經濟部中央標準局員工消費合作社印装 A7 B7 五、發明説明（1 ) 本案係關於一種電極之製作方法，尤指一種銥/鈀氧 化物鍍層之鈦電極製法。 電極是化學分析以及電化學工業所不可或缺的，電極 材料之開發至今仍在不斷的進行以能更加符合實際應用之 需求。良好的電極材料必須具有適當的壽命，不易損壞， 良好導電性以及對預期產生之反應具催化活性。電極材料 於使用時，以陽極材料面臨之環境較嚴苛，其必須考慮的 因素較多，除了溶液環境之侵蝕外，尙可能因電解反應而 產生大量氧氣或氯氣，純金屬材料抑或石墨等均可能參與 電化學反應或遭溶液侵蝕，而影響使用壽命。 金屬氧化物鍍層電極由於可能具有髙電化學催化活 性，良好導電性以及良好耐蝕性或化學穩定性，因此自 1 9 6 9年科學家成功地發展出金屬氧化物鍍層之後，即有各 種不同的氧化物鍍層見諸於文獻中，例如二氧化鈦、五氧 化二釩、五氧化二鈮、二氧化錳、二氧化釕、二氧化銥、 二氧化錫、二氧化鉛等，並且已被應用於許多電化學工 業，例如海水電解，鹸氯工業，金屬廢水處理或回收，有 機電化學合成，有機物分解等•上述各種氧化物可取代於 低氯化氫溶液中容易分解之石墨電極，以及易與氫氯酸溶 蝕成各種鹽類反應之白金，此雖有其他金靥如鈦、鈮、鉅 等可克服部份問題，卻可能因價格太髙或易形成穩定鈍化 膜造成電阻，減低電流密度而不見用於工業界。 銥以及鈀甚或其氧化物具有不錯的催化性，氧化銥被 應用於酸性水電解反應；鈀的催化特性常被應用爲化學工 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裟_ 訂 經濟部中央標準局員工消費合作社印製 294728 B7 五、發明説明（2) 業的催化劑，其曾被製作於白金與玻璃碳，或以電化學方 法與氧化銥共同鍍於玻璃碳。氧化銥鍍層電極的製作方法 有很多種，見諸於文獻者包括眞空反應濺鍍，金屬銥恆電 位循環氧化，熱分解法，電化學循環電位法，電漿熔射， 雷射披覆等。上述各方法中，電化學方法以外之方法所得 之電極因顆粒大小不均勻，極易造成損壞：而且氧化銥在 髙電位時（相對於標準氫電極1.6Volt)，極容易溶於酸性 液中，此有礙於使用氧化銥爲催化劑。 本發明之目的是以循環電位法，於金靥鈦製作銥/鈀 氧化物鍍層電極，以取代玻璃碳，獲致較玻璃碳具更佳機 械性質之電極，並藉氧化鈀提升電極穩定性，以循環電位 法克服鈦金屬置於水溶液中易氧化的問題。 本發明爲一種銥/鈀氧化物鍍層之鈦電極製法，其步 驟包括：a)準備一鈦金屬基材；b)取一銥/鈀氧化物；c) 應用該銥/鈀氧化物爲材料，並利用循環電位析鍍法，使 之附著於該鈦金屬基材表面；以及d)經適度熱處理後，即 可得一覆蓋銥/鈀氧化物鍍層之鈦電極。 當然，其中該鈦金屬基材之大小爲20X20X2mm ; 該鈦金靥基材需焊上鈦導線。 當然，其中該鈦金屬基材於使用前需先淸除其上之氧 化物雜質，該淸除步驟包括： a) 先以砂紙硏磨除去大量氧化物雜質； b) 繼之於適當有機溶劑中，藉超音波洗淨可能附著之 有機物； 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -----^---：---， 装------訂 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 294728 A7 ___ B7 五、發明説明（3 ) C)隨後以去離子蒸餾純水淸洗之； d) 再使用氫氟酸溶液浸漬鈦金靥，以破壞鈦金靥表面 立即生成之附著性極強之氧化物鈍化膜： e) 最後再以去離子蒸餾純水淸洗殘留之化學溶液。 當然，該銥/鈀氧化物鍍層之鈦電極製法更包括下列 步驟： a) 調配銥/鈀氧化物成析鍍溶液； b) 將該鈦金屬基材置入該銥/鈀氧化物析鍍溶液中； 以及 c) 利用循環電位析鍍法，在該鈦金屬基材表面鍍上銥 /鈀氧化物層》 當然，其中該熱處理是於大氣中在一般熱處理爐中進 行。 本發明得藉下述說明參閱所附圖式而得較佳之瞭解： 第一圖：係本發明實施例一之析鍍鍍層生成反應所對 應之循環電位Ι-E(電流-電壓）圖； 第二圖：係本發明實施例二所得之鍍層表面圖； 第三圖：係本發明所得之鍍層經X-光繞射之分析圖； 第四圖：係本發明所得之電極，於硫酸溶液中，進行 極化測試之實施例結果圖： 第五圖：係本發明所得之電極，於硫酸溶液中，進行 穩定性測試之實施例結果圖。 由於本發明之鈦金屬基材極易氧化，此亦爲其表面不 易藉由電化學析鍍於其上的原因，故金靥鈦基材在使用 (請先閲讀背面之注意事項再填寫本頁) -L— · 装· 訂 本紙張尺度適用中國國家梯準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 i、發明説明（4 ) 前，須先予前處理。亦即鈦金屬基材（2〇x2〇x2ram)經焊 以鈦導線後，表面以80〜1000號砂紙硏磨以除去大量氧化 物雜質，繼之於適當有機溶劑中，例如丙酮，藉超音波洗 淨可能附著之有機物並以去離子蒸餾純水淸洗。如此淸洗 乾淨之鈦金屬表面仍立即生成附著性極強的氧化物鈍化 膜，其會影響銥/鈀氧化物鍍層的析鍍反應與附著性，此 鈍化膜必須以氫氟酸溶液才易破壞之，本發明是以氫氟 酸：硝酸= 1:3至1:4(例如1:3)濃度比的溶液浸漬鈦電 極；並依序分別以氫氟酸40〜60g/l(例如55g/l)，及重 鉻酸250〜300g/l(例如290g/l)的混合溶液，以及氫氟 酸及醋酸混合溶液短時間浸漬（例如各二分鐘），此處理可 使鈦金靥表面於開始析鍍之前具有活性。基材隨後再以去 離子蒸餾純水淸洗殘留化學溶液。循環電位析鍍（Cycl ic Voltammetric Deposition)製作銥/钯氧化物的條 件、反應與結果，如以下實施例所示。 實施例一： 循環電位析鍍以恆電位儀控制掃描電位範圍於950至 -400mV(例如900至300mV)(相對於標準甘汞電極， SCE)，控制電位掃描速度於40〜6QmV/sec(例如 50mV/sec)，析鍍溫度控制在室溫至80〇C(例如60eC)， 析度時間最長達四小時。銥/鈀氧化物的析鍍溶液以 K2IrCl6&PdCl2爲主要成份，溶液濃度爲〇.〇5〜 0·2ιηΜ(例如 O.lmM)之 K2IrCl6，0.1 〜〇.4mM(例如 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 装. 訂 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（5 ) 0.21111〇之？(1(：12，0.211之1[2804及0.^之11(：1’原始酸 鹸度爲PHI · 2。 在上述製程條件析鍍之鍍層生成反應所對應的循環電 位Ι-E圖如圖一所示，反應持續進行下，Ι-E圖所涵蓋的面 積隨析鍍時間增長而增大，此係由於鍍層成長，表面積增 大，鑛層活性面積增加，因此電量增加。 實施例二： 上述所處理及實施例一之條件所製作之電極，經適度 熱處理之後可得附著性良好的鍍層。未熱處理之鍍層其附 著性極差，熱處理爲獲致具良好附著性鍍層所必需的過 程。熱處理是於一般熱處理爐於大氣中進行，適度控制升 溫速度於3 °C/min至6 °C/min(例如3 °C/min)範圍內，自 室溫升至400〜6Q()°C (例如5Q0°C)，維持於所欲溫度50 分鐘至三小時（例如一小時），隨即於爐中自然冷卻至室 溫。升溫速度大於6°C/min，熱處理溫度低於400 °C，熱 處理時間少於50分鐘，其所得鍍層附著性均不佳》 上述處理條件所得之鍍層如圖二所示，鍍層表面呈顆 粒狀組織形態，與一般金屬鍍層之平滑外觀不同；色澤則 爲灰黑色。由於此顆粒狀組織之成長，使得電極具有較大 的表面活性面積，因此鍍層成長時，圖一的Ι-E圖曲線涵蓋 面積隨之增加。此鍍層甫析鍍時，其爲金屬銥固溶於金靥 鈀之鑛層，適當熱處理之後所得附著性良好之鍍層，如圖 三所示，經X-光繞射分析顯示其爲氧化銥及氧化鈀的混合 鍍層。 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） (請先閱讀背面之注意事項再填寫本頁) -I衣. 訂 A7 B7 29^728 五、發明説明（6 ) 本發明所製作之鍍層電極具有優良電化學催化作用， 及極佳之化學穩定性。 以下爲電化學催化作用及穩定性說明之實例。 功效實例一： 本實例是以上述方法製作之銥/鈀氧化物鍍層之鈦電 極，於PHI，PH4之硫酸溶液中進行極化測試其電化學行 爲，測試結果顯示其具有優良電化學催化行爲。 如圖四所示，在硫酸溶液中，其極化行爲具有鈍化現 象，此鈍化行爲與金靥鈦上之金屬鈀電鍍層的電化學行爲 類似，此顯示鍍層電極經過還原電位掃描之後，有部份氧 化鈀還原成金靥鈀，而進一步氧化成鈀的兩種氧化狀態， 由於鈀具有催化性，因而此氧化-還原的行爲極有利於此 電極的電催化作用。 