plutonium combination to form an equivalent i-film electrode assembly Example 3 To demonstrate the consistency of the catalyst made according to Example 1, Comparative Example 1 will be used The improved batches of catalysts were compared for the method, and the rotary disk electrode (RDE) was used to obtain the electrochemical data independent of the experimental battery test. Preparation = Rare earth sulfide-supported carbon-based thin ink. 33 mg of the supported catalyst was mixed with 25 ml of isopropanol and 25 ml of M water. In total! Microliters of this ink were applied to the peaks of glassy carbon rotating electrodes (6mm diameter) 2 to 3 times. Once the ink dries, apply another layer of 5% Nafion® ionomer solution (10 μl) and evaporate ^ 电 电 = (H discharge ~ 5% HC1 at room temperature. Turn the counter electrode and standard calomel ^ ^ electrode ( SCE), together with the turntable, is connected to the pAR 373 potentiometer. At various two =: one = potential scanning, the wave potentials of the flat two ΐ ^ 2 代表 2 halves representing the reduction of dissolved oxygen are recorded (see Figure 1 ), Used as a catalyst for oxygen reduction and reaction analysis. The higher the positive potential, the greater the convenience of oxygen reduction. # / I 二 Ϊ The catalyst made by the method of Example L or Comparative Example 1 To produce a true K test _: ί 1 3 gas diffusion electrode. The obtained gas diffusion electrode makes the cold μ μ / 忒 as follows. The electrolysis experiment is configured according to Example 2. The electrode surface of the storm circuit, titanium mesh, and ru The live dagger 4 is Nafi〇n 324. The anode is the amount of water at ~ 5cm. The stoichiometric excess of 2.5 times the flow is known as 5. The anode is fed to the cathode at 4 pressure, and 1 3 to 1 5 % Hydrogenated water is soluble in mbar. Unless otherwise specified, 0.372 ffl3 / hr / cm2 'back pressure 20. kA / m2 recorded. All electrical pressure equalization is. After three days of operation, at 4 Maintaining the temperature 5 5 t ± 5 t =., Wood flow resistance correction vegetarian. Electrolysis cell and

576755 _案號 91132842_ 年 月 g-__ 五、發明說明（10) 第3圖表示在1/2高度的RDE波型電位對實驗電池電壓 之曲線圖。為顧及衍自氣體擴散電極的製作再現率，至實 驗測試電池的統計再現率之變數範圍，在1 / 2高度的波型 電壓與實驗電池電壓間之相關性，表示RDE方法很好。當 RDE的分析指標朝正電位移動，實驗電池操作電壓即降低 。此項相關性確定分析指標為在實驗系統中觸媒績效之相 關度量。 多抵觸媒使用RDE方法測試，使用比較例1製成的1 5批 平均’與使用實施例1製成的1 0批加以比較。表1綜列RDE 法所得結果。576755 _ Case No. 91132842_ Year Month g -__ V. Description of the invention (10) Figure 3 shows the curve of RDE wave potential at 1/2 height versus the experimental battery voltage. In order to take into account the variable reproduction rate derived from the gas diffusion electrode and the range of the statistical reproduction rate of the experimental test battery, the correlation between the waveform voltage at the height of 1/2 and the experimental battery voltage indicates that the RDE method is good. When the analysis index of RDE moves toward a positive potential, the operating voltage of the experimental battery decreases. This correlation determines that the analysis indicator is a relevant measure of catalyst performance in the experimental system. The multi-resistance catalyst was tested using the RDE method, and an average of 15 batches made using Comparative Example 1 was compared with 10 batches made using Example 1. Table 1 summarizes the results obtained by the RDE method.

