201223634 六、發明說明： 【發明所屬之技術領域】 本發明係關於觸媒，更特別關於此觸 形成方法，以及此觸媒於燃料電池之應用 【先前技術】 媒之組成比例與201223634 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a catalyst, more particularly to the method of forming the touch, and the application of the catalyst to a fuel cell. [Prior Art] Composition ratio of the medium
直接曱醇燃料電池(DMFC)，為一種直接使用燃料在 溫操作之供電裝置，由於在低溫條件操作下，必低 媒使其達到理想發電效率。由於質子交拖π 用觸 (PEMFC)主要使用氫氣作為燃料來源，然後純= 电池 儲存上都有其難度，因此多半使用重組器 氧於運輪與 一.......... 曱醇或是其The direct oxime fuel cell (DMFC) is a kind of power supply device that operates directly at the temperature of the fuel. Because it operates under low temperature conditions, it must be low to achieve the desired power generation efficiency. Since proton exchange π-touch (PEMFC) mainly uses hydrogen as a fuel source, then pure = battery storage has its difficulty, so most of the recombiner oxygen is used in the transport wheel with a .......... 曱Alcohol or its
碳氫燃料轉換為所需之燃料氣體，而這些纟然》尺具他 有一氧化碳(co)或是二氧化碳(coo等不純·物料乳體往往帶 接反應的直接曱醇燃料電池(DMFC)即受到备、因此簡單直 主要分為主動式與被動式，主動式燃料雷^ / 曰別發展 -，也糸统 毕通常設計在10W以上，適用於定置型產σ 醇濃度（1Μ)下操作。對於低功率和1W 卜的產 發展出被動式燃料電池系統，適用於攜帶型產 高曱醇濃度（5Μ)下操作。雖然傳統上多使用品 料，亦具有良好的電化學特性，但金屬鉑含息 也居高不下，使的實際應用變的困難，gp使^ 形成Pt-M為陰極觸媒，減少鉑的使用量，作』、、仙弗二金屬 或是被動式系統，仍面臨陽極曱醇穿透至降不'^在主動式 媒被一氧化碳(CO)毒化的問題，導致降 込成陰極觸 &，媒活，· 無雙 5ι|在·、 又至】重硯。然 的輪出功 般於低曱 品需求則 ，—般於 鉑當電極材 有限而價袼 加第 邮慨 平^…嘗扣的問題，導致降低觸 從唧 全失去催化能力。因此價格較便宜的鈀遂舌性甚至完 201223634 而鈀本身催化活性不佳，目前已有一些探討鈀為主體的觸 媒，但大部份所得之觸媒氧還原能力都不佳，或是為低負 載董，低負載1於塗佈時因為需塗佈較厚的觸媒層，而面 臨質傳問題。 美國專利US 7713910利用合成PtM降低成本’但仍 無法避免曱醇穿透所造成的毒化問題。目前一般研究pd系 的觸媒合金多於低負載量下探討，這是由於低負載量因為 容易分散與合成’可達到較佳之活性’但於實際應用時需 塗較厚的觸媒層導致質傳問題，使實際應用不易。美國專 利US 7632601所合成的pdCo雖可達到與Pt相近之活性， 但是此觸媒合成的負載量即是僅約20wt°/〇〜30wt%，因此仍 有其不足之處。US7498286則是以碳為載體合成之 PdCoMo，雖活性與穩定度皆有提升，但是金屬負載量約為 20wt°/〇，因此也難以實際應用至DMFC系統。除此之外此 文獻為使用化學還原法還原Pd和Co的前趨物(ammonium hexachlororpalladate and cobalt nitrate)於碳載體（XC-72R) 上形成PdCo/C，再使用含浸法（Impregnation Method)將 Mo(ammonium heptamolybdate)含浸上 PdCo/C，為兩步驟合 成之方法。其元素組成比例為Pd介於60-80原子％，Co 介於10-30原子％，Mo則介於5-15原子％。此方法之缺點 為兩步製程，且Mo的含量較高。 綜上所述，目前亟需新的觸媒組成及製法解決上述問 題。 【發明内容】 201223634 本發月t施例提供-種觸媒，包括碳载體，·以及合 金觸媒吸附於碳載體表面上，其中合金觸縣由％原子％ 至98原子％之纪、2原子％至3〇原子％之銘、及讀原子 %至小於5原子％之鉬組成。 【實施方式】 本發明之實施例提供一種觸媒的形成方法。首先將石炭 载體分^於乙二醇巾，形成碳載體分㈣。碳載體可為活 f生反碳黑、碳奈米粒、碳奈米管、碳奈米纖維、爐黑、 a墨碳黑、石墨、或上述之組合。在本發明一實施例中， 碳載體之表面積介於1〇m2/gi2〇〇〇m2/g。若碳載體之表面 積過】則觸媒負載量將下降且觸媒顆粒會有不均勻分散 ^載體上的現象。若碳載體之表面積過大，則通常具有較 夕微孔，對分散上幫助不大，孔洞還容易被觸媒阻塞。 接著將鈀鹽、鈷鹽、及鉬鹽之水溶液加入該碳載體分 散液中。在一實施例中，鈀鹽可為PdCl2、Pd.(N〇3)2、The hydrocarbon fuel is converted into the required fuel gas, and these 纟 》 具 他 他 他 他 尺 尺 尺 尺 尺 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一 有一It is mainly divided into active and passive, active fuel mines / / screening development - and is also designed to be more than 10W, suitable for fixed-type sigma alcohol concentration (1 Μ) operation. The power and 1W production of the passive fuel cell system is suitable for the operation of the carrier-type sterol concentration (5 Μ). Although traditionally used materials, it also has good electrochemical properties, but the metal platinum also contains The high level of application makes it difficult to apply. Gp makes Pt-M a cathode catalyst and reduces the amount of platinum used. As a singular, sinus metal or passive system, it still faces anode sterol penetration. The problem of poisoning of the active medium by carbon monoxide (CO) leads to the reduction of the cathode into the cathodic contact &, the media, the unparalleled 5ι| in the ·, and again] heavy. Low