201143194 六、發明說明： 【發明所屬之技術領域】 本發明係關於燃料電池用電極觸媒之製造方法、燃料 電池用電極觸媒及其用途。 【先前技術】 固體高分子型燃料電池，是具有以陽極與陰極夾持固 體高分子電解質’並將燃料供給至陽極，將氧或空氣供給 至陰極’使氧在陰極還原而取出電之形式的燃料電池。燃 料主要是使用氫或甲醇等。 以往’爲了提高燃料電池的反應速度並提升燃料電池 的能量轉換效率，係在燃料電池的陰極（空氣極）表面或 陽極（燃料極）表面設置含有觸媒之層（以下亦記載爲「 燃料電池用觸媒層」。 該觸媒一般是使用貴金屬，貴金屬中，主要是使用高 電位下爲安定且活性高之鉑、鈀等之貴金屬。然而，此等 貴金屬的價格高且資源量有限，故逐漸尋求可替代觸媒之 開發。 此外’陰極表面中所使用之貴金屬，在酸性環境下有 時會溶解’而存在著不適合於要求長時間耐久性之用途的 問題。因此’係強烈地尋求在酸性環境下不會腐蝕，耐久 性佳且具有高氧還原能之觸媒的開發。 貴金屬替代觸媒，係提出有完全不使用貴金屬之卑金 屬碳化物、卑金屬氧化物、卑金屬碳氮氧化物、硫族元素 -3- 201143194 化合物及碳觸媒等（例如參照專利文獻1〜專利文獻4 )。 此等材料與鉑等之貴金屬材料相比，便宜且資源量豐富。 然而，專利文獻1及專利文獻2中，含有卑金屬材料之 此等觸媒，仍有實用上無法獲得充分的氧還原能之問題點 〇 此外，專利文獻3及專利文獻4中，雖顯示出高氧還原 觸媒活性，但仍存在著在燃料電池運轉條件下的觸媒安定 性極低之問題點。 此般貴金屬替代觸媒，專利文獻5及專利文獻6中之Nb 及Ti碳氮氧化物可有效地顯現出上述性能，故特別受到囑 目。 專利文獻5及專利文獻6所揭示之觸媒，與以往的貴金 屬替代觸媒相比具有極高性能，但在其製造步驟的一部分 中，必須在1600 °C ~ 1 8 00 °C的高溫下進行加熱處理（例如 專利文獻5的實施例1或專利文獻6的實施例1 )。 此般高溫加熱處理，雖然工業上並非不可能，但亦伴 隨著困難度，導致設備成本的提高和運轉管理的困難，且 使製造成本上升，因而要求一種能夠更便宜地製造之方法 〇 與本發明相對接近之習知技術，可列舉出專利文獻7 。專利文獻7中，係報告一種關於含有含氮及氧的碳之氮 氧化鈦的製造之技術。 然而，專利文獻7所記載之製造方法中，爲了製造出 含有碳之氮氧化鈦，必須進行依據含氮有機化合物與鈦前 -4- 201143194 驅物之反應所進行之氮氧化鈦的製造、與依據酚樹脂與氮 氧化鈦前驅物之反應所進行之含有碳之氮氧化鈦的製造之 兩階段合成，其步驟極爲複雜。尤其是氮氧化鈦前驅物的 • 製造，必須在80°C下經過攪拌、過熱、回流、冷卻及減壓 濃縮等複雜步驟，該製造成本高。 此外，酚樹脂爲具有三維網目結構之熱硬化性樹脂， 故難以與金屬氧化物均一地混合並反應。尤其酚樹脂的熱 分解溫度爲400°c〜900°c，故亦具有在1000°C以下難以發 生酚樹脂完全分解而引起之碳化反應之問題點。 再者，專利文獻7中，僅記載太陽光集熱器用薄膜作 爲其用途者，並未探討具有作爲電極觸媒之用途性高的粒 狀或纖維狀等形狀之金屬碳氮氧化物的製造方法及其用途 〇 先前技術文獻 專利文獻1:日本特開2004-303664號公報 專利文獻2:日本國際公開第07/072665號手冊 專利文獻3 : US 2004/00967828 專利文獻4:日本特開2005-1 9332號公報 ' 專利文獻5 :日本國際公開第2009/03 1 383號手冊 專利文獻6:日本國際公開第2009/107518號手冊 專利文獻7:日本特開2009-23887號公報 【發明內容】 (發明所欲解決之課題） -5- 201143194 本發明係以解決此般先前技術中的問題點者爲課題° 亦即，本發明之目的在於提供一種不須設置高溫下的熱處 理（燒結）步驟，而製造出採用過渡金屬（鈦等）之具有 高觸媒活性的燃料電池用電極觸媒之方法。 此外，本發明之其他目的在於提供一種能夠以低成本 來製造出具有高觸媒活性的燃料電池用電極觸媒之燃料電 池用電極觸媒之製造方法。 (用以解決課題之手段） 本發明例如關於下列（1 )至（1 7 )。 (1) 一種燃料電池用電極觸媒之製造方法，其特徵 爲：在500至1100 °C、含氮氣的氣體環境下，對分子中不 含氮之有機化合物與分子中含有氧之含過渡金屬的化合物 之混合物進行熱處理。 (2) 如（1)之燃料電池用電極觸媒之製造方法，其 中分子中不含氮之有機化合物，係選自由醇類、羥基類、 過氧類、酮類、醛類、醚類、羧類、酯類 '羰類、硫醇類 、磺酸基類、醣類及不含氮之5員及6員雜環化合物、以及 具有前述雜環化合物可組合2個以上之環狀結構之化合物 及錯合物所組成之群組的一種以上。 (3) 如（1)之燃料電池用電極觸媒之製造方法，其 中分子中不含氮之有機化合物，係選自由藉由（2)之化 合物的聚合反應所得之高分子化合物所組成之群組的—種 以上。 -6- 201143194 (4) 如（1)之燃料電池用電極觸媒之製造方法，其 中分子中不含氮之有機化合物，係選自由聚乙烯醇、聚丙 烯酸、聚環氧乙烷、乙二醇、聚乙二醇、檸檬酸、蘋果酸 、琥珀酸、富馬酸、酒石酸、草酸、葡萄糖、甘露糖、纖 維素、果糖、半乳糖、麥芽糖、蔗糖、乳糖、丁酸、戊酸 、己酸、辛酸、十二酸所組成之群組的一種以上。 (5) 如（1)至（4)中任一項之燃料電池用電極觸 媒之製造方法，其中分子中含有氧之含過渡金屬的化合物 ，係由含有下列金屬之金屬氧化物或金屬氫氧化物或前述 金屬氧化物及金屬氫氧化物的混合物所構成，該金屬是選 自由鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、銷、鈮、鉬 、钽及鎢所組成之群組的一種以上之金屬（以下亦稱爲「 金屬Μ」或僅稱爲「M」：含有2種以上的金屬時，稱爲「 金屬Ml」或僅稱爲「Ml」並於Μ後方記載數字）。 (6) 如（1)至（5)中任一項之燃料電池用電極觸 媒之製造方法，其中分子中不含氮之有機化合物（2種以 上時爲全部有機化合物的總和莫耳數；高分子化合物時以 單體爲基準）與分子中含有氧之含過渡金屬的化合物（2 種以上時爲全部金屬的總和莫耳數）之混合物中之前述有 機化合物與前述含過渡金屬的化合物之混合比率，當將前 述有機化合物及前述含過渡金屬的化合物之莫耳數分別設 爲X、y時，爲0.01Sx/yS100之範圍。 (7) 如（1)至（6)中任一項之燃料電池用電極觸 媒之製造方法，其中含氮氣的氣體中之氮氣的含量爲1〇至 201143194 100體積％。 (8) 如（1)至（7)中任一項之燃料電池用電極觸 媒之製造方法’其中相對於全氣體含氮氣的氣體更含有 0.01至5體積％的氮氣β (9) 如（1)至（8)中任一項之燃料電池用電極觸 媒之製造方法，其中相對於全氣體含氮氣的氣體更含有 0.01至10體積％的氧氣。 (10) —種燃料電池用電極觸媒，爲藉由（D至（9 )中任一項之燃料電池用電極觸媒之製造方法所製造的燃 料電池用電極觸媒，其特徵爲：當將構成該燃料電池用電 極觸媒之過渡金屬元素、碳、氮及氧的原子數比（過渡金 屬元素：碳：氮：氧）設爲1: X: y: Ζ時，爲〇<χ$3，0 <y$2， 0<z^3。 (11) —種燃料電池用電極觸媒，爲藉由（1)至（9 )中任一項之燃料電池用電極觸媒之製造方法所製造的燃 料電池用電極觸媒，其特徵爲：當將構成該燃料電池用電 極觸媒之過渡金屬元素Ml、過渡金屬元素M2 (惟Ml是選 自由鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、鉻、鈮、鉬 、鉬及鎢所組成之群組的一種金屬’ M2是與選自前述群組 之Ml爲不同的至少1種金屬）、碳、氮及氧的原子數比（ 過渡金屬元素Ml:過渡金屬元素M2:碳：氮：氧）設爲 (1 - a ) : a: X: y: z時’爲 0<aS0.5，0<x$3，0<y$ 2，0 < z S 3。 (12) 如前述（10)或（11)之燃料電池用電極觸媒 -8- 201143194 ，其中以BET法所計算出之比表面積爲30〜400m2/g。 (13) —種燃料電池用觸媒層，其特徵爲：含有（10 )至（12)中任一項之燃料電池用電極觸媒。 (14) 如（I3)之燃料電池用觸媒層，其中更含有電 子傳導性物質。 (15) —種電極，爲具有燃料電池用觸媒層與多孔質 支撐層之電極，其特徵爲：前述燃料電池用觸媒層爲（14 )項之燃料電池用觸媒層。 (16) —種膜電極接合體，爲具有陰極與陽極與配置 在前述陰極及前述陽極之間之電解質膜之膜電極接合體， 其特徵爲：前述陰極及/或前述陽極爲（15)之電極。 (17) —種燃料電池，其特徵爲：具備（16)之膜電 極接合體。 發明之效果： 根據本發明之燃料電池用電極觸媒之製造方法，可在 較以往的方法更爲低溫下製造出燃料電池用電極觸媒，故 可降低製造成本並提昇製造步驟的安定性。 【實施方式】 <燃料電池用電極觸媒之製造方法> 本發明之燃料電池用電極觸媒之製造方法的特徵，是 在5 00〜1100 °C、含氮氣的氣體環境下，對分子中不含氮之 有機化合物與分子中含有氧之含過渡金屬的化合物之混合 -9 - 201143194 物進行熱處理者。 前述分子中含有氧之含過渡金屬的化合物，係含有選 自由例如鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、锆、鈮 、鉬、鉬及鎢所組成之群組的一種以上之金屬（以下亦稱 爲「金屬M」或僅稱爲「M」：含有2種以上的金屬時，稱 爲「金屬Ml」或僅稱爲「Ml」並於Μ後方記載數字）作 爲過渡金屬元素。 此等當中，就成本及所得之觸媒的性能之觀點來看， 較佳爲鈦、锆、鈮及鉬，更佳爲鈦及锆。 分子中含有氧之含過渡金屬的化合物，可列舉出前述 過渡金屬的氧化物或氫氧化物，亦可爲氧化物及氫氧化物 的混合物。 合成上述金屬的氧化物、氫氧化物或此等的混合物之 手法並無特別限定，例如可藉由採用沉澱法或水解法來合 成上述過渡金屬的烷氧化物或金屬鹽。此外，可在形成過 渡金屬的錯合物並混合有機化合物後進行合成。後者的手 法中，可抑制所得之氧化物、氫氧化物或此等的混合物之 凝聚，而製得具有高純度、高均質性之與有機化合物的混 合物。用以形成過渡金屬的錯合物所使用者，只要於分子 中不含氮，則無特別限定，例如可列舉出乙醯丙酮、乙二 醇等。 前述過渡金屬的烷氧化物並無特別限定，較佳爲前述 過渡金屬的甲氧化物、乙氧化物、丙氧化物、異丙氧化物 、丁氧化物及異丁氧化物，尤佳爲乙氧化物、異丙氧化物 -10- 201143194 及丁氧化物。前述過渡金屬烷氧化物，可具有1種烷氧基 或是2種以上的烷氧基。 上述過渡金屬的金屬鹽並無特別限定，可列舉出上述 過渡金屬的氯化物、硝酸鹽、乙酸鹽、碳酸鹽 '硫化物、 氰化物、硼酸鹽、磷酸鹽、側氧金屬酸鹽、溴化物、碳化 物、氮化物、或此等之混合物。尤佳爲氯化物、硝酸鹽及 乙酸鹽。 分子中不含氮之有機化合物，只要是不會因50 0〜1100 °C下的熱處理產生熱分解者，則無特別限制。 當中較佳爲選自由聚乙烯醇、聚丙烯酸、聚環氧乙烷 、乙二醇、聚乙二醇、檸檬酸、蘋果酸、琥珀酸、富馬酸 、酒石酸、草酸、葡萄糖、甘露糖、纖維素、果糖、半乳 糖、麥芽糖、蔗糖、乳糖、丁酸、戊酸、己酸、辛酸、十 二酸所組成之群組的一種以上。此外，亦佳者爲選自由藉 由上述化合物的聚合反應所得之高分子化合物所組成之群 組的一種以上。 再者，上述當中，較佳爲聚乙烯醇、聚丙烯酸、聚環 氧乙烷等之水溶性高分子，葡萄糖、纖維素、果糖等之糖 質，檸檬酸、蘋果酸、琥珀酸、富馬酸、酒石酸等之有機 酸。此等化合物可混合2種以上使用。 本發明中，使用分子中不含氮之有機化合物者，是爲 了將燃料電池用電極觸媒的氮源設定爲僅來自於構成熱處 理環境氣之含氮氣的氣體。以往，爲了在氮氣環境下使金 屬或金屬化合物與氮進行反應，必須在較氮分子的解離溫 -11 - 201143194 度之1 200 °C更高之溫度下進行熱處理，但藉由使用分子中 不含氮之有機化合物’並在含氮氣的氣體中進行熱處理， 可在更低的熱處理溫度下，使金屬或金屬化合物與氮進行 反應。 {^分子中不含氮之有機化合物與分子中含有氧之含過 渡金屬的化合物混合之方法，只要可分別均一地混合者即 可’並無特別限定’例如在將各化合物分別溶解於溶劑中 或分散於分散溶劑中後，混合各化合物並去除溶劑或分散 溶劑來進行。此外，可在任一方的溶液或分散溶劑中將另 —方混合後，去除溶劑或分散溶劑。 將分子中不含氮之有機化合物（2種以上時爲全部有 機化合物的總和莫耳數；高分子化合物時以單體爲基準） 以及分子中含有氧之含過渡金屬的化合物（2種以上時爲 全部過渡金屬的總和莫耳數）之莫耳數分別設爲X、y，並 將此等之比率設爲x/y時，各混合比率，較佳爲〇.〇lSx/y $1〇〇，尤佳爲O.lSx/ySlO。當混合比率位於前述範圍內 時’乃具有藉由熱處理容易使氮進入於含過渡金屬的化合 物之傾向。 前述混合物的熱處理溫度，較佳爲500-1100 °C之範圍 ，尤佳爲8 00~ 1 050°C之範圍，更佳爲900〜lOOOt之範圍。 當熱處理溫度位於前述範圍內時，就所得之燃料電池用電 極觸媒的結晶性及均一性良好之方面來看較佳。此外，可 達成製造成本的降低及製造步驟安全性的提升。前述熱處 理溫度未達500 °C時，分子中不含氮之有機化合物與分子 -12- 201143194 中含有氧之含過渡金屬的化合物之混合物的前驅物與燒結 氣體中的氮氣之反應性變差’使氮難以進入於生成物中。 高於1 1 0 0 °c時，有粒徑變大而使比表面積變小之傾向，並 且無法達成製造成本的降低及製造步驟安全性的提升。 本發明之燃料電池用電極觸媒之製造方法中，如上述 般，可藉由在較以往的方法更爲低溫下之熱處理而製得燃 料電池用電極觸媒。因此，本發明之燃料電池用電極觸媒 之製造方法中，可安全且在低成本下製得燃料電池用電極 觸媒。本發明中，即使藉由如此低溫下的熱處理，結晶性 及均一性亦良好而能夠製得活性高的燃料電池用電極觸媒 者，可考量爲由於在1 loot以下的溫度範圍中，依據有機 化合物的熱分解達到活性化之碳及燒結氣體中的氮氣容易 與金屬氧化物或金屬氫氧化物進行反應，並與金屬氧化物 或金屬氫氧化物之一部分的氧進行取代，而能夠製得具有 較佳的過渡金屬元素、碳、氮及氧的組成比之燃料電池用 電極觸媒之故。 前述混合物的熱處理，是在含氮氣的氣體環境下進行 。藉由在含氮氣的氣體環境下進行熱處理，在伴隨著作爲 原料之含過渡金屬的化合物之有機化合物的熱分解，使碳 化反應進行，同時使依據氮氣之氮化反應進行。含氮氣的 氣體，只要是可藉由熱處理有效率地製造出燃料電池用電 極觸媒者即可，並無特別限制，除了氮氣之外，可列舉出 氮氣與氫氣之混合氣體以及氮氣與氬氣之混合氣體等，亦 可含有氧氣。 -13- 201143194 含氮氣的氣體中之氮氣的含量，較佳爲10〜100體積％ ，尤佳爲50〜100體積％。 當含氮氣的氣體含有氫氣時，氫氣的含量較佳爲 0.01~5體積 ％。 此外，含氮氣的氣體可含有0.01 ~1〇體積％的氧氣。 熱處理環境氣的壓力並無特別限定，考量到製造安定 性與成本等，可在大氣壓下進行熱處理。 關於前述混合物的熱處理，至前述記載的燒結溫度爲 止之升溫速度並無特別限定，例如較佳爲1〜100°c /分，尤 佳爲5~5 0°c /分。此外，升溫後的保持時間，只要是可進 行碳化反應及氮化反應者即可，並無特別限制，考量所得 到之燃料電池用電極觸媒的粒子大小及製造成本等，較佳 爲10分鐘~5小時，尤佳爲30分鐘~3小時。 燃料電池用電極觸媒的形狀，只要是具有較佳的過渡 金屬元素、碳、氮及氧的組成比，且具有作爲燃料電池用 電極觸媒的充分氧還原能者即可，並無特別限定，例如可 列舉出粒子狀、纖維狀、薄片狀、多孔體結構等。 燃料電池用電極觸媒’係要求高導電性、安定性及高 比表面積。因此’在上述製造步驟中或步驟後，可將燃料 電池用電極觸媒撐持於撐體上。撐體，只要是導電性及安 定性高且比表面積大者即可，並無特別限定，例如可列舉 出碳黑、碳奈米管、碳奈米纖維、多孔體碳、碳奈米錐、 富勒烯、石墨、石墨烯、碳陶料、導電性陶瓷及多孔體導 電性陶瓷等。撐體的形狀及大小並無特別限定，考量到所 * 14 - 201143194 撐持之燃料電池用電極觸媒的觸媒活性等，撐體的: 佳爲10~1 000nm，尤佳爲10〜lOOnm» 此外，因前述分子中不含氮之有機化合物或前: 中含有氧之含過渡金屬的化合物之性狀的不同，藉I 理所得之觸媒的凝聚狀態有時會不均一。此時，可; 前述觸媒磨碎而得到細微且粒徑更均一之觸媒。 將燃料電池用電極觸媒磨碎之方法並無特別限: 如可使用滾轉動硏磨機、球磨機、小徑球磨機（珠j 、媒體攪拌硏磨機、氣流粉碎機、硏缽、自動捏合] 槽解機及噴射硏磨機，觸媒爲少量時，較佳爲使用ί 自動捏合硏缽、或是分批式的球磨機，觸媒爲多量. 地混合來進行磨碎處理時，較佳爲使用噴射硏磨機。 <觸媒> 本發明之燃料電池用電極觸媒的特徵，在於使用 本發明之燃料電池用電極觸媒之製造方法所製造出（ 亦將藉由上述本發明之燃料電池用電極觸媒之製造方 製造出的燃料電池用電極觸媒撐爲「觸媒（Α)」）‘ 當將構成前述觸媒（Α)之過渡金屬元素、碳、 氧的原子數比表示爲過渡金屬元素：碳：氮：氧=1: :ζ時，較佳爲 0<x$3，0<yS2，0<ζ$3。 就電極觸媒的活性高之方面來看，x的範圍尤佳 SxS2.5，更佳爲 〇.5$χ$2·0，特佳爲 0.7$χ$1·5 範圍尤佳爲0.01SyS1.5，更佳爲0.02Sy$0.5，特 徑較 分子 熱處 由將 ，例 機） 鉢、 鉢、 連續 上述 以下 '法所 > 氮及 X : y 爲〇 · 3 ，丫的 佳爲 -15- 201143194 0.03$丫$0.4，2的範圍尤佳爲0.2$2$2.5’更佳爲0.3$2 $2.0，特佳爲 〇·5$ζ$1·5。 此外，當前述觸媒（A)含有選自由鈦、釩、鉻、錳 、鐵、銘、鎳、銅、鋅 '鉻、鈮、鉬、钽及鎢所組成之群 組的一種以上之過渡金屬元素Ml及與選自前述群組之過渡 金屬元素Ml爲不同的至少1種過渡金屬元素M2作爲前述過 渡金屬元素時’構成前述觸媒（A)之過渡金屬元素M1、 過渡金屬元素M2、碳、氮及氧的原子數比’表示爲過渡金 屬元素Ml :過渡金屬元素M2:碳：氮：氧=(l-a) ： a ： x : y ： z 時，較佳爲 〇<a$0.5，0<x^3> 0<y^2> 0<z S3。