表1 :在1/2平台高度的RDE高峯位置（VS，SCE) 硫化錢製法 卜一 比較例1 I實施例1 I相差 丨樣品數 I 〜 I在半 I 的 丨標準 I--- 高度 向峯 對照SCE 位置 + 15 10 + 一Table 1: RDE peak position (VS, SCE) at 1/2 platform height. Method of vulcanization. Comparative Example 1 I Example 1 I differ 丨 number of samples I ~ I at half I 丨 standard I-height direction Peak control SCE position + 15 10 + 1

1 6 OmV +1 6 OmV +

230mV230mV

~ Η---- I I 7 OmV Η I Η 相對 差 、 —— __ 標準差 ————J— —_ 24 I 19 Η —— + 15% + 8. 3% Η I Η~ Η ---- I I 7 OmV Η I Η Relative difference —— __ Standard deviation ———— J— —_ 24 I 19 Η —— + 15% + 8. 3% Η I Η

-* 一—-~~- - —ι— ^ I ~~--— — — J__—__ 和金ΐ ί，明改進碳分散、觸媒先質氣化铑回流，和對々 和金屬k施加超音波，可提供觸媒改進績效（半波平均于增-* 一 —- ~~--—ι— ^ I ~~ --—— — — J __—__ and Jin ΐ 明, Ming improved carbon dispersion, catalyst precursor gasification rhodium reflow, and the application of thorium and metal k Ultrasound, which can provide catalyst to improve performance

576755 _案號91132842_年月曰 修正_ 五、發明說明（11) 加70mV)和一致性（相對標準由15%降至8· 3%)。 實施例4 由只有回流或只有分散（分散加超音波）增量製成的觸 媒，亦加以測試。 第4圖表示各製程修飾可得之典型改進。雖然只施以 原料塩回流，或只有碳黑分散，已明確顯示改進，惟此等 附加製程步驟的組合，提供更大的益處。 本發明電觸媒可有各種修飾，不違其精神和範圍，須 知本發明旨在只以申請專利範圍界定為限。576755 _ Case No. 91132842_ Year Month Amendment _ V. Description of the invention (11) plus 70mV) and consistency (relative standard reduced from 15% to 8.3%). Example 4 Catalysts made with only reflow or only dispersion (dispersion plus ultrasound) increments were also tested. Figure 4 shows the typical improvements that can be obtained for each process modification. Although the use of only raw material recirculation, or only carbon black dispersion, has clearly shown improvements, the combination of these additional process steps provides greater benefits. The electrocatalyst of the present invention may have various modifications without departing from its spirit and scope. It should be noted that the present invention is intended to be limited only by the scope of patent application.

第16頁 576755 案號 91132842 修正 圖式簡單說明 端 第1圖為硫化铑觸媒樣品承載於轉 並經電壓掃描所得典型流體動力電壓圖^電-極（RDE)尖 飽和甘汞參考電極(SCE)，和鉑絲抗衡&電。三電严組成二用 ，在飽和空氣的室溫測試。在半平a古極。，谷液為5/°HC 1 分析電壓❶ 在牛十口阿度之半波位置用作 一第2圖為使用氧去極化氣體擴散電極，從HC1產生Cl2所 採用氣體擴散電極測試系統簡單流程圖。 第3圖為使用實施例1或比較例1之方法製成的一系列 觸媒，並添加於實施例2 (b)氣體擴散電極内衍生之曲線 圖。各觸媒使用RDE評估，再於第2圖組成中測試的氣體擴 散電極内評估。曲線圖把來自RDE(E 1/2)的分析電壓與同 樣觸媒用的實驗電池内所得加以比較。 第4圖表示比較例1觸媒，以只有原料塩回流製成的觸 媒，以只有碳黑分散和混合物的聲波降解法製成的觸媒’ 以及兼具回流和分散/聲波降解法製成的觸媒之半波位置 比較。 第5圖RhCl3 · ηΗ20剛溶解之溶液和回流2. 5小時後所得 典型UV/VIS譜。Page 16 576755 Case No. 91132842 Simple illustration of the modified diagram. The first picture is a typical hydrodynamic voltage diagram obtained by carrying a rhodium sulfide catalyst sample on a rotating shaft and scanning it with voltage. ^ Electrode-pole (RDE) tip saturated calomel reference electrode (SCE) ), And platinum wire & electricity. The three-electricity unit is used for two purposes and tested at room temperature in saturated air. In Banping a ancient pole. The valley fluid is 5 / ° HC 1 analysis voltage. It is used as a half-wave position at ten degrees of cattle. Figure 2 shows a gas diffusion electrode test system using oxygen depolarized gas diffusion electrode to generate Cl2 from HC1. flow chart. Figure 3 is a graph of a series of catalysts made using the method of Example 1 or Comparative Example 1 and added to the gas diffusion electrode of Example 2 (b). Each catalyst was evaluated using RDE, and then evaluated in the gas diffusion electrode tested in the composition of Figure 2. The graph compares the analytical voltage from RDE (E 1/2) with that obtained in the same experimental battery for the catalyst. Fig. 4 shows the catalyst of Comparative Example 1. The catalyst made by reflowing only the raw material 塩, the catalyst made by sonic degradation using only carbon black dispersion and mixture, and the catalyst having both reflow and dispersion / sonic degradation. Comparison of the half-wave position of the catalyst. Figure 5. Typical UV / VIS spectrum obtained after the RhCl3 · ηΗ20 solution was dissolved and refluxed 2.5 hours later.