demand for products, like platinum The electrode material is limited and the price is increased, and the problem of the button is reduced, which leads to the loss of the catalytic ability of the catalyst. Therefore, the cheaper palladium tongue is even finished 201223634 and the palladium itself has poor catalytic activity. There are some catalysts that explore palladium as the main component, but most of the catalysts have poor oxygen reduction ability, or low load Dong, low load 1 because of the need to apply a thick catalyst layer during coating. In the face of quality problems, US Patent US Pat. No. 7,739,910 uses synthetic PtM to reduce cost's, but it still cannot avoid the poisoning problem caused by sterol penetration. At present, it is generally studied that the catalytic alloy of pd system is more than low load, which is due to Low loading is easy to disperse and synthesize 'can achieve better activity' but in the actual application, it is necessary to apply thicker catalyst layer to cause quality problem, which makes the practical application difficult. The pdCo synthesized by US Pat. No. 7,632,601 can reach Pt is similar in activity, but the loading of this catalyst synthesis is only about 20wt ° / 〇 ~ 30wt%, so there are still some shortcomings. US7498286 is a carbon-based synthesis of PdCoMo, although the activity and The degree of improvement is improved, but the metal loading is about 20wt ° / 〇, so it is difficult to practically apply to the DMFC system. In addition, this document is the use of chemical reduction to reduce the precursor of Pd and Co (ammonium hexachlororpalladate and cobalt Nitrate) PdCo/C is formed on a carbon support (XC-72R), and Mo (ammonium heptamolybdate) is impregnated with PdCo/C by an Impregnation Method, which is a two-step synthesis method. The elemental composition ratio is Pd. At 60-80 at%, Co is between 10 and 30 at%, and Mo is between 5 and 15 at%. The disadvantage of this method is a two-step process with a high Mo content. In summary, there is an urgent need for new catalyst composition and methodologies to solve the above problems. SUMMARY OF THE INVENTION 201223634 The present invention provides a catalyst, including a carbon carrier, and an alloy catalyst adsorbed on the surface of a carbon support, wherein the alloy touches from % atom% to 98 atom%, 2 The atomic % to 3 〇 atomic %, and the reading atomic % to less than 5 atomic % of molybdenum. Embodiments of the present invention provide a method of forming a catalyst. First, the charcoal carrier is divided into ethylene glycol towels to form a carbon carrier (4). The carbon support may be a live anti-carbon black, a carbon nanoparticle, a carbon nanotube, a carbon nanofiber, a furnace black, an ink black, graphite, or a combination thereof. In an embodiment of the invention, the surface area of the carbon support is between 1 〇 m 2 / gi 2 〇〇〇 m 2 / g. If the surface of the carbon support accumulates, the amount of catalyst loading will decrease and the catalyst particles will be unevenly dispersed. If the surface area of the carbon support is too large, it usually has a micropore, which does little to disperse, and the pores are easily blocked by the catalyst. An aqueous solution of a palladium salt, a cobalt salt, and a molybdenum salt is then added to the carbon carrier dispersion. In one embodiment, the palladium salt can be PdCl2, Pd. (N〇3)2.