功效實例二： 如圖五所示，鍍層電極的功能及化學穩定性顯示於1N 硫酸溶液中水電解的Tafel Plot(塔伏圖），此圖顯示此 陽極電極具有固定斜率0.48，此斜率一直維持至2. 3伏特 (相對於甘汞標準電極）；達此電位之後，電極表面才出現 裂解現象，因而此電極於至少1N的硫酸溶液中可穩定使用 至髙達2 . 3伏特的條件。 如上所述，本發明已成功地於鈦金屬基材，藉循環電 位法製作銥/鈀氧化物鍍層電極，此鍍層電極於酸性溶液 中具有極佳之電化學功能及穩定性。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) "Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1) This case relates to a method of making an electrode, especially a method of making a titanium electrode coated with iridium / palladium oxide. Electrodes are indispensable for chemical analysis and the electrochemical industry. The development of electrode materials is still ongoing to meet the needs of practical applications. A good electrode material must have an appropriate life span, be less susceptible to damage, have good electrical conductivity, and be catalytically active for the reactions expected to occur. When the electrode material is used, the environment faced by the anode material is harsher, and there are many factors that must be considered. In addition to the erosion of the solution environment, a large amount of oxygen or chlorine gas may be generated due to the electrolytic reaction, pure metal materials or graphite, etc. May participate in the electrochemical reaction or be eroded by the solution, which affects the service life. Since metal oxide coating electrodes may have high electrochemical catalytic activity, good electrical conductivity, and good corrosion resistance or chemical stability, since scientists successfully developed metal oxide coatings in 1959, there have been various oxidations. Object coatings are found in the literature, such as titanium dioxide, vanadium pentoxide, niobium pentoxide, manganese dioxide, ruthenium dioxide, iridium dioxide, tin dioxide, lead dioxide, etc., and have been used in many electrochemical Industry, such as seawater electrolysis, chlorine industry, metal waste water treatment or recycling, organic electrochemical synthesis, organic matter decomposition, etc. • The above-mentioned various oxides can replace graphite electrodes that are easily decomposed in low hydrogen chloride solution, and are easily eroded into hydrochloric acid Platinum of various salt reactions, although there are other gold compounds such as titanium, niobium, giant, etc. that can overcome some of the problems, they may cause resistance due to high prices or easy formation of a stable passivation film, reducing the current density and not used in industry. . Iridium and palladium or even its oxides have good catalytic properties. Iridium oxide is used in the electrolysis of acidic water; the catalytic properties of palladium are often used as chemical engineering papers. The standard is China National Standard (CNS) A4 (210X297mm) ( Please read the precautions on the back before filling out this page) 裟 _ Order 294728 B7 printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Invention description (2) The catalyst for the industry, which was made in platinum and glassy carbon, or Electrochemical method and iridium oxide are co-plated on glassy carbon. There are many ways to make iridium oxide coating electrodes. Those found in the literature include empty reactive sputtering, metal iridium constant potential cyclic oxidation, thermal decomposition, electrochemical cyclic potential method, plasma spraying, and laser coating. Among the above methods, electrodes obtained by methods other than electrochemical methods are very likely to be damaged due to uneven particle size: and iridium oxide is very soluble in acidic solution when it is at a high potential (1.6 Volt relative to the standard hydrogen electrode). This