前述觸媒（A)含有該過渡金屬元素M2時，更可提 高性能。 就電極觸媒的活性高之方面來看，X、y及z的較佳範 圍如上述般，a的範圍較佳爲0.01Sa‘0.5，更佳爲0.02$ aS0.4，特佳爲 0.03SaS0.3。 前述a、X、丫及Z之値，爲藉由後述實施例所採用之方 法進行測定時之値。 <由於過渡金屬元素M2的存在可預料到所能夠發揮之效果 > 由於過渡金屬元素M2 (與選自由鈦、釩、鉻、錳、鐵 、鈷、鎳、銅、鋅、锆、鈮、鉬、鉬及鎢所組成之群組的 過渡金屬元素Ml爲不同的至少1種金屬元素）的存在可預 料到之效果如下》 -16- 201143194 (1 )過渡金屬元素M2或含有過渡金屬元素M2之化合 物，當合成電極觸媒時，係作用爲用以形成過渡金屬元素 Ml原子與氮原子之鍵結的觸媒。 (2) 即使在使過渡金屬元素Ml溶出之高電位、高氧 化性環境下使用電極觸媒，由於過渡金屬元素M2的鈍態化 ，可防止過渡金屬元素Ml更進一步的溶出。 (3) 熱處理時，防止熱處理物的燒結，亦即防止比 表面積的降低》 (4) 藉由在電極觸媒中存在過渡金屬元素Ml及過渡 金屬元素M2，在兩者金屬元素相鄰接之部位中，產生電荷 的偏向，因而產生在僅具有過渡金屬元素Ml作爲金屬元素 之電極觸媒中所不會形成之基質的吸附或反應、或是生成 物的脫離。 本發明之觸媒（A)，較佳是具有過渡金屬元素、碳 、氮及氧的各原子，並具有前述過渡金屬元素的氧化物、 碳化物或氮化物單獨或是此等中的複數種結晶構造。從依 據X射線繞射分析對前述觸媒（A )所進行之結晶構造解 析的結果、以及元素分析的結果來判斷，前述觸媒（A ) 可推測爲：具有前述過渡金屬元素的氧化物結構、或是以 碳原子或氮原子來取代氧化物結構的氧原子部位之結構， 或者是具有前述過渡金屬元素的碳化物、氮化物或碳氮化 物結構、或是氧原子來取代碳原子或氮原子部位之結構， 或者是含有此等結構之混合物。 -17- 201143194 < BET比表面積> 根據本發明之燃料電池用電極觸媒之製造方法，可製 造出比表面積大之燃料電池用電極觸媒，本發明之觸媒（ A )以BET法所計算出之比表面積，較佳爲3〇〜4〇〇m2/g， 尤佳爲50〜350m2/g，更佳爲1〇〇〜300m2/g。 前述觸媒（A )依循下列測定法（A )所測定之氧還 原起始電位’以可逆氫電極爲基準時，較佳爲〇.5 V ( 乂3.111^)以上，尤佳爲〇.6乂（^3.111^)以上，更佳爲〇.7¥ (vs.RHE)以上。 〔測定法（A )： 以使分散於作爲電子傳導性物質的碳之觸媒成爲1質 量％之方式，將該觸媒與碳投入於溶劑中，以超音波攪拌 而得懸浮液。碳係使用碳黑（比表面積100〜300m2/g (例 如Cabot公司製的XC-72 )，並以使觸媒與碳的質量比成爲 95 : 5之方式進行分散。此外，溶劑係使用異丙醇：水（ 質量比）=2 : 1者。 一邊施以超音波一邊採集1〇μί前述懸浮液，並迅速滴 入至玻璃碳電極（直徑：5.2mm )上，在120 °C下進行5分 鐘的乾燥。藉由乾燥而含有觸媒之燃料電池用觸媒層，被 形成於玻璃碳電極上。進行該滴入及乾燥操作直到碳電極 表面上形成有l.Omg以上的燃料電池用觸媒層爲止。 接著以異丙醇將NAFION (註冊商標）（DuPont公司 製、5%NAFION (註冊商標）溶液（DE521 ))稀釋10倍 ，並將此稀釋液1〇μί滴入至前述燃料電池用觸媒層上。在 -18- 201143194 120°C下將此進行1小時的乾燥。 使用如此製得之電極，在氧氣環境及氮氣環境下，於 0.5mol/L的硫酸水溶液中，在30°C的溫度下，將同一濃度 的硫酸水溶液中之可逆氫電極設定爲參考電極並以5m V/秒 的電位掃描速度進行分極，藉此測定電流-電位曲線，將 此時在氧氣環境下的還原電流與氮氣環境下的還原電流之 間開始顯現〇.2μΑ/(；ιη2以上的差之電位，設爲氧還原起始 電位。〕 本發明中，氧還原電流密度可藉由下列方式求取。 首先從上述測定法（Α)的結果中，計算出在0.65 V ( vs.RHE)時之氧氣環境下的還原電流與氮氣環境下的還原 電流之差。然後再將以電極面積除上計算出之値後的値， 設爲氧還原電流密度（mA/cm2 )。 此外，本發明之燃料電池用電極觸媒的氧還原電流密 度，較佳爲〇.〇2mA/cm2以上，尤佳爲〇_5mA/cm2以上，特 佳爲1.0mA/cm2以上。此外，氧還原電流密度愈高愈佳， 其上限並無特別限制，可爲1〇〇 mA/cm2。 <用途〉 本發明之觸媒（A)，可使用作爲鉑觸媒的替代觸媒 〇 本發明之燃料電池用觸媒層的特徵，在於含有前述觸 媒（A)。 燃料電池用觸媒層，有陽極觸媒層與陰極觸媒層，前 19 201143194 述觸媒（A)可使用在任一種中。前述觸媒（A)，其耐 久性佳且氧還原能大，故較佳係使用在陰極觸媒層。 本發明之燃料電池用觸媒層中，較佳更含有電子傳導 性粉末。當含有前述觸媒（A)之燃料電池用觸媒層更含 有電子傳導性粉末時，更能夠提高還原電流。電子傳導性 粉末，可考量爲在前述觸媒（A)中產生用以激發電化學 反應之電性接點，所以可提高還原電流之故。 前述電子傳導性粒子，通常用做爲觸媒的撐體。 前述觸媒（A)雖具有某種程度的導電性，但爲了藉 由觸媒（A)賦予更多電子，或使反基質從觸媒（A)接 收更多電子，可將用以賦予導電性之撐體粒子混合於觸媒 (A) » 電子傳導性粒子的材質，可列舉出碳、導電性高分子 、導電性陶瓷、金屬或氧化鎢或氧化銥等之導電性無機氧 化物，此等可單獨使用1種或組合使用。尤其是由碳所構 成之電子傳導性粒子，該比表面積較大，可容易且便宜地 取得小粒徑者，且耐藥性、耐高電位性佳，故較佳爲碳單 獨或碳與其他電子傳導性粒子之混合物。亦即，燃料電池 用觸媒層，較佳係含有前述觸媒（A)及碳。 碳，可列舉出碳黑、石墨、碳陶料、活性碳、碳奈米 管、碳奈米纖維、碳奈米錐、富勒烯、多孔體碳、石墨烯 等。由碳所構成之電子傳導性粒子的粒徑，過小時不易形 成電子傳導路徑，過大時有引起燃料電池用觸媒層之氣體 擴散性的降低或觸媒利用率的降低之傾向，故較佳爲 -20- 201143194 5~1000nm，尤佳爲 10 〜l〇〇nm。 當電子傳導性粒子由碳構成時，前述觸媒（A)與電 子傳導性粒子之重量比（觸媒：電子傳導性粒子），較佳 爲 4 : 1〜1000 : 1。 前述導電性高分子並無特別限定，例如可列舉出聚乙 炔 '聚對苯、聚苯胺、聚烷基苯胺、聚吡咯、聚噻吩、聚 吲哚、聚-1，5-二胺基蒽醌 '聚胺基聯苯、聚（鄰苯二胺） 、聚（喹啉）鹽、聚吡啶、聚喹喔啉、聚苯基喹喔啉等。 此等當中，較佳爲聚吡咯、聚苯胺、聚噻吩，尤佳爲聚吡 咯。 前述高分子電解質，只要是燃料電池用觸媒層中所一 般使用者即可，並無特別限定。具體而言，可列舉出具有 磺酸基之全氟碳聚合物（例如NAFION (註冊商標）（ DuPont公司製、5%NAFI0N (註冊商標）溶液（DE521) 等）、具有磺酸基之烴系高分子化合物、摻雜有磷酸等的 無機酸之高分子化合物、一部分經質子傳導性官能基所取 代之有機/無機混成聚合物、將磷酸溶液或硫酸溶液含浸 於高分子基質之質子傳導體等。此等當中，較佳爲 NAFION (註冊商標）（DuPont公司製、5%NAFION (註 冊商標）溶液（DE521 ))。 本發明之燃料電池用觸媒層，可使用在陽極觸媒層與 陰極觸媒層的任一種中。本發明之燃料電池用觸媒層，具 有高氧還原能，且含有在酸性電解質中即使爲高電位亦不 易腐蝕之觸媒，故對於用作爲燃料電池的陰極上所設置之 -21 - 201143194 觸媒層（陰極觸媒層）爲有用。尤其適合於用在固 子型燃料電池所具備之膜電極接合體的陰極上所設 媒層。 將前述觸媒（A)分散於作爲撐體的前述電子 粒子上之方法，可列舉出氣流分散、液中分散等方 中分散，由於可將溶劑中分散有觸媒（A)及電子 粒子之分散液使用在燃料電池用觸媒層形成步驟中 佳。液中分散可列舉出依據孔口收縮流之方法，依 切變流之方法或依據超音波之方法等。液中分散時 用之溶劑，只要是不會侵蝕觸媒（A)和電子傳導 並可分散者即可，並無特別限制，一般可使用揮發 體有機溶劑或水等。 此外，將觸媒（A)分散於作爲撐體的前述電 性粒子上時，更可同時使前述電解質與分散劑分散 燃料電池用觸媒層的形成方法並無特別限制， 列舉出將含有前述觸媒（A)與電子傳導性粒子與 之懸浮液，塗佈於後述電解質膜或氣體擴散層之方 述塗佈方法，可列舉出浸泡法、網版印刷法、輥塗 噴霧法等。此外，可列舉出將含有前述觸媒（A) 傳導性粒子與電解質之懸浮液，藉由塗佈法或過媳 料電池用觸媒層形成於基材後，以轉印法將燃料電 媒層形成於電解質膜之方法。 本發明之電極的特徵，在於具有前述燃料電池 層與多孔質支撐層。 體高分 置之觸 傳導性 法。液 傳導性 ，故較 據旋轉 ，所使 性粒子 性的液 子傳導 〇 例如可 電解質 法。前 佈法、 與電子 法將燃 池用觸 用觸媒 -22- 201143194 本發明之電極，可使用在陰極與陽極的任一種電極中 。本發明之電極，由於耐久性佳且觸媒能大，故使用在陰 極時，在產業上的優勢更高。 所謂多孔質支撐層，爲使氣體擴散之層（以下亦稱爲 「氣體擴散層」）。氣體擴散層只要是具有電子傳導性， 氣體擴散性高且耐腐蝕性高者即可，並無特別限制，一般 爲使用碳紙、碳布等之碳系多孔質材料，或爲了達到輕量 化而使用被覆有不鏽鋼、耐腐蝕材之鋁箔。 本發明之膜電極接合體，爲具有陰極與陽極與配置在 前述陰極及前述陽極之間之電解質膜之膜電極接合體，其 特徵在於前述陰極及/或前述陽極爲前述電極。 電解質膜，一般係使用例如使用全氟磺酸系之電解質 膜或烴系電解質膜等，亦可使用將液體電解質含浸於高分 子微多孔膜之膜、或是將高分子電解質充塡於多孔質體之 膜等。 此外，本發明之燃料電池的特徵在於具備前述膜電極 接合體。 燃料電池的電極反應，是在所謂三相界面（電解質-電極觸媒-反應氣體）上所引起。燃料電池可由所使用之 電解質等的不同而分成數種，有熔融碳酸鹽型（MCFC ) 、磷酸型（PAFC)、固體氧化物型（SOFC)、固體高分 子型（PEFC)等。當中，本發明之膜電極接合體較佳係使 用在固體高分子型燃料電池。 使用本發明之觸媒（A )之燃料電池，其性能高，在 -23- 201143194 與使用鉑做爲觸媒時相比時，具有極便宜之特徵。本發明 之燃料電池，可提升具備具有選自由發電功能、發光功能 、發熱功能、音響產生功能、運動功能、顯示功能及充電 功能所組成之群組的至少一項功能之燃料電池之物品的性 能，尤其可提升可攜式物品的性能。前述燃料電池，較佳 係在物品的表面或內部所具備。 <具備本發明之燃料電池之物品的具體例> 可具備本發明之燃料電池之前述物品的具體例，可列 舉出大樓、住家、帳篷等建築物、螢光燈、LED等、有機 電致發光裝置、路燈、室內照明、訊號機等之照明器具、 機械、車輛及含有其本身之汽車用機器、家電製品、農業 機械、電子機器、包含行動電話等之可攜式資訊終端、美 容機材、可搬運式工具、衛浴用品等之衛生機材、家具、 玩具、裝飾品、公佈欄、冷卻器盒體、室外發電機等之戶 外用品、教材、人造花卉、物件、心臟起搏器用電源、具 備熱電轉換元件之加熱及冷卻器用電源。 實施例 以下藉由實施例更詳細地說明本發明，但本發明並不 限定於此等實施例。 此外，實施例及比較例的各項測定，係藉由下列方法 來進行。 〔分析方法〕 -24- 201143194 1. 粉末χ射線繞射 使用理學電機公司製的Rot a flex，進行試樣的粉末X射 線繞射。 各試樣的粉末X射線繞射中之繞射線峰値的個數，係 將可偵測出2個以上之訊號（S )與雜訊（N )之比（S/N ) 的信號視爲1個峰値來計數。 雜訊（N)係設爲基線的寬度。 2. 元素分析 碳：量取約〇. 1 g的試樣，以堀場製作所公司製的 EMIA-1 10進行測定。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electrode catalyst for a fuel cell, an electrode catalyst for a fuel cell, and use thereof. [Prior Art] A polymer electrolyte fuel cell has a form in which a solid polymer electrolyte is sandwiched between an anode and a cathode and fuel is supplied to an anode, and oxygen or air is supplied to a cathode to reduce oxygen at a cathode to take out electricity. The fuel cell. The fuel is mainly made of hydrogen or methanol. In the past, in order to improve the reaction speed of the fuel cell and improve the energy conversion efficiency of the fuel cell, a catalyst-containing layer is provided on the surface of the cathode (air electrode) or the anode (fuel electrode) of the fuel cell (hereinafter also referred to as "fuel cell" The catalyst layer is used. The catalyst is generally a noble metal. In the precious metal, a noble metal such as platinum or palladium which is stable at a high potential and has high activity is used. However, these precious metals are expensive and have limited resources. Gradually, the development of alternative catalysts is being sought. In addition, the precious metal used in the cathode surface sometimes dissolves in an acidic environment, and there is a problem that it is not suitable for applications requiring long-term durability. Therefore, it is strongly sought The development of a catalyst that does not corrode in an acidic environment and has excellent durability and high oxygen reduction energy. The replacement of the catalyst by the noble metal is proposed by the use of a noble metal carbide, a sulphur metal oxide, and a sulphur metal carbon oxynitride. Compound, chalcogen element-3-201143194 compound, carbon catalyst, etc. (for example, refer to Patent Document 1 to Patent Document 4). The material is cheaper and more resource-rich than a noble metal material such as platinum. However, in Patent Document 1 and Patent Document 2, such a catalyst containing a base metal material has a problem that sufficient oxygen reduction energy cannot be obtained practically. Further, in Patent Document 3 and Patent Document 4, although the activity of the high oxygen reduction catalyst is exhibited, there is still a problem that the stability of the catalyst under the operating conditions of the fuel cell is extremely low. The Nb and Ti oxycarbonitrides in Patent Document 5 and Patent Document 6 are particularly effective in exhibiting the above-described properties. The catalysts disclosed in Patent Documents 5 and 6 disclose substitutions with conventional precious metals. The medium has extremely