Pd(NH3)Cl2 · h2〇、Pd (C2H3〇2)2、Pd(C5H702)2、Pd(CN)2、Pd(NH3)Cl2 · h2〇, Pd (C2H3〇2)2, Pd(C5H702)2, Pd(CN)2
PdS04或上述之組合，鈷鹽可為c〇(N〇3)2 . 6H2〇、c〇cl2 . 6H2〇、C〇(C2H3〇2)2、2CoC03.3Co(OH)2.H20、 C〇C〇3.Co(〇H)2、CoS04.7H20、CoS04 · H20 或上述之組 合，翻鹽可為（NH4)6Mo7〇24 . 4H20、（NH4)2Mo04、MoC15、 MoC13 . 3H2〇、Mo(C2h3〇2)2 或上述之組合。 合成方法可為含浸法、初濕含浸法、溶膠_凝膠法、濺 錢法或化學還原法等’本發明即以含浸法與使用乙二醇為 洛劑之化學還原法合成觸媒。 201223634 調整乙二醇水溶液之pH值，使纪鹽、銘鹽、及顧趟 還原並吸附到碳載體上，形成合金觸媒。在本發明一實ς j中，上述乙二醇水溶液之PH值係調整至8至13之間。 若乙二醇水溶液之pH值過高，則觸媒表面電位將不^吸 附至碳材表面。若乙二醇水溶液之pH值過低，則合成之 觸媒顆粒會變大，減少表面觸媒活性中心。 尸产過濾上述溶液，清洗濾餅即得合金觸媒。接著於還原 氣氛下熱處理合金觸媒，可減少觸媒表面氧化層並有助提 3穩定性。在本發明一實施例中，還原氣氛為氫氣、或 虱氣與鈍氣之混合氣體。上述鈍氣可為氬氣、氮氣、或上 述之組合。在本發明-實施例中，於還原氣氛下進行孰處 理的温度介於 i 75Gt之間。錢處理之溫度過高.， 則顆粒聚集變成大齡，導致活性巾^減少而降低活性。 若熱處理之溫度過低’則觸媒合金化程度不足使的穩定度 也不足。 經上述步驟後，可形成PdCGMG合金觸媒吸附於碳載 體上。在本發明一實施例中，合金觸媒與碳載體之重量比 ”於40.6G至8G:2G之間’另-實施例中合金觸媒與碳載體 之重量比介於40:60至70:30。若合金觸媒之比例過高，則 合金觸媒顆粒聚集將導致觸媒實際使用率下降。若合金觸 媒之比例過低’則塗佈ME A時需塗較厚的觸媒層導致質傳 問題。合金觸媒係由50原子％至98原子％之鈀、2原子0/〇 至30原子％之鈷、及0.01原子％至小於5原子％之鉬組成， 另一實施例中合金觸媒係由75-95原子％之鈀、5_25原子0/〇 之鈷、0.03-3原子％之鉬組成。若鉬之用量小於〇 〇1原子 201223634 % ’則Mo作用將不顯著，活性將類似於pdc〇。若鉬之用 量大於或等於5% ’則會降低合金觸媒之活性與穩定性。 上述吸附於碳載體上的合金觸媒可作為燃料電池之陰 極。關於燃料電池及陰極之製作方法，可參考US7498286。 為了讓本發明之上述和其他目的、特徵、和優點能更 明顯易懂’下文特舉數實施例配合所附圖示，作詳細說明 如下： 【實施例】 • 觸媒樣品之合成方法： 取KetjenBlackECP300作為碳載體分散於乙二醇中， 以磁石攪拌30分鐘形成碳載體分散液。將所需之pdC丨2、PdS04 or a combination thereof, the cobalt salt may be c〇(N〇3)2. 6H2〇, c〇cl2. 6H2〇, C〇(C2H3〇2)2, 2CoC03.3Co(OH)2.H20, C〇 C〇3.Co(〇H)2, CoS04.7H20, CoS04·H20 or a combination thereof, the salt can be (NH4)6Mo7〇24. 4H20, (NH4)2Mo04, MoC15, MoC13. 3H2〇, Mo( C2h3〇2) 2 or a combination of the above. The synthesis method may be an impregnation method, an incipient wetness method, a sol-gel method, a splash method or a chemical reduction method. The present invention synthesizes a catalyst by an impregnation method and a chemical reduction method using an ethylene glycol as a catalyzed agent. 201223634 Adjust the pH value of the aqueous solution of ethylene glycol to reduce and adsorb the salt, salt and yttrium onto the carbon support to form an alloy catalyst. In an embodiment of the present invention, the pH of the aqueous solution of ethylene glycol is adjusted to be between 8 and 13. If the pH of the aqueous solution of ethylene glycol is too high, the surface potential of the catalyst will not be absorbed to the surface of the carbon material. If the pH of the aqueous solution of ethylene glycol is too low, the synthesized catalyst particles become large, reducing the active center of the surface catalyst. The cadaver filters the solution and cleans the filter cake to obtain an alloy catalyst. Subsequent heat treatment of the alloy catalyst in a reducing atmosphere reduces the oxide layer on the surface of the catalyst and helps to improve stability. In an embodiment of the invention, the reducing atmosphere is hydrogen gas or a mixed gas of helium gas and inert gas. The above-mentioned inert gas may be argon gas, nitrogen gas, or a combination thereof. In the present invention-embodiment, the temperature at which the enthalpy treatment is carried out under a reducing atmosphere is between i 75 Gt. If the temperature of the money treatment is too high, the aggregation of the particles becomes older, resulting in a decrease in the active towel and a decrease in activity. If the temperature of the heat treatment is too low, the degree of alloying of the catalyst is insufficient to make the stability