第17頁Page 17

Claims (1)

)/f)755) / f) 755 曰Say 構物九一種硫化姥電觸媒，係由錄塩水溶液加熱到獲得異 者。w疋分配，再把硫化氫噴入溶液内，形成硫化铑而得 之者。2·如申請專利範圍第！項之觸媒，其中加熱是在回流為 種形^·如/請專利範圍第1項之電觸媒，係承載於石墨、各 7式的碳，以及其他微細化載體等導電性惰性載體上者。 ^ · 一種硫化姥電觸媒，澱積於高度分散碳黑上者。 惰性载 6 · 一種電觸媒，由锘士台p、〜、士， 、7· 一種電觸媒之形成方表歲積於而度分散碳黑上者。 /夜，將溶液加熱得铑異構物 括形成可/谷性铑塩之溶 溶液，以沉析硫化鍺，加以回^疋分配，把硫化氫喷經所得 8 ·如申請專利範圍第7項之 高度分散之碳黑上者。 万法，其中硫化铑係澱積在 9 · 種溥膜電極組成，JL古由、 媒澱積在導電性惰性載體上者、。有申請專利範圍第1項之電觸 1 〇 ·如申晴專利範圍第9項 n.如申請專利範圍第10項之其：載體為碳黑者。 散者。 、之、，且成，其中碳黑為高度分The structure is a kind of thallium sulfide electrocatalyst, which is heated from the recording water solution to obtain the alien. W 疋 Distribute, and then spray hydrogen sulfide into the solution to form rhodium sulfide. 2 · If the scope of patent application is the first! The catalyst of item, in which the heating is in the form of a reflow ^ · The electric catalyst of item 1 in the scope of patent, etc., is supported on conductive inert carriers such as graphite, each type 7 carbon, and other refined carriers. By. ^ · A thorium sulfide catalyst, deposited on highly dispersed carbon black. Inert load 6 · An electric catalyst, which is formed by the Shishitai p, ~, Shi,, 7. · The electric catalyst is dispersed on the carbon black. / Night, the solution is heated to obtain rhodium isomers to form a soluble solution of glutenic rhodium rhenium, to precipitate germanium sulfide, distribute it back, and spray the hydrogen sulfide through it. The highly dispersed carbon black. Wanfa, in which rhodium sulfide is deposited on 9 kinds of rhenium membrane electrodes, and JL is composed of a dielectric deposited on a conductive inert carrier. Electric contact with item 1 in the scope of patent application 1 〇 If item 9 in the scope of patent application n. If item 10 in the scope of patent application: the carrier is carbon black. Casual. ， 之 ，， 成 成 ， wherein carbon black is highly divided