high performance, but in a part of the manufacturing steps, it is necessary to perform heat treatment at a high temperature of 1600 ° C to 1 800 ° C (for example, the embodiment of Patent Document 5 or the example of Patent Document 6) 1). Such high-temperature heat treatment, although not industrially impossible, is accompanied by difficulties, resulting in increased equipment costs and operational management difficulties, and increased manufacturing costs, thus A method which can be manufactured more cheaply, and a technique which is relatively close to the present invention, is exemplified by Patent Document 7. In Patent Document 7, a technique for producing a titanium oxynitride containing carbon containing nitrogen and oxygen is reported. However, in the production method described in Patent Document 7, in order to produce titanium oxynitride containing carbon, it is necessary to produce titanium oxynitride based on the reaction of the nitrogen-containing organic compound with the titanium precursor-4-201143194. The two-stage synthesis of the production of carbon-containing titanium oxynitride based on the reaction of the phenol resin with the titanium oxynitride precursor is extremely complicated. In particular, the manufacture of the titanium oxynitride precursor must be carried out at 80 ° C. The production process is expensive by complicated steps such as stirring, superheating, reflux, cooling, and concentration under reduced pressure. Further, the phenol resin is a thermosetting resin having a three-dimensional network structure, so that it is difficult to uniformly mix and react with the metal oxide. In particular, the phenol resin has a thermal decomposition temperature of 400 ° C to 900 ° C, and therefore has a problem that it is difficult to cause a carbonization reaction caused by complete decomposition of the phenol resin below 1000 ° C. In addition, in Patent Document 7, only a film for a solar collector is used as a user, and a method for producing a metal oxycarbonitride having a shape such as a granular or fibrous shape which is highly useful as an electrode catalyst is not considered. And the use of the prior art. Patent Document 1: JP-A-2004-303664 Patent Document 2: Japanese International Publication No. 07/072665, Patent Document 3: US 2004/00967828 Patent Document 4: JP-A-2005-1 [Patent Document 5: Japanese Patent Laid-Open Publication No. 2009/03 1 383 pp. Patent Document 6: Japanese International Publication No. 2009/107518. Patent Document 7: Japanese Patent Laid-Open Publication No. 2009-23887. The problem to be solved is -5-201143194 The present invention is directed to solving the problems of the prior art. That is, the object of the present invention is to provide a heat treatment (sintering) step without setting a high temperature. A method of using an electrode catalyst for a fuel cell having a high catalytic activity using a transition metal (titanium or the like) is produced. Further, another object of the present invention is to provide a method for producing a fuel cell electrode catalyst which can produce a fuel cell electrode catalyst having high catalytic activity at low cost. (Means for Solving the Problem) The present invention relates to the following (1) to (17), for example. (1) A method for producing an electrode catalyst for a fuel cell, characterized in that an organic compound containing no nitrogen in a molecule and a transition metal containing oxygen in a molecule are contained in a gas atmosphere containing nitrogen at 500 to 1100 °C. The mixture of compounds is heat treated. (2) The method for producing an electrode catalyst for a fuel cell according to (1), wherein the organic compound containing no nitrogen in the molecule is selected from the group consisting of alcohols, hydroxyls, peroxys, ketones, aldehydes, ethers, Carboxyls, esters, carbonyls, thiols, sulfonic acids, saccharides, and nitrogen-free 5 and 6 membered heterocyclic compounds, and the above heterocyclic compounds may be combined with two or more cyclic structures. More than one group consisting of a compound and a complex. (3) The method for producing an electrode catalyst for a fuel cell according to (1), wherein the organic compound containing no nitrogen in the molecule is selected from the group consisting of polymer compounds obtained by polymerization of the compound of (2) Group - more than one. -6- 201143194 (4) The method for producing an electrode catalyst for a fuel cell according to (1), wherein the organic compound containing no nitrogen in the molecule is selected from the group consisting of polyvinyl alcohol, polyacrylic acid, polyethylene oxide, and ethylene. Alcohol, polyethylene glycol, citric acid, malic acid, succinic acid, fumaric acid, tartaric acid, oxalic acid, glucose, mannose, cellulose, fructose, galactose, maltose, sucrose, lactose, butyric acid, valeric acid, More than one group consisting of acid, octanoic acid and dodecanoic acid. (5) The method for producing an electrode catalyst for a fuel cell according to any one of (1) to (4) wherein the transition metal-containing compound containing oxygen in the molecule is a metal oxide or metal hydrogen containing the following metal An oxide or a mixture of the foregoing metal oxides and metal hydroxides selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, pin, niobium, molybdenum, niobium and tungsten. One or more metals of the group (hereinafter also referred to as "metal enamel" or simply "M": when two or more metals are contained, it is called "metal Ml" or simply "Ml" and The number is recorded in the rear). (6) The method for producing an electrode catalyst for a fuel cell according to any one of (1) to (5), wherein the organic compound containing no nitrogen in the molecule (when two or more kinds are the total molar number of all the organic compounds; The polymer compound and the transition metal-containing compound in a mixture of a polymer compound containing a transition metal-containing compound containing oxygen in the molecule (in the case of two or more kinds of moles of all metals) The mixing ratio is a range of 0.01 Sx/yS 100 when the number of moles of the organic compound and the transition metal-containing compound is X and y, respectively. (7) The method for producing an electrode catalyst for a fuel cell according to any one of (1) to (6) wherein the content of nitrogen in the nitrogen-containing gas is from 1 〇 to 201143194 100% by volume. (8) The method for producing an electrode catalyst for a fuel cell according to any one of (1) to (7) wherein the gas contains more than 0.01 to 5% by volume of nitrogen β (9) with respect to the gas containing nitrogen gas as a whole (eg) The method for producing an electrode catalyst for a fuel cell according to any one of (1), wherein the gas containing nitrogen gas of the whole gas further contains 0.01 to 10% by volume of oxygen. (10) The electrode catalyst for a fuel cell, which is an electrode catalyst for a fuel cell produced by the method for producing a fuel cell electrode for fuel cell according to any one of (D), which is characterized in that: The atomic ratio (transition metal element: carbon: nitrogen: oxygen) of the transition metal element, carbon, nitrogen, and oxygen constituting the fuel cell electrode catalyst is 1: X: y: Ζ, 〇 <χ$3,0 <y$2, 0 <z^3. (11) An electrode catalyst for a fuel cell, which is produced by the method for producing a fuel cell electrode catalyst according to any one of (1) to (9), characterized in that: When the transition metal element M1 and the transition metal element M2 constituting the electrode catalyst for the fuel cell are to be formed (only M1 is selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, chromium, lanthanum, molybdenum, a metal 'M2 of a group consisting of molybdenum and tungsten is at least one metal different from M1 selected from the aforementioned group), an atomic ratio of carbon, nitrogen and oxygen (transition metal element M1: transition metal element M2) : carbon: nitrogen: oxygen) is set to (1 - a ) : a: X: y: z when ' is 0 <aS0.5,0 <x$3,0 <y$ 2,0 < z S 3. (12) The electrode catalyst for fuel cell according to (10) or (11) above, wherein the specific surface area calculated by the BET method is 30 to 400 m 2 /g. (13) A catalyst layer for a fuel cell, comprising: the electrode catalyst for a fuel cell according to any one of (10) to (12). (14) The catalyst layer for a fuel cell according to (I3), which further contains an electron conductive substance. (15) An electrode comprising a fuel cell catalyst layer and a porous support layer, wherein the fuel cell catalyst layer is the fuel cell catalyst layer of (14). (16) The membrane electrode assembly is a membrane electrode assembly having a cathode and an anode and an electrolyte membrane disposed between the cathode and the anode, wherein the cathode and/or the anode are (15) electrode. (17) A fuel cell comprising: the membrane electrode assembly of (16). According to the method for producing an electrode catalyst for a fuel cell of the present invention, the electrode catalyst for a fuel cell can be produced at a lower temperature than the conventional method, so that the manufacturing cost can be reduced and the stability of the manufacturing step can be improved. [Embodiment] <Manufacturing Method of Electrode Catalyst for Fuel Cell> The method for producing an electrode catalyst for a fuel cell according to the present invention is characterized in that nitrogen is not contained in a molecule in a nitrogen-containing gas atmosphere at 500 to 1100 °C. Mixture of an organic compound with a transition metal-containing compound containing oxygen in the molecule - 201143194. The transition metal-containing compound containing oxygen in the molecule contains a group selected from the group consisting of, for example, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, hafnium, molybdenum, molybdenum, and tungsten. One or more metals (hereinafter also referred to as "metal M" or simply "M": when two or more metals are contained, it is called "metal Ml" or simply "Ml" and the number is indicated after the Μ) Transition metal element. Among these, titanium, zirconium, hafnium and molybdenum are preferable, and titanium and zirconium are more preferable from the viewpoint of cost and performance of the obtained catalyst. The transition metal-containing compound containing oxygen in the molecule may, for example, be an oxide or hydroxide of the transition metal or a mixture of an oxide and a hydroxide. The method of synthesizing the oxide, hydroxide or a mixture of the above metals is not particularly limited. For example, the alkoxide or metal salt of the above transition metal can be synthesized by a precipitation method or a hydrolysis method. Further, the synthesis can be carried out after forming a complex of the transition metal and mixing the organic compound. In the latter method, agglomeration of the obtained oxide, hydroxide or a mixture thereof can be suppressed, and a mixture with an organic compound having high purity and high homogeneity can be obtained. The user of the complex compound for forming a transition metal is not particularly limited as long as it does not contain nitrogen in the molecule, and examples thereof include acetamidine acetone and ethylene glycol. The alkoxide of the transition metal is not particularly limited, and is preferably a methoxide, an ethoxylate, a propoxide, an isopropoxide, a butoxide or an isobutyloxide of the transition metal, and particularly preferably an ethoxylate. , isopropoxide-10-201143194 and butoxide. The transition metal alkoxide may have one type of alkoxy group or two or more types of alkoxy groups. The metal salt of the transition metal is not particularly limited, and examples thereof include a chloride, a nitrate, an acetate, a carbonate 'sulfide, a cyanide, a borate, a phosphate, a side oxymetallate, and a bromide of the transition metal. , carbide, nitride, or a mixture of these. Particularly preferred are chlorides, nitrates and acetates. The organic compound containing no nitrogen in the molecule is not particularly limited as long as it does not cause thermal decomposition by heat treatment at 50 0 to 1100 °C. Preferably, it is selected from the group consisting of polyvinyl alcohol, polyacrylic acid, polyethylene oxide, ethylene glycol, polyethylene glycol, citric acid, malic acid, succinic acid, fumaric acid, tartaric acid, oxalic acid, glucose, mannose, One or more groups consisting of cellulose, fructose, galactose, maltose, sucrose, lactose, butyric acid, valeric acid, caproic acid, caprylic acid, and dodecanoic acid. Further, it is preferably one or more selected from the group consisting of polymer compounds obtained by polymerization of the above compounds. Further, among the above, water-soluble polymers such as polyvinyl alcohol, polyacrylic acid, and polyethylene oxide, and saccharides such as glucose, cellulose, and fructose, and citric acid, malic acid, succinic acid, and Fumar are preferable. An organic acid such as acid or tartaric acid. These compounds can be used in combination of 2 or more types. In the present invention, the use of an organic compound containing no nitrogen in the molecule is to set the nitrogen source of the electrode catalyst for the fuel cell to be a gas containing only nitrogen which constitutes the heat treatment atmosphere. In the past, in order to react a metal or a metal compound with nitrogen in a nitrogen atmosphere, it is necessary to carry out heat treatment at a temperature higher than the dissociation temperature of the nitrogen molecule of -11 - 201143194 degrees at a temperature of 1 200 ° C, but by using no molecules in the molecule. The nitrogen-containing organic compound' is heat-treated in a nitrogen-containing gas to react the metal or metal compound with nitrogen at a lower heat treatment temperature. The method of mixing the organic compound containing no nitrogen in the molecule with the compound containing a transition metal containing oxygen in the molecule is not particularly limited as long as it can be uniformly mixed, for example, in dissolving each compound in a solvent. Alternatively, after dispersing in a dispersion solvent, each compound is mixed and the solvent or dispersion solvent is removed. Further, the solvent or the dispersion solvent may be removed after mixing in another solution or dispersion solvent. An organic compound containing no nitrogen in the molecule (when two or more are the total molar number of all organic compounds; a polymer compound based on a monomer) and a compound containing a transition metal containing oxygen in the molecule (two or more types) When the number of moles of the total molar amount of all transition metals is set to X and y, respectively, and the ratio is set to x/y, each mixing ratio is preferably 〇.