insufficient. After the above steps, a PdCGMG alloy catalyst can be formed and adsorbed on the carbon carrier. In an embodiment of the invention, the weight ratio of the alloy catalyst to the carbon support is "between 40.6G and 8G: 2G". In another embodiment, the weight ratio of the alloy catalyst to the carbon carrier is between 40:60 and 70: 30. If the proportion of the alloy catalyst is too high, the aggregation of the alloy catalyst particles will lead to a decrease in the actual use rate of the catalyst. If the proportion of the alloy catalyst is too low, a thick catalyst layer is required to coat the ME A. The problem of mass transfer is that the alloy catalyst is composed of 50 atom% to 98 atom% of palladium, 2 atoms of 0/〇 to 30 atom% of cobalt, and 0.01 atom% to less than 5 atom% of molybdenum, and the alloy of another embodiment. The catalyst is composed of 75-95 atom% of palladium, 5-25 atomic 0/〇 cobalt, and 0.03-3 atom% of molybdenum. If the amount of molybdenum is less than 〇〇1 atom 201223634% ', the Mo effect will be insignificant and the activity will be Similar to pdc〇. If the amount of molybdenum is greater than or equal to 5%, the activity and stability of the alloy catalyst are reduced. The above-mentioned alloy catalyst adsorbed on the carbon carrier can be used as the cathode of the fuel cell. For the production method, refer to US7498286. In order to make the above and other objects of the present invention, The features and advantages can be more clearly understood. The following detailed description of the embodiments together with the accompanying drawings will be described in detail as follows: [Examples] • Synthesis of catalyst samples: Ketjen BlackECP300 was dispersed as carbon carrier in ethylene glycol. , stirring the magnet for 30 minutes to form a carbon carrier dispersion. The desired pdC 丨 2
Co(N03)2 . 6H20 與(NH4)6Mo7 0 24.4 H2〇 溶解於 NaCl 水溶 液中，形成金屬鹽水溶液。將金屬鹽水溶液逐滴加入上述 之碳載體分散液後，持續攪拌1〇分鐘再超音波震盪3〇分 鐘。接著以溶解於乙二醇之Na0H (1M)調整上述震盪後的 _ 溶液PH值。於氬氣下使用磁石攪拌上述鹼液，並於150。(： 迴流加熱上述鹼液2小時，使鹼液中的金屬鹽還原吸附至 碳載體上。將上述鹼液降至室溫後進行過濾，清洗濾餅可 得粗產物（PdCoMo/C)。接著於2%氫氣和98%氬氣的混 合氣氛下熱處理（350。〇上述粗產物兩個小時，即得最終使 用之產物：吸附於碳載體上之合金觸媒(Pdc〇M〇/c)。 觸媒樣品之元素分析：Co(N03)2 . 6H20 and (NH4)6Mo7 0 24.4 H2〇 are dissolved in an aqueous solution of NaCl to form an aqueous metal salt solution. The aqueous metal salt solution was added dropwise to the above carbon carrier dispersion, and stirring was continued for 1 minute and then ultrasonically oscillated for 3 minutes. Next, the pH of the _ solution after the shaking was adjusted with Na0H (1 M) dissolved in ethylene glycol. The above lye was stirred using a magnet under argon at 150. (: The above-mentioned alkali solution was heated under reflux for 2 hours to reduce the adsorption of the metal salt in the alkali solution onto the carbon carrier. The above-mentioned alkali solution was cooled to room temperature, filtered, and the filter cake was washed to obtain a crude product (PdCoMo/C). The product was heat-treated under a mixed atmosphere of 2% hydrogen and 98% argon (350. 〇 the above crude product for two hours to obtain the final product: an alloy catalyst (Pdc〇M〇/c) adsorbed on a carbon support. Elemental analysis of catalyst samples:
PdCoMo之元素組成比例由能量散佈分析儀（EDS)測 201223634 得。 製備測試樣品： 將0.07 g下述實施例或比較例製備之觸媒分散於μ g 去離子水與0.0524 g Nafion®的溶液中，以超音波震盈均勻 後’取10 μΐ^之觸媒分散液滴於玻璃碳電極上。待上述觸 媒分散液乾燥後，即可依不同條件測試觸媒性質。 測試條件： 首先將上述表面覆有觸媒之電極置於0.5 M H2S04水 溶液中’並將氮氣通入硫酸水溶液進行CV活化掃描20 圈。接著將氧氣通入硫酸水溶液，以轉速2500 rpm旋轉電 極，進行觸媒之氧化還原反應活性測試。 抗甲醇測試條件： 將上述表面覆有觸媒之電極置於0.5 M H2S04水溶液 中，並將氮氣通入硫酸水溶液進行CV活化知*描20圈。接 著將電極取出置入1 Μ甲醇水溶液，將氧氣通入曱醇水溶 液’以轉速25〇〇 rpm旋轉電極’進彳于觸媒之氧化退原反應 活性測試。 耐久測試： 將上述表面覆有觸媒之電極置於〇.5 Μ Η4〇4水溶液 中，並將氮氣通入硫酸水溶液進行CV活化掃描20圈。接 著將氧氣通入硫酸水溶液，以轉速2500 rPm旋轉電極一段 時間後，再以定電壓0.7 V進行觸媒之放電測試。 201223634 抗曱醇耐久測試： 將上述表面覆有觸媒之電極置於0.5 M H2S04水溶液 中，並將氮氣通入硫酸水溶液進行CV活化掃描20圈。接 著將電極取出置入1 Μ曱醇水溶液，將氧氣通入曱醇水溶 液，以轉速2500 rpm旋轉電極一段時間後，再以定電壓0.7 V進行觸媒之放電測試。 實施例1 φ 依觸媒樣品合成方法合成合金觸媒PdCoMo。其中The elemental composition ratio of PdCoMo was measured by an energy dispersive analyzer (EDS) 201223634. Preparation of test samples: 0.07 g of the catalyst prepared in the following examples or comparative examples was dispersed in a solution of μ g of deionized water and 0.0524 g of Nafion® to obtain a 10 μΐ^ catalyst dispersion after ultrasonic shock uniformity. The droplets are on the glassy carbon electrode. After the above-mentioned catalyst dispersion is dried, the catalyst properties can be tested under different conditions. Test conditions: First, the above-mentioned catalyst-coated electrode was placed in a 0.5 M H2S04 aqueous solution, and nitrogen gas was passed through a sulfuric acid aqueous solution for CV activation scanning for 20 cycles. Then, oxygen gas was introduced into an aqueous sulfuric acid solution, and the electrode was rotated at a rotation speed of 2,500 rpm to carry out a redox reaction activity test of the catalyst. Resistance to methanol test conditions: The above electrode coated with a catalyst was placed in an aqueous solution of 0.5 M H2S04, and nitrogen gas was passed through an aqueous solution of sulfuric acid to carry out CV activation for 20 cycles. Then, the electrode was taken out and placed in a 1 Torr aqueous methanol solution, and oxygen was introduced into a methanol solution to rotate the electrode at a rotation speed of 25 rpm to carry out an oxidation-reduction reaction activity test of the catalyst. Durability test: The above electrode coated with a catalyst was placed in an aqueous solution of 〇.5 Μ Η4〇4, and nitrogen gas was passed through a solution of sulfuric acid for 20 cycles of CV activation scanning. Then, oxygen was introduced into the aqueous sulfuric acid solution, and the electrode was rotated at a rotation speed of 2,500 rPm for a period of time, and then the catalyst was discharged at a constant voltage of 0.7 V. 201223634 Anti-sterol endurance test: The above electrode coated with a catalyst was placed in an aqueous solution of 0.5 M H2S04, and nitrogen gas was passed through an aqueous solution of sulfuric acid for 20 cycles of CV activation scanning. Then, the electrode was taken out and placed in an aqueous solution of sterol, oxygen was introduced into a methanol solution, and the electrode was rotated at a rotation speed of 2,500 rpm for a while, and then a catalyst discharge test was performed at a constant voltage of 0.7 V. Example 1 φ The alloy catalyst PdCoMo was synthesized by a catalyst sample synthesis method. among them