prevents the use of iridium oxide as a catalyst. The purpose of the present invention is to produce an electrode of iridium / palladium oxide coating on gold-titanium titanium by cyclic potential method to replace glassy carbon, to obtain an electrode with better mechanical properties than glassy carbon, and to improve the stability of the electrode by palladium oxide. The cyclic potential method overcomes the problem that titanium metal is easily oxidized when placed in an aqueous solution. The invention is a method for manufacturing a titanium electrode coated with iridium / palladium oxide. The steps include: a) preparing a titanium metal substrate; b) taking an iridium / palladium oxide; c) applying the iridium / palladium oxide as a material, And using the cyclic potential precipitation method to make it adhere to the surface of the titanium metal substrate; and d) After moderate heat treatment, a titanium electrode covered with iridium / palladium oxide coating can be obtained. Of course, the size of the titanium metal substrate is 20X20X2mm; the titanium gold tantalum substrate needs to be welded with titanium wire. Of course, the titanium metal substrate needs to be stripped of oxide impurities before it is used. The removal steps include: a) first remove a large amount of oxide impurities with sandpaper; b) followed by a suitable organic solvent ， Using ultrasound to clean the organic matter that may be attached; The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ----- ^ ---: ---, Packing ------ order (Please read the precautions on the back before filling out this page) 294728 A7 ___ B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (3) C) Then wash it with deionized distilled pure water; d) Then Use a hydrofluoric acid solution to impregnate the titanium gold tantalum to destroy the extremely strong oxide passivation film immediately formed on the surface of the titanium gold tantalum: e) Finally, rinse the remaining chemical solution with deionized distilled pure water. Of course, the titanium electrode manufacturing method of the iridium / palladium oxide plating layer further includes the following steps: a) preparing an iridium / palladium oxide plating solution; b) placing the titanium metal substrate into the iridium / palladium oxide plating solution Medium; and c) Using the cyclic potential electroplating method, the surface of the titanium metal substrate is plated with an iridium / palladium oxide layer. Of course, the heat treatment is performed in a general heat treatment furnace in the atmosphere. The present invention can be better understood by referring to the attached drawings by the following description: The first figure: is the cyclic potential Ι-E (current-voltage) diagram corresponding to the formation reaction of the deposition plating layer in the first embodiment of the present invention; Figure 2: The surface of the coating obtained in Example 2 of the present invention; Figure 3: The analysis of the X-ray diffraction of the coating obtained by the present invention; Figure 4: The electrode obtained by the present invention in sulfuric acid solution The result graph of the example for performing the polarization test: Fifth graph: It is the result graph of the example for performing the stability test in the sulfuric acid solution of the electrode obtained by the present invention. Because the titanium metal substrate of the present invention is easily oxidized, this is also the reason why its surface is not easy to be electroplated on it, so the titanium substrate is in use (please read the precautions on the back before filling this page ) -L— · The size of the bound paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm). The A7 B7 i, invention description (4) must be given before printing the A7 B7 i, invention description (4) Pre-treatment. That is, after the titanium metal substrate (2〇x2〇x2ram) is welded with titanium wire, the surface is polished with 80 ~ 1000 # sandpaper to remove a large amount of oxide impurities, followed by an appropriate organic solvent, such as acetone, by ultrasound Wash any organic matter that may be attached and wash with deionized distilled pure water. Such a clean titanium surface still immediately forms an oxide passivation film with strong adhesion, which will affect the deposition reaction and adhesion of the iridium / palladium oxide coating. The passivation film must be hydrofluoric acid solution to be easily damaged In short, the present invention impregnates the titanium electrode with a solution of a concentration ratio of hydrofluoric acid: nitric acid = 1: 3 to 1: 4 (for example, 1: 3); and sequentially takes hydrofluoric acid of 40 to 60 g / l (for example, 55 g / l), and the mixed solution of dichromic acid 250 ~ 300g / l (such as 290g / l), and the mixed solution of hydrofluoric acid and acetic acid for a short period of time (for example, two minutes each), this treatment can make the surface of titanium gold tantalum start Active before deposition. The substrate is then rinsed with deionized distilled water to remove the remaining chemical solution. The conditions, reactions and results of Cyclic Voltammetric Deposition to produce iridium / palladium oxide are shown in the following examples. Embodiment 1: Cyclic potentiometric plating uses a potentiostat to control the scanning potential range from 950 to -400mV (for example 900 to 300mV) (relative to the standard calomel electrode, SCE), and controls the potential scanning speed at 40 to 6QmV / sec (for example 50mV / sec), the deposition temperature is controlled at room temperature to 80 ℃ (for example, 60eC), and the resolution time is up to four hours. The plating solution of iridium / palladium oxide is mainly composed of K2IrCl6 & PdCl2, and the concentration of the solution is K2IrCl6 from 0.05 to 0.2 m (for example, 0.1 mM), 0.1 to 0.4 mM (for example, this paper size is suitable for China Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling in this page) Pack. Order A7 B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Invention description (5) 0.21111〇? (1 (: 12, 0.211-1 [2804 and 0. ^ 11 (: 1 'original acid halide degree is PHI · 2. The cyclic potential Ι-E diagram corresponding to the plating reaction of the plating layer generated under the above process conditions is as follows As shown in Figure 1, as the reaction continues, the area covered by the Ι-E diagram increases with the growth of the plating time. This is due to the growth of the plating layer, the increase in surface area, and the increase in the active area of the ore layer, so the amount of electricity increases. : The electrode prepared under the conditions described above and the conditions of Example 1 can obtain a coating with good adhesion after moderate heat treatment. The adhesion of the unheated coating is very poor, and heat treatment is a necessary process to obtain a coating with good adhesion. Heat treatment The general heat treatment furnace is carried out in the atmosphere, and the temperature rise rate is moderately controlled within the range of 3 ° C / min to 6 ° C / min (for example, 3 ° C / min), from room temperature to 400 ~ 6Q () ° C (for example, 5Q0 ° C), maintain the desired temperature for 50 minutes to three hours (for example, one hour), and then naturally cool to room temperature in the furnace. The heating