〇lSx/y $1〇〇 , especially good for O.lSx/ySlO. When the mixing ratio is within the above range, there is a tendency that nitrogen is easily introduced into the transition metal-containing compound by heat treatment. The heat treatment temperature of the above mixture is preferably in the range of 500 to 1100 ° C, particularly preferably in the range of 00 to 1 050 ° C, more preferably in the range of 900 to 100 Torr. When the heat treatment temperature is within the above range, it is preferable in terms of the crystallinity and uniformity of the obtained electrode catalyst for a fuel cell. In addition, a reduction in manufacturing costs and an increase in the safety of the manufacturing steps can be achieved. When the heat treatment temperature is less than 500 ° C, the reactivity of the precursor of the nitrogen-free organic compound in the molecule with the transition metal compound containing oxygen in the molecule -12-201143194 is deteriorated with the nitrogen in the sintering gas. It is difficult for nitrogen to enter the product. When the temperature is higher than 1 1 0 0 °c, the particle diameter becomes large, and the specific surface area tends to be small, and the reduction in the production cost and the improvement in the safety of the production step cannot be achieved. In the method for producing an electrode catalyst for a fuel cell of the present invention, as described above, an electrode catalyst for a fuel cell can be obtained by heat treatment at a lower temperature than the conventional method. Therefore, in the method for producing an electrode catalyst for a fuel cell of the present invention, an electrode cell for a fuel cell can be produced safely and at low cost. In the present invention, even if the heat treatment at such a low temperature is performed, the crystallinity and the uniformity are good, and the electrode catalyst for a fuel cell having high activity can be obtained, and it can be considered that the temperature is in the temperature range of 1 loot or less, based on the organic The thermal decomposition of the compound reaches the activated carbon and the nitrogen in the sintering gas easily reacts with the metal oxide or the metal hydroxide, and is substituted with the metal oxide or a part of the metal hydroxide, thereby being able to produce Preferred composition ratios of transition metal elements, carbon, nitrogen and oxygen are electrode catalysts for fuel cells. The heat treatment of the foregoing mixture is carried out under a nitrogen-containing gas atmosphere. By performing heat treatment in a nitrogen-containing gas atmosphere, the carbonization reaction proceeds while thermal decomposition of the organic compound containing the transition metal-containing compound as a raw material, and the nitridation reaction according to nitrogen gas is carried out. The nitrogen-containing gas is not particularly limited as long as it can efficiently produce an electrode catalyst for a fuel cell by heat treatment, and a mixed gas of nitrogen and hydrogen and nitrogen and argon are exemplified in addition to nitrogen. The mixed gas or the like may also contain oxygen. -13- 201143194 The content of nitrogen in the nitrogen-containing gas is preferably from 10 to 100% by volume, particularly preferably from 50 to 100% by volume. When the nitrogen-containing gas contains hydrogen, the hydrogen content is preferably 0.01 to 5% by volume. Further, the nitrogen-containing gas may contain 0.01 to 1% by volume of oxygen. The pressure of the heat-treated ambient gas is not particularly limited, and heat treatment can be performed under atmospheric pressure in consideration of manufacturing stability and cost. In the heat treatment of the mixture, the temperature increase rate to the sintering temperature described above is not particularly limited, and is, for example, preferably 1 to 100 ° C /min, particularly preferably 5 to 50 ° C /min. In addition, the holding time after the temperature rise is not particularly limited as long as it can carry out the carbonization reaction and the nitridation reaction, and the particle size and the production cost of the electrode catalyst for the fuel cell obtained are preferably 10 minutes. ~5 hours, especially 30 minutes to 3 hours. The shape of the electrode catalyst for a fuel cell is not particularly limited as long as it has a composition ratio of a transition metal element, carbon, nitrogen, and oxygen, and has sufficient oxygen reducing energy as an electrode catalyst for a fuel cell. For example, a particulate form, a fibrous form, a sheet form, a porous body structure, etc. are mentioned. The electrode catalyst for fuel cells requires high conductivity, stability, and high specific surface area. Therefore, the electrode catalyst for the fuel cell can be supported on the support during or after the above manufacturing steps. The support is not particularly limited as long as it has high conductivity and stability and a large specific surface area, and examples thereof include carbon black, carbon nanotube, carbon nanofiber, porous carbon, and carbon nanocone. Fullerene, graphite, graphene, carbon ceramics, conductive ceramics, and porous conductive ceramics. The shape and size of the support are not particularly limited, and the catalytic activity of the electrode catalyst for the fuel cell supported by the *14 - 201143194 is considered, and the support: preferably 10 to 1 000 nm, particularly preferably 10 to 100 nm » Further, depending on the properties of the organic compound containing no nitrogen in the molecule or the transition metal-containing compound containing oxygen in the former, the aggregation state of the catalyst obtained by the above may be uneven. At this time, the catalyst may be ground to obtain a fine and uniform particle size catalyst. The method of grinding the fuel cell electrode catalyst is not particularly limited: For example, a roller honing machine, a ball mill, a small diameter ball mill (bead j, a media agitating honing machine, a jet mill, a crucible, an automatic kneading) can be used. For the trough dissolving machine and the jet honing machine, when the amount of the catalyst is small, it is preferable to use the automatic kneading crucible or the batch type ball mill, and the catalyst is a large amount. When mixing and grinding, it is preferably Use a jet honing machine. <Catalyst> The electrode catalyst for a fuel cell of the present invention is produced by using the method for producing an electrode catalyst for a fuel cell of the present invention (also using the electrode catalyst for a fuel cell of the present invention described above) The electrode catalyst for the fuel cell manufactured by the manufacturer is a "catalyst (")". When the atomic ratio of the transition metal element, carbon, and oxygen constituting the catalyst (Α) is expressed as a transition metal element: Carbon: nitrogen: oxygen = 1:: ζ, preferably 0 <x$3,0 <yS2,0 <ζ$3. In terms of the high activity of the electrode catalyst, the range of x is particularly preferably SxS2.5, more preferably 〇.5$χ$2·0, especially preferably 0.7$χ$1·5, particularly preferably 0.01 SyS1.5. More preferably, it is 0.02Sy$0.5, and the specific diameter is higher than that of the molecular heat. The 以下, 钵, and the above are the following 'methods> Nitrogen and X: y are 〇·3, 丫的佳为-15- 201143194 The range of 0.03$丫$0.4,2 is particularly preferably 0.2$2$2.5', preferably 0.3$2 $2.0, and especially good for 〇·5$ζ$1·5. Further, when the catalyst (A) contains one or more transition metals selected from the group consisting of titanium, vanadium, chromium, manganese, iron, indium, nickel, copper, zinc 'chromium, antimony, molybdenum, niobium and tungsten When the element M1 and at least one transition metal element M2 different from the transition metal element M1 selected from the group are used as the transition metal element, the transition metal element M1, the transition metal element M2, and the carbon constituting the catalyst (A) The atomic ratio of nitrogen and oxygen is expressed as a transition metal element M1 : transition metal element M2: carbon: nitrogen: oxygen = (la) : a : x : y : z, preferably 〇 <a$0.5,0 <x^3> 0 <y^2> 0 <z S3. When the catalyst (A) contains the transition metal element M2, it is possible to improve the performance. The preferred range of X, y, and z is as described above, and the range of a is preferably 0.01 Sa'0.5, more preferably 0.02 $ aS0.4, and particularly preferably 0.03 SaS0. .3. The above a, X, 丫 and Z are measured by the method used in the examples described later. <Effects that can be exerted due to the presence of the transition metal element M2> due to the transition metal element M2 (and selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, hafnium, The presence of a transition metal element M1 of a group consisting of molybdenum, molybdenum and tungsten is different from at least one metal element). The effect is as follows: -16- 201143194 (1) Transition metal element M2 or transition metal element M2 The compound, when synthesizing the electrode catalyst, acts as a catalyst for forming a bond between the transition metal element M1 atom and the nitrogen atom. (2) Even when the electrode catalyst is used in a high potential or high oxidizing atmosphere in which the transition metal element M1 is eluted, the transition metal element M2 is prevented from being further eluted due to the passivation of the transition metal element M2. (3) In the heat treatment, the sintering of the heat-treated material is prevented, that is, the reduction of the specific surface area is prevented. (4) By the presence of the transition metal element M1 and the transition metal element M2 in the electrode catalyst, the metal elements are adjacent to each other. In the portion, a charge is generated, and thus adsorption or reaction of the substrate which is not formed in the electrode catalyst having only the transition metal element M1 as the metal element, or detachment of the product is generated. The catalyst (A) of the present invention is preferably an atom having a transition metal element, carbon, nitrogen and oxygen, and having an oxide, a carbide or a nitride of the above transition metal element alone or in plural of the above Crystal structure. It is judged from the result of analysis of the crystal structure of the catalyst (A) by X-ray diffraction analysis and the result of elemental analysis that the catalyst (A) is presumed to have an oxide structure having the transition metal element. Or a structure in which a carbon atom or a nitrogen atom is substituted for an oxygen atom portion of the oxide structure, or a carbide, a nitride or a carbonitride structure having the aforementioned transition metal element, or an oxygen atom instead of a carbon atom or nitrogen The structure of an atomic part, or a mixture containing such structures. -17- 201143194 < BET specific surface area> According to the method for producing an electrode catalyst for a fuel cell of the present invention, an electrode catalyst for a fuel cell having a large specific surface area can be produced, and the catalyst (A) of the present invention is calculated by the BET method. The specific surface area is preferably from 3 Torr to 4 Torr m 2 /g, particularly preferably from 50 to 350 m 2 /g, more preferably from 1 Torr to 300 m 2 /g. The catalyst (A) is preferably 〇.5 V (乂3.111^) or more, more preferably 〇.6, based on the reversible hydrogen electrode as measured by the following measurement method (A).乂 (^3.111^) or more, more preferably 〇.7¥ (vs.RHE) or more. [Measurement method (A): The catalyst and carbon are placed in a solvent so that the catalyst for carbon dispersed as the electron conductive material is 1% by mass, and the suspension is obtained by ultrasonic stirring. For the carbon system, carbon black (specific surface area: 100 to 300 m 2 /g (for example, XC-72 manufactured by Cabot Co., Ltd.) is used, and the mass ratio of the catalyst to carbon is 95:5. Further, the solvent is isopropyl. Alcohol: Water (mass ratio) = 2 : 1. Collect 1 μμί of the above suspension while applying ultrasonic waves, and quickly drip onto a glassy carbon electrode (diameter: 5.2 mm) at 5 °C. Drying in a minute. The fuel cell catalyst layer containing the catalyst is dried and formed on the glassy carbon electrode. The dropping and drying operations are carried out until a fuel cell contact of 1.0 mg or more is formed on the surface of the carbon electrode. Next, the NAFION (registered trademark) (manufactured by DuPont, 5% NAFION (registered trademark) solution (DE521)) was diluted 10-fold with isopropyl alcohol, and the diluted solution was added dropwise to the aforementioned fuel cell. On the catalyst layer, this was dried for 1 hour at -18-201143194 120 ° C. Using the electrode thus obtained, in an oxygen atmosphere and a nitrogen atmosphere, in a 0.5 mol/L aqueous sulfuric acid solution, at 30 At the temperature of °C, the same concentration of sulfuric acid in the aqueous solution The reverse hydrogen electrode was set as a reference electrode and polarized at a potential scanning speed of 5 mV/sec, thereby measuring a current-potential curve, and the reduction current at the time in the oxygen environment and the reduction current under a nitrogen atmosphere were started to appear. .2μΑ/(; the potential difference of iπη2 or more is set as the oxygen reduction onset potential.] In the present invention, the oxygen reduction current density can be obtained by the following method. First, from the results of the above measurement method (Α), The difference between the reduction current in the oxygen environment at 0.65 V (vs. RHE) and the reduction current in the nitrogen atmosphere, and then the calculated 电极 of the electrode area divided by the electrode area is set as the oxygen reduction current density ( Further, the oxygen reduction current density of the electrode catalyst for a fuel cell of the present invention is preferably 〇2 mA/cm 2 or more, more preferably 〇 5 mA/cm 2 or more, and particularly preferably 1.0 mA/cm 2 . Further, the higher the oxygen reduction current density, the higher the upper limit is not particularly limited and may be 1 〇〇 mA/cm 2 . <Applications> The catalyst (A) of the present invention can be used as a substitute catalyst for a platinum catalyst. The catalyst layer for a fuel cell of the present invention is characterized in that it contains the above-mentioned catalyst (A). The catalyst layer for a fuel cell has an anode catalyst layer and a cathode catalyst layer, and the catalyst (A) can be used in any of the above. The above catalyst (A) is preferably used in a cathode catalyst layer because of its excellent durability and large oxygen reduction energy. The catalyst layer for a fuel cell of the present invention preferably further contains an electron conductive powder. When the fuel cell catalyst layer containing the catalyst (A) further contains an electron conductive powder, the reduction current can be further increased. The electron conductive powder can be considered to have an electrical contact for exciting an electrochemical reaction in the above-mentioned catalyst (A), so that the reduction current can be increased. The aforementioned electron conductive particles are generally used as a support for a catalyst. Although the above-mentioned catalyst (A) has a certain degree of conductivity, in order to impart more electrons by the catalyst (A), or to allow the counter substrate to receive more electrons from the catalyst (A), it can be used to impart conductivity. The support particles are mixed with the catalyst (A). » The material of the electron conductive particles includes carbon, a conductive polymer, a conductive ceramic, a metal, or a conductive inorganic