Pd、Co、與Mo之原子比為92.59 : 6.97 : 0.44，且合金觸 媒與碳載體之重量比為64:36。此觸媒於0.5M之硫酸水溶 液與0.75V之電壓下的活性為68A/g，且於0.5M之硫酸水 溶液與0.8V之電壓下的活性為46A/g。此觸媒於1M之曱 醇水溶液與0.75V之電壓下的活性為47A/g，且於1M之曱 醇水溶液與0.8V之電壓下的活性為27A/g。此觸媒置於 0.5M之硫酸水溶液3小時後的活性為38A/g，且置於1M φ 之曱醇水溶液3小時後的活性為17A/g。 實施例2 合成Pd、Co、與Mo之原子比為95.1 1 : 4.86 : 0.03 之PdCoMo合金觸媒，且合金觸媒與碳載體之重量比為 64:36。此觸媒於0.5M之硫酸水溶液與0.75V之電壓下的 活性為63A/g，且於0.5M之硫酸水溶液與0.8V之電壓下 的活性為40A/g。此觸媒於1M之曱醇水溶液與0.75V之電 壓下的活性為45A/g，且於1M之甲醇水溶液與0.8V之電 壓下的活性為33A/g。此觸媒置於0.5M之硫酸水溶液3小 201223634 時後的活性為28A/g，且置於1M之甲醇水溶液3小時後的 活性為26A/g。 實施例3 合成Pd、Co、與Mo之原子比為91.73 : 5.58 : 2.69 之PdCoMo合金觸媒，且合金觸媒與碳載體之重量比為 62: 38。此觸媒於0.5M之硫酸水溶液與0.75V之電壓下的 活性為60A/g，且於0.5M之硫酸水溶液與0.8V之電壓下 的活性為37A/g。此觸媒置於0.5M之硫酸水溶液3小時後 的活性為21 A/g 實施例4 合成Pd、Co、與Mo之原子比為81.67 : 13.95 : 4.38 之PdCoMo合金觸媒，且合金觸媒與碳載體之重量比為 64 : 36。此觸媒於0.5M之硫酸水溶液與0.75V之電壓下的 活性為47A/g，且於0.5M之硫酸水溶液與0.8V之電壓下 的活性為32A/g。此觸媒於1M之曱醇水溶液與0.75V之電 壓下的活性為38A/g，且於1M之曱醇水溶液與0.8V之電 壓下的活性為26A/g。 實施例5 合成Pd、Co、與Mo之原子比為88.38 : 11.61 : 0.01 之PdCoMo合金觸媒，且合金觸媒與碳載體之重量比為 64 : 36。此觸媒於0.5M之硫酸水溶液與0.75V之電壓下的 活性為61A/g，且於0.5M之硫酸水溶液與0.8V之電壓下 的活性為37A/g。此觸媒置於0.5M之硫酸水溶液3小時後 的活性為17A/g。 比較例1 201223634 合成Pd、Co、與Mo之原子比為86.15 : 7.84 : 6之 PdCoMo合金觸媒，且合金觸媒與碳載體之重量比為61 : 39。此觸媒於0.5M之硫酸水溶液與0.75V之電壓下的活性 為47A/g，且於0.5M之硫酸水溶液與0.8V之電壓下的活 性為32A/g。此觸媒於1M之曱醇水溶液與0.75V之電壓下 的活性為32A/g，且於〗Μ之曱醇水溶液與0.8V之電壓下 的活性為14A/g。此觸媒置於0.5Μ之硫酸水溶液3小時後 的活性為6.8A/g，且置於1M之曱醇水溶液3小時後的活 • 性為8A/g。 比較例2 合成Pd、Co、與Mo之原子比為73.3 : 13.5 : 13.2之 PdCoMo合金觸媒，且合金觸媒與碳載體之重量比為61 : 39。此觸媒於0.5M之硫酸水溶液與0.75V之電壓下的活性 為28A/g，且於0.5M之硫酸水溶液與0.8V之電壓下的活 性為15A/g。此觸媒於1M之甲醇水溶液與0.75V之電壓下 的活性為22A/g，且於1M之曱醇水溶液與0.8V之電壓下 Φ 的活性為12A/g。此觸媒置於0.5M之硫酸水溶液3小時後 的活性為5.3A/g，且置於1M之曱醇水溶液半小時後的活 性為 1.5 A/g。 比較例3 合成Pd與Co之原子比為91.65 : 8.35之PdCo合金觸 媒，且合金觸媒與碳載體之重量比為61: 39。此觸媒於0.5M 之硫酸水溶液與0.75V之電壓下的活性為26A/g，且於0.5M 之硫酸水溶液與0.8V之電壓下的活性為8A/g。此觸媒於 1M之曱醇水溶液與0.75V之電壓下的活性為22A/g，且於 201223634 1M之曱醇水溶液與〇 8v之電壓下的活性為5A/g。此觸媒 置於0.5M之硫酸水溶液2 5小時後的活性為2 3A/g。 比較例4 pt觸媒為商用觸媒。此觸媒於0·5Μ之硫酸水溶液與 0.75V之電壓下的活性為41A/g，且於〇 5μ之硫酸水溶液 與0.8V之電壓下的活性為35A/g。此觸媒於 1Μ之甲醇水 /容液與0.75V之電壓下的活性為，且於1Μ之甲醇水 /合液與0.8V之電壓下的活性為〇A/g。此觸媒置於〇·5Μ之 硫酸水溶液3小時後的活性為20A/g，且置於1Μ2甲醇水 溶液的活性為〇 A/g。 上述貫施例與比較例之觸媒於硫酸下的活性比較圖如 第1圖所不，於甲醇下的活性比較圖如第2圖所示，於硫 西夂下的耐久度如第3圖所示，且於甲醇下的耐久度如第4 圖所示。 。由上述可知，本案合成之觸媒金屬負載量可達60 wtfo解决一般化學還原法無法達到高負載量或高負載量 t活性不佳之問題，此外本案*元素組成關較前案低， 需為5 ’活性、穩定性與抗甲醇毒化才有較佳 表現Ik著Mo tl素比例上升，活性與穩定性皆有減弱的 趨f，M〇比例到達13原子％時，保守估計活性僅剩Mo 3里比例5原子％以下之觸媒的二分之―，穩定度於三小 時時僅剩五分之一。 雖然本發明已以數個較佳實施例揭露如上，然其並非 用乂限疋本發明，任何熟習此技藝者，在不脫離本發明之 精神和fei)内，當可作任意之更動與潤飾，因此本發明之 201223634 保護範圍當視後附之申請專利範圍所界定者為準The atomic ratio of Pd, Co, and Mo is 92.59: 6.97 : 0.44, and the weight ratio of the alloy catalyst to the carbon carrier is 64:36. The activity of the catalyst in a 0.5 M aqueous solution of sulfuric acid and a voltage of 0.75 V was 68 A/g, and the activity at a voltage of 0.5 M aqueous sulfuric acid solution and a voltage of 0.8 V was 46 A/g. The activity of the catalyst in a 1 M aqueous solution of alcohol and a voltage of 0.75 V was 47 A/g, and the activity in a 1 M aqueous solution of decyl alcohol and a voltage of 0.8 V was 27 A/g. The activity of the catalyst after being placed in a 0.5 M aqueous sulfuric acid solution for 3 hours was 38 A/g, and the activity after being placed in a 1 M φ aqueous solution of decyl alcohol for 3 hours was 17 A/g. Example 2 A PdCoMo alloy catalyst having an atomic ratio of Pd, Co and Mo of 95.1 1 : 4.86 : 0.03 was synthesized, and the weight ratio of the alloy catalyst to the carbon carrier was 64:36. The activity of the catalyst in a 0.5 M aqueous sulfuric acid solution at a voltage of 0.75 V was 63 A/g, and the activity at a voltage of 0.5 M aqueous sulfuric acid solution and a voltage of 0.8 V was 40 A/g. The activity of the catalyst in a 1 M aqueous solution of sterol and a voltage of 0.75 V was 45 A/g, and the activity in a 1 M aqueous methanol solution at a voltage of 0.8 V was 33 A/g. The activity of this catalyst after placing it in