rate is greater than 6 ° C / min, the heat treatment temperature is less than 400 ° C, and the heat treatment time is less than After 50 minutes, the adhesion of the resulting coating is not good. "The coating obtained under the above treatment conditions is shown in Figure 2. The surface of the coating is in the form of a granular structure, which is different from the smooth appearance of the general metal coating; the color is gray-black. Because of this particle The growth of the microstructure makes the electrode have a larger surface active area. Therefore, when the coating layer grows, the area covered by the curve of the Ι-E diagram in Figure 1 increases accordingly. When this coating layer is deposited, it is solid metal iridium dissolved in gold. The palladium ore layer, after proper heat treatment, has a coating with good adhesion. As shown in Figure 3, X-ray diffraction analysis shows that it is a mixed coating of iridium oxide and palladium oxide. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (21〇X 297mm) (Please read the precautions on the back before filling this page) -I clothing. Order A7 B7 29 ^ 728 5. Description of the invention (6) The plated electrode made by the present invention has excellent electrochemical catalysis, and electrode Good chemical stability. The following is an example of electrochemical catalysis and stability description. Effect example 1: This example is a titanium electrode of iridium / palladium oxide coating produced by the above method, carried out in a sulfuric acid solution of PHI and PH4 Polarization test its electrochemical behavior, the test results show that it has excellent electrochemical catalytic behavior. As shown in Figure 4, in the sulfuric acid solution, the polarization behavior has a passivation phenomenon, this passivation behavior is similar to the electrochemical behavior of the metal palladium electroplating layer on the titanium titanium, which shows that after the reduction electrode scans Partial palladium oxide is reduced to gold and palladium, and further oxidized to two oxidation states of palladium. Because palladium is catalytic, this oxidation-reduction behavior is very beneficial to the electrocatalysis of this electrode. Example 2 of efficacy: As shown in Figure 5, the function and chemical stability of the plated electrode are shown in the Tafel Plot (tower plot) of water electrolysis in 1N sulfuric acid solution. This figure shows that the anode electrode has a fixed slope of 0.48, and this slope has been maintained To 2.3 volts (compared to calomel standard electrode); after this potential is reached, the surface of the electrode cracks, so this electrode can be used stably up to 2.3 volts in a sulfuric acid solution of at least 1N. As described above, the present invention has been successfully used to produce iridium / palladium oxide coated electrodes on a titanium metal substrate. This coated electrode has excellent electrochemical function and stability in an acidic solution. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling this page) "
*tT 經濟部中央標準局員工消費合作社印褽 五、發明説明（ A7 B7 本發明得由熟悉本技藝之人士，任施匠思而爲諸般修 飾，然皆不脫如附申請專利範圍所欲保護者。 (請先閱讀背面之注意事項再填寫本頁) 衣.* tT Printed by Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (A7 B7 This invention can be modified by any person familiar with this skill, as a matter of course, but not as protected as the scope of the patent application (Please read the precautions on the back before filling out this page).
*tT 經濟部中央標準局員工消費合作社印策 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）* tT Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs This paper standard applies to China National Standard (CNS) A4 (210X297mm)