a 0.5 M aqueous solution of sulfuric acid at 3 hours 201223634 was 28 A/g, and the activity after being placed in a 1 M aqueous methanol solution for 3 hours was 26 A/g. Example 3 A PdCoMo alloy catalyst having an atomic ratio of Pd, Co, and Mo of 91.73: 5.58: 2.69 was synthesized, and the weight ratio of the alloy catalyst to the carbon carrier was 62:38. The activity of the catalyst in a 0.5 M aqueous sulfuric acid solution at a voltage of 0.75 V was 60 A/g, and the activity at a voltage of 0.5 M sulfuric acid aqueous solution and a voltage of 0.8 V was 37 A/g. The activity of the catalyst after being placed in a 0.5 M aqueous sulfuric acid solution for 3 hours was 21 A/g. Example 4 Synthesis of Pd, Co, and atomic ratio of Mo to 81.67: 13.95: 4.38 PdCoMo alloy catalyst, and alloy catalyst and The carbon carrier weight ratio is 64:36. The activity of the catalyst in a 0.5 M aqueous solution of sulfuric acid at a voltage of 0.75 V was 47 A/g, and the activity at a voltage of 0.5 M aqueous sulfuric acid and a voltage of 0.8 V was 32 A/g. The activity of the catalyst in a 1 M aqueous solution of decyl alcohol at a voltage of 0.75 V was 38 A/g, and the activity at a voltage of 1 M aqueous decyl alcohol and a voltage of 0.8 V was 26 A/g. Example 5 A PdCoMo alloy catalyst having an atomic ratio of Pd, Co, and Mo of 88.38: 11.61 : 0.01 was synthesized, and the weight ratio of the alloy catalyst to the carbon carrier was 64:36. The activity of the catalyst in a 0.5 M aqueous sulfuric acid solution at a voltage of 0.75 V was 61 A/g, and the activity at a voltage of 0.5 M aqueous sulfuric acid solution and a voltage of 0.8 V was 37 A/g. The activity of this catalyst after placing it in a 0.5 M aqueous sulfuric acid solution for 3 hours was 17 A/g. Comparative Example 1 201223634 A PdCoMo alloy catalyst having an atomic ratio of Pd, Co, and Mo of 86.15: 7.84:6 was synthesized, and the weight ratio of the alloy catalyst to the carbon carrier was 61:39. The activity of the catalyst in a 0.5 M aqueous solution of sulfuric acid and a voltage of 0.75 V was 47 A/g, and the activity at a voltage of 0.5 M aqueous sulfuric acid and a voltage of 0.8 V was 32 A/g. The activity of the catalyst in a 1 M aqueous solution of sterol and a voltage of 0.75 V was 32 A/g, and the activity of the aqueous solution of decyl alcohol at a voltage of 0.8 V was 14 A/g. The activity of the catalyst after being placed in a 0.5 Torr sulfuric acid aqueous solution for 3 hours was 6.8 A/g, and the activity after leaving the 1 M sterol aqueous solution for 3 hours was 8 A/g. Comparative Example 2 A PdCoMo alloy catalyst having an atomic ratio of Pd, Co and Mo of 73.3: 13.5: 13.2 was synthesized, and the weight ratio of the alloy catalyst to the carbon carrier was 61:39. The activity of the catalyst in a 0.5 M aqueous sulfuric acid solution at a voltage of 0.75 V was 28 A/g, and the activity at a voltage of 0.5 M sulfuric acid solution and a voltage of 0.8 V was 15 A/g. The activity of the catalyst in a 1 M aqueous methanol solution at a voltage of 0.75 V was 22 A/g, and the activity of Φ in a 1 M aqueous solution of decyl alcohol and a voltage of 0.8 V was 12 A/g. The activity of the catalyst after placing it in a 0.5 M aqueous sulfuric acid solution for 3 hours was 5.3 A/g, and the activity after placing it in a 1 M aqueous solution of decyl alcohol for half an hour was 1.5 A/g. Comparative Example 3 A PdCo alloy catalyst having an atomic ratio of Pd to Co of 91.65: 8.35 was synthesized, and the weight ratio of the alloy catalyst to the carbon carrier was 61:39. The activity of the catalyst in a 0.5 M aqueous sulfuric acid solution at a voltage of 0.75 V was 26 A/g, and the activity at a voltage of 0.5 M sulfuric acid solution and a voltage of 0.8 V was 8 A/g. The activity of the catalyst in a 1 M aqueous solution of sterol and a voltage of 0.75 V was 22 A/g, and the activity at a voltage of 23 8 volts of 201223634 1 M was 5 A/g. The activity of the catalyst after being placed in a 0.5 M aqueous sulfuric acid solution for 25 hours was 23 A/g. Comparative Example 4 The pt catalyst was a commercial catalyst. The activity of the catalyst in a sulfuric acid aqueous solution of 0. 5 Torr and a voltage of 0.75 V was 41 A/g, and the activity at a voltage of 0.8 V in an aqueous solution of 〇 5 μ was 35 A/g. The activity of the catalyst in the methanol/water solution at a voltage of 0.75 V and the activity at a voltage of 0.8 V at a voltage of 0.8 V was 〇A/g. The activity of the catalyst after being placed in a sulfuric acid aqueous solution of 〇·5Μ for 3 hours was 20 A/g, and the activity of the solution in a 1 M aqueous solution of methanol was 〇 A/g. The comparison of the activity of the above-mentioned catalysts and the catalysts of the comparative examples under sulfuric acid is shown in Fig. 1. The activity comparison diagram under methanol is shown in Fig. 2, and the durability under thioxime is shown in Fig. 3. As shown, the durability under methanol is shown in Figure 4. . It can be seen from the above that the catalyst metal loading in this case can reach 60 wtfo to solve the problem that the general chemical reduction method can not achieve high load or high load t activity, and the composition of this case is lower than the previous case, which needs to be 5 'Activity, stability and anti-methanol poisoning have better performance. Ik increases the proportion of Mo tl, and the activity and stability are weakened. When the ratio of M〇 reaches 13 atom%, the conservative estimation activity is only Mo 3 A ratio of 5 atomic percent or less of the catalyst is two-thirds of the stability, and only one-fifth of the stability is three hours. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention, and any one skilled in the art can make any changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of protection of 201223634 of the present invention is subject to the definition of the patent application scope attached thereto.
13 201223634 【圖式簡單說明】 第1圖係本發明之實施例中，具有不同含量的觸 媒於⑽硫酸下與G.75V之轉下的活性比較圖； 拔於2圖^、本發明之貫施例中，具有不同Mg含量的觸 媒於=甲醇下與〇·75ν之電壓下的活性比較圖； 以及 1具有不同Mo含量的觸 媒本發明之實施例巾，具有不同_含量的觸 媒於7.5Μ硫酸的耐久度__ 第4圖係本發明之實施例中 媒於1Μ曱醇下的耐久度比較圖 主要元件符號說明】13 201223634 [Simplified description of the drawings] Fig. 1 is a comparison diagram of activities of catalysts having different contents in (10) sulfuric acid and G.75V in the examples of the present invention; In the examples, the comparison of the activity of the catalyst having different Mg contents at the voltage of 甲醇·75ν under the pressure of methanol; and 1 the catalyst having different Mo contents, the embodiment of the invention, having different _ content of the touch Durability of 7.5 Μ sulfuric acid in the medium __ Figure 4 is a comparison of the durability of the medium under the sterol in the embodiment of the present invention.