oxide such as tungsten oxide or ruthenium oxide. They may be used alone or in combination. In particular, the electron conductive particles composed of carbon have a large specific surface area, and can easily and inexpensively obtain a small particle diameter, and are excellent in chemical resistance and high potential resistance, and therefore are preferably carbon alone or carbon and others. A mixture of electron conducting particles. That is, the catalyst layer for a fuel cell preferably contains the above-mentioned catalyst (A) and carbon. Examples of the carbon include carbon black, graphite, carbon ceramics, activated carbon, carbon nanotubes, carbon nanofibers, carbon nanotubes, fullerenes, porous carbons, and graphene. When the particle diameter of the electron conductive particles made of carbon is too small, the electron conduction path is less likely to form, and when it is too large, the gas diffusibility of the fuel cell catalyst layer is lowered or the catalyst utilization rate is lowered. It is -20-201143194 5~1000nm, especially preferably 10~l〇〇nm. When the electron conductive particles are composed of carbon, the weight ratio of the catalyst (A) to the electron conductive particles (catalyst: electron conductive particles) is preferably 4:1 to 1000:1. The conductive polymer is not particularly limited, and examples thereof include polyacetylene 'poly(p-phenylene), polyaniline, polyalkylaniline, polypyrrole, polythiophene, polyfluorene, poly-1,5-diamino fluorene. 'Polyaminobiphenyl, poly(o-phenylenediamine), poly(quinoline) salt, polypyridine, polyquinoxaline, polyphenylquinoxaline and the like. Among these, polypyrrole, polyaniline, polythiophene, and preferably polypyrrole are preferable. The polymer electrolyte is not particularly limited as long as it is generally used in a fuel cell catalyst layer. Specifically, a perfluorocarbon polymer having a sulfonic acid group (for example, NAFION (registered trademark) (available from DuPont, 5% NAFI0N (registered trademark) solution (DE521), etc.), and a hydrocarbon group having a sulfonic acid group a polymer compound, a polymer compound doped with a mineral acid such as phosphoric acid, an organic/inorganic hybrid polymer partially substituted with a proton conductive functional group, or a proton conductor in which a phosphoric acid solution or a sulfuric acid solution is impregnated into a polymer matrix. Among these, NAFION (registered trademark) (manufactured by DuPont, 5% NAFION (registered trademark) solution (DE521)) is preferred. The fuel cell catalyst layer of the present invention can be used in the anode catalyst layer and the cathode. In any one of the catalyst layers, the catalyst layer for a fuel cell of the present invention has high oxygen reduction energy and contains a catalyst which is not easily corroded even in a high temperature in an acidic electrolyte, and thus is used as a cathode for a fuel cell. The 21 - 201143194 catalyst layer (cathode catalyst layer) is useful, and is particularly suitable for use in a dielectric layer provided on the cathode of a membrane electrode assembly provided in a solid fuel cell. The method of dispersing the catalyst (A) on the electron particles as a support may be dispersed in a gas stream or in a liquid dispersion, and the catalyst (A) and the electron particles may be dispersed in a solvent. The dispersion is preferably used in the catalyst layer forming step for a fuel cell. The dispersion in the liquid may be a method according to the orifice shrinkage flow, a method of changing the flow according to the slit, or a method according to ultrasonic waves, etc. It is not particularly limited as long as it does not erode the catalyst (A) and electron conduction and can be dispersed. Generally, a volatile organic solvent or water can be used. Further, the catalyst (A) is dispersed as a support. In the case of the above-mentioned electric particles, the method of forming the catalyst layer for dispersing the fuel cell and the dispersant is not particularly limited, and the catalyst (A) and the electron conductive particles are suspended therein. The coating method to be applied to the electrolyte membrane or the gas diffusion layer to be described later may be a soaking method, a screen printing method, a roll coating method, etc., and the above-mentioned catalyst (A) may be contained. A method in which a suspension of particles and an electrolyte is formed on a substrate by a coating method or a catalyst layer for a battery, and a fuel dielectric layer is formed on the electrolyte membrane by a transfer method. The fuel cell layer and the porous support layer are provided. The contact conductivity method of the body height distribution is liquid conductivity, so that the liquid-conducting liquid-conducting enthalpy is made of, for example, an electrolyte method. Electrolytic method for using a catalyst for a fuel cell-22- 201143194 The electrode of the present invention can be used in any of the cathode and the anode. The electrode of the present invention is used because of its excellent durability and large catalyst energy. In the case of a cathode, the industrial advantage is higher. The porous support layer is a layer that diffuses gas (hereinafter also referred to as a "gas diffusion layer"). The gas diffusion layer is not particularly limited as long as it has electron conductivity, high gas diffusibility, and high corrosion resistance, and generally carbon-based porous materials such as carbon paper or carbon cloth are used, or in order to reduce the weight. Use aluminum foil coated with stainless steel and corrosion resistant material. The membrane electrode assembly of the present invention is a membrane electrode assembly having a cathode and an anode and an electrolyte membrane disposed between the cathode and the anode, wherein the cathode and/or the anode are the electrodes. For the electrolyte membrane, for example, a perfluorosulfonic acid-based electrolyte membrane or a hydrocarbon-based electrolyte membrane may be used, or a liquid electrolyte may be impregnated into the polymer microporous membrane or the polymer electrolyte may be filled in the porous membrane. Body film, etc. Further, the fuel cell of the present invention is characterized by comprising the above-described membrane electrode assembly. The electrode reaction of a fuel cell is caused by a so-called three-phase interface (electrolyte-electrode catalyst-reaction gas). The fuel cell can be divided into several types depending on the electrolyte to be used, and the like, and there are a molten carbonate type (MCFC), a phosphoric acid type (PAFC), a solid oxide type (SOFC), a solid high molecular type (PEFC), and the like. Among them, the membrane electrode assembly of the present invention is preferably used in a polymer electrolyte fuel cell. The fuel cell using the catalyst (A) of the present invention has high performance and is extremely inexpensive when compared with when -23-201143194 is used as a catalyst. The fuel cell of the present invention can improve the performance of an article having a fuel cell having at least one function selected from the group consisting of a power generation function, a light emission function, a heat generation function, an acoustic generation function, a motion function, a display function, and a charging function. In particular, it can improve the performance of portable items. The fuel cell is preferably provided on the surface or inside of the article. <Specific Example of the Article Containing the Fuel Cell of the Present Invention> Specific examples of the article including the fuel cell of the present invention include a building, a house, a tent, and the like, a fluorescent lamp, an LED, and the like, and an organic battery. Lighting fixtures, street lamps, indoor lighting, signal conditioners, lighting fixtures, machinery, vehicles and their own automotive equipment, home appliances, agricultural machinery, electronic equipment, portable information terminals including mobile phones, beauty equipment Outdoor products, teaching materials, artificial flowers, objects, power supply for pacemakers, etc., sanitary tools, furniture, toys, decorations, bulletin boards, cooler boxes, outdoor generators, etc. A power supply for heating and cooling of thermoelectric conversion elements. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. Further, the measurements of the examples and comparative examples were carried out by the following methods. [Analytical method] -24- 201143194 1. Powder X-ray diffraction The powder X-ray diffraction of the sample was carried out using Rot a flex manufactured by Rigaku Corporation. The number of ray peaks in the powder X-ray diffraction of each sample is regarded as a signal that can detect two or more signals (S) and noise (N) ratio (S/N). 1 peak to count. The noise (N) is set to the width of the baseline. 2. Elemental analysis Carbon: A sample of about 1 g was taken and measured by EMIA-1 10 manufactured by Horiba, Ltd.
氮·氧：量取約〇.lg的試樣，密封於Ni-Cup後，以ON 分析裝置進行測定》 鈦：將約0.1 g的試樣量取至鉑皿’加入酸並進行加熱 分解。將該加熱分解物進行定容後稀釋’以ICP-MS進行定 量分析。 3. BET比表面積 採集0.15g的試樣，以全自動BET比表面積測定裝置 Macsorb (Mountech公司製）進行比表面積測定。前處理 時間及前處理溫度分別設定爲30分鐘、200°C。 〔實施例1〕 1.觸媒的調製 將30%硫酸鈦溶液（和光純藥公司製）18.24g加入於 蒸餾水中，製作出1 〇〇ml的溶液。將製作出的溶液滴入於 -25- 201143194 2 8 %氨水（和光純藥公司製）1 〇 〇 m 1與蒸餾水2 〇 〇 m 1之混合 溶液，而得氫氧化鈦的沉澱。將含有所得之氫氧化鈦的反 應液進行離心分離，藉此得到膠體狀氫氧化鈦。將聚乙烯 醇（和光純藥公司製、平均聚合度1000) 2.008g溶解於蒸 餾水50ml，並與所得之膠體狀氫氧化鈦6.5g混合》然後去 除溶劑。於管狀爐中，在1 ooot、氮氣環境下對所得之混 合粉末進行3小時的熱處理，藉此製得燃料電池用電極觸 媒（以下亦記載爲「觸媒（1)」）。 第1圖係顯示觸媒（1 )的粉末X射線繞射光譜。可觀 測到具有立方晶結構之鈦化物及具有金紅石型結構之氧化 鈦的繞射線峰値。 此外，第1表係表示觸媒（1)的元素分析結果。可確 認到碳、氮及氧的存在，並確認到氮在熱處理溫度1 〇〇〇 °c 下反應而進入於結晶晶格內。 觸媒（1)的BET比表面積爲2 13m2/g。 2.燃料電池用電極的製造 將觸媒（1 ) 〇.〇95g與碳（Cabot公司製的XC-72 ) 0.005g放入於以異丙醇：純水=2 : 1的質量比混合之溶液 1 Og，以超音波進行攪拌使其懸浮並混合。將該混合物 30μ1塗佈於玻璃碳電極（Tokai Carbon公司製、直徑： 5.2mm )，在1 2 0 °C下進行1小時的乾燥，而在碳電極表面 形成有l.Omg以上的燃料電池觸媒層。再者，以異丙醇將 NAFION (註冊商標）（DuPont公司製、5%NAFION (註 冊商標）溶液（DE521 ))稀釋10倍，並塗佈此稀釋液 -26- 201143194 1〇μ1，在120°C下進行1小時的乾燥，而得燃料電池用電極 (1 )。 3·氧還原能的評估 將所製作之燃料電池用電極（1 )，在氧氣環境及氮 氣環境下，於〇.5mol/L的硫酸水溶液中，在30。〇下以5mV/ 秒的電位掃描速度進行分極，並測定電流-電位曲線。此 時將同一濃度的硫酸水溶液中之可逆氫電極設定爲參考電 極。 從上述測定結果中，將在氧氣環境下的還原電流與氮 氣環境下的還原電流之間開始顯現〇.2pA/cm2以上的差之 電位，設爲氧還原起始電位。此外，計算出在0.65 V ( vs.RHE)時之氧氣環境下的還原電流與氮氣環境下的還原 電流之差。然後再將以電極面積除上計算出之値後的値， 設爲氧還原電流密度（mA/cm2 )。 藉由氧還原起始電位及氧還原電流密度，評估所製作 之燃料電池用電極（1)的觸媒能。 亦即，氧還原起始電位愈高，氧還原電流密度愈大， 則表示燃料電池用電極中之觸媒的觸媒能愈高。 第9圖係顯示藉由上述測定所得之電流一電位曲線。 實施例1中所製作之觸媒（1)，其氧還原起始電位爲 0.83 V ( vs.RHE )，氧還原電流密度爲 〇· 1 8mA/cm2 » 〔實施例2〕 1.觸媒的調製 -27- 201143194 將30%硫酸鈦溶液（和光純藥公司製）18.24g加入於 蒸餾水中，製作出100ml的溶液。將製作出的溶液滴入於 28%氨水（和光純藥公司製）100ml與蒸餾水200ml之混合 溶液，而得氫氧化鈦的沉澱。將含有所得之氫氧化鈦的反 應液進行離心分離，藉此得到膠體狀氫氧化鈦。將聚乙烯 醇（和光純藥公司製、平均聚合度1000 ) 2.008 g溶解於蒸 餾水50ml，並與所得之膠體狀氫氧化鈦6.5g混合。然後去 除溶劑。於管狀爐中，在8 00 °C、氮氣環境下對所得之混 合粉末進行3小時的熱處理，藉此製得燃料電池用電極觸 媒（以下亦記載爲「觸媒（2 )」）。 第2圖係顯示觸媒（2)的粉末X射線繞射光譜。可觀 測到具有立方晶結構之鈦化物、具有銳鈦礦型結構之氧化 鈦及具有金紅石型結構之氧化鈦的繞射線峰値》 此外，第1表係表示觸媒（2)的元素分析結果。可確 認到碳、氮及氧的存在，並確認到氮在熱處理溫度800 °C 下反應而進入於結晶晶格內。 觸媒（2)的BET比表面積爲243m2/g。 2. 燃料電池用電極的製造 除了使用前述觸媒（2)之外，其他與實施例1相同而 得燃料電池用電極（2 )。 3. 氧還原能的評估 除了使用前述燃料電池用電極（2)之外，其他與實 施例1相同來評估觸媒能。 第1 〇圖係顯示藉由上述測定所得之電流一電位曲線。 -28- 201143194 實施例2中所製作之觸媒（2)，其氧還原起始電位爲 0.78V ( vs.RHE) ’氧還原電流密度爲 0.〇8mA/cm2。 〔實施例3〕 1. 觸媒的調製 將30%硫酸鈦溶液（和光純藥公司製）18.24g加入於 蒸餾水中’製作出l〇〇ml的溶液。將製作出的溶液滴入於 28%氨水（和光純藥公司製）100ml與蒸餾水200ml之浪合 溶液，而得氫氧化鈦的沉澱。將含有所得之氫氧化鈦的反 應液進行離心分離，藉此得到膠體狀氫氧化鈦。將葡萄糖 (純正化學公司製）1.3 96g溶解於蒸餾水50ml，並與所得 之膠體狀氫氧化鈦6.5g混合。然後去除溶劑。於管狀爐中 ，在1000 °C、氮氣環境下對所得之混合粉末進行3小時的 熱處理，藉此製得燃料電池用電極觸媒（以下亦記載爲「 觸媒（3 )」）。 第3圖係顯示觸媒（3 )的粉末X射線繞射光譜。可觀 測到具有立方晶結構之鈦化物及具有金紅石型結構之氧化 鈦的繞射線峰値。 此外，第1表係表示觸媒（3)的元素分析結果。可確 認到碳、氮及氧的存在，並確認到氮在熱處理溫度1 〇 〇 〇 °c 下反應而進入於結晶晶格內。 觸媒（3)的BET比表面積爲223m2/g。 2. 燃料電池用電極的製造 除了使用前述觸媒（3 )之外，其他與實施例1相同而 -29- 201143194 得燃料電池用電極（3 )。 3.氧還原能的評估 除了使用前述燃料電池用電極（3)之外，其他與實 施例1相同來評估觸媒能。 第11圖係顯示藉由上述測定所得之電流-電位曲線。 實施例3中所製作之觸媒（3 )，其氧還原起始電位爲 0.86V ( vs.RHE)，氧還原電流密度爲 0.5 9m A/cm2。 〔實施例4〕 1-觸媒的調製 將30%硫酸鈦溶液（和光純藥公司製）18.24g及乙酸 鐵（Aldrich公司製）1.8 23 g加入於蒸餾水中，製作出 100ml的溶液。將製作出的溶液滴入於2 8 %氨水（和光純藥 公司製）l〇〇ml與蒸餾水200ml之混合溶液，而得氫氧化鈦 的沉澱。將含有所得之氫氧化鈦的反應液進行離心分離， 藉此得到膠體狀氫氧化鈦。將聚乙烯醇（和光純藥公司製 、平均聚合度1000) 2.008g溶解於蒸餾水5 0ml，並與所得 之膠體狀氫氧化鈦6.5g混合。然後去除溶劑。於管狀爐中 ，在1 000 °C、氮氣環境下對所得之混合粉末進行3小時的 熱處理，藉此製得燃料電池用電極觸媒（以下亦記載爲「 觸媒（4)」）》 第4圖係顯不觸媒（4)的粉末X射線繞射光譜。可觀 測到具有立方晶結構之鈦化物及具有金紅石型結構之氧化 欽的繞射線峰値。 -30- 201143194 此外’第1表係表示觸媒（4)的元素分析結果。可確 認到碳、氮及氧的存在’並確認到氮在熱處理溫度丨〇 〇 〇。〇 下反應而進入於結晶晶格內。 觸媒（4)的BET比表面積爲210m2/g。 2.燃料電池用電極的製造 除了使用即述觸媒（4)之外，其他與實施例1相同而 得燃料電池用電極（4 )。 3 .氧還原能的評估 除了使用前述燃料電池用電極（4)之外，其他與實 施例1相同來評估觸媒能。 第1 2圖係顯示藉由上述測定所得之電流—電位曲線。 實施例4中所製作之觸媒（4)，其氧還原起始電位爲 0.83 V ( vs.RHE ) ’氧還原電流密度爲 0.3 9m A/cm2 » 〔比較例1〕 1.觸媒的調製 將30%硫酸鈦溶液（和光純藥公司製）18.24g加入於 蒸餾水中，製作出100ml的溶液。將製作出的溶液滴入於 28%氨水（和光純藥公司製）100ml與蒸餾水200ml之混合 溶液，而得氫氧化鈦的沉澱。將含有所得之氫氧化鈦的反 應液進行離心分離，藉此得到膠體狀氫氧化鈦。將聚乙烯 醇（和光純藥公司製、平均聚合度10 〇〇) 2.008 g溶解於蒸 餾水50ml，並與所得之膠體狀氫氧化鈦6.5g混合。然後去 除溶劑。於管狀爐中，在l〇〇〇°C、氬氣環境下對所得之混 -31 - 201143194 合粉末進行3小時的熱處理，藉此製得燃料電池用電極觸 媒（以下亦記載爲「觸媒（5 )」）。 第5圖係顯示觸媒（5 )的粉末X射線繞射光譜。僅觀 測到具有金紅石型結構之氧化鈦的繞射線峰値。 此外，第1表係表示觸媒（5)的元素分析結果。可確 認到碳及氧的存在。當將熱處理環境氣設爲氬氣時，由於 無氮氣源，故確認到氮未進入於結晶晶格內。 觸媒（5)的BET比表面積爲187m2/g。 2 .燃料電池用電極的製造 除了使用前述觸媒（5)之外，其他與實施例1相同而 得燃料電池用電極（5 ) ^ 3 ·氧還原能的評估 除了使用前述燃料電池用電極（5)之外，其他與實 施例1相同來評估觸媒能。 第1 3圖係顯示藉由上述測定所得之電流-電位曲線。 比較例1中所製作之觸媒（5 )，其氧還原起始電位爲 0.75 V ( VS.RHE )，氧還原電流密度爲〇.〇4m A/cm2 ’在氬 氣環境下進行熱處理者，與在氮氣環境下進行熱處理者相 比，可得知觸媒能較低。 〔比較例2〕 1.觸媒的調製 將30%硫酸鈦溶液（和光純藥公司製）H24g加入於 蒸餾水中，製作出l〇〇ml的溶液。將製作出的溶液滴入於 -32- 201143194 28%氨水（和光純藥公司製）1 00ml與蒸餾水200ml之混合 溶液，而得氫氧化鈦的沉澱。將含有所得之氫氧化鈦的反 應液進行離心分離’藉此得到膠體狀氫氧化鈦。不將所得 之膠體狀氫氧化鈦6.5 g與有機化合物混合，而在8 0 °C進行 真空乾燥。於管狀爐中，在1 000 °C、氮氣環境下對所得之 粉末進行3小時的熱處理，藉此製得燃料電池用電極觸媒 (以下亦記載爲「觸媒（6 )」）。 第6圖係顯示觸媒（6 )的粉末X射線繞射光譜。僅觀 測到具有金紅石型結構之氧化鈦的繞射線峰値。 此外，第1表係表示觸媒（6)的元素分析結果。僅確 認到氧的存在。因此，當未使用有機化合物時，即使熱處 理環境氣爲氮氣，亦不會與氮反應，而確認到氮未進入於 結晶晶格內。. 觸媒（6)的BET比表面積爲12m2/g。 2.燃料電池用電極的製造 除了使用前述觸媒（6)之外，其他與實施例1相同而 得燃料電池用電極（6 )。 3 .氧還原能的評估 除了使用前述燃料電池用電極（6)之外，其他與實 施例1相同來評估觸媒能。 第1 4圖係顯示藉由上述測定所得之電流-電位曲線。 比較例2中所製作之觸媒（6 )，其氧還原起始電位爲 0.60V ( vs.RHE)，氧還原電流密度爲OmA/cm2，未使用 有機化合物者，與使用有機化合物者相比，可得知觸媒能 -33- 201143194 極低。 〔比較例3〕 1 .觸媒的調製 將30%硫酸鈦溶液（和光純藥公司製）18.24g加入於 蒸餾水中，製作出l〇〇ml的溶液。將製作出的溶液滴入於 28%氨水（和光純藥公司製）100ml與蒸餾水200ml之混合 溶液，而得氫氧化鈦的沉澱。將含有所得之氫氧化鈦的反 應液進行離心分離，藉此得到膠體狀氫氧化鈦。將聚乙烯 醇（和光純藥公司製、平均聚合度1000) 2.008g溶解於蒸 餾水50ml，並與所得之膠體狀氫氧化鈦6.5 g混合。然後去 除溶劑。於管狀爐中，在1 2 0 0 °C、氮氣環境下對所得之混 合粉末進行3小時的熱處理，藉此製得燃料電池用電極觸 媒（以下亦記載爲「觸媒（7)」）。 第7圖係顯示觸媒（7)的粉末X射線繞射光譜《未觀 測到具有金紅石型結構之氧化鈦的繞射線峰値，僅觀測到 具有立方晶結構之鈦碳氮氧化物的繞射線峰値。 此外，第1表係表示觸媒（7)的元素分析結果。可確 認到碳、氮及氧的存在，並確認到在熱處理溫度丨2 〇〇。(：下 ’與氮更加進行反應，使氮多量地進入於結構內而使氧有 減少之傾向。 觸媒（7)的BET比表面積爲162m2/g。 2·燃料電池用電極的製造 除了使用前述觸媒（7)之外’其他與實施例1相同而 -34- 201143194 得燃料電池用電極（7 )。 3.氧還原能的評估 除了使用前述燃料電池用電極（7)之外，其他與實 施例1相同來評估觸媒能。 第15圖係顯示藉由上述測定所得之電流-電位曲線。 比較例3中所製作之觸媒（7 )，其氧還原起始電位爲 0.73V ( vs.RHE )，氧還原電流密度爲OmA/cm2，當熱處 理溫度從l〇〇〇°C提高至120(TC時，可得知觸媒能降低。 〔比較例4〕 1.觸媒的調製 以硏缽將氧化鈦（昭和電工公司製、Super Titania F6 )3.52g與碳（Cabot公司製、Vulcan 72 ) 1.32g充分地粉 碎並混合。於管狀爐中，在1 000 °C、氮氣環境下對該混合 粉末進行3小時的熱處理之後。在管狀爐中，在1〇〇〇 °C， 由2體積％之氧氣、4體積％之氫氣及94體積％之氮氣所構成 之含氮氣體環境下對所得之粉末l.Og進行3小時熱處理， 藉此製得燃料電池用電極觸媒（以下亦記載爲「觸媒（8 )j ) ° 第8圖係顯示觸媒（8 )的粉末X射線繞射光譜。僅觀 測到具有金紅石型結構之氧化鈦的繞射線峰値。 此外，第1表係表示觸媒（8 )的元素分析結果。僅確 認到氧的存在。因此，可得知在該合成條件下，碳不會與 氧化鈦反應，熱處理環境的氮亦未進入於結構內。 -35- 201143194 觸媒（8)的BET比表面積爲8m2/g» 2. 燃料電池用電極的製造 除了使用前述觸媒（8)之外，其他與實施例1相同而 得燃料電池用電極（8 )。 3. 氧還原能的評估 除了使用前述燃料電池用電極（8)之外’其他與實 施例1相同來評估觸媒能。 第1 6圖係顯示藉由上述測定所得之電流-電位曲線。 比較例4中所製作之觸媒（8)，其氧還原起始電位爲 0.66V ( vs.RHE )，氧還原電流密度爲0.02mA/cm2，可得 知在該合成條件下，作爲觸媒的氧還原能極低》 第2表係彙總顯示出前述實施例及比較例中所得之燃 料電池用電極觸媒的氧還原起始電位及氧還原電流密度。 〔第1表〕各燃料電池用電極觸媒的元素分析結果（質量％)Nitrogen and oxygen: A sample of about 〇. lg was weighed and sealed in a Ni-Cup and measured by an ON analyzer. Titanium: A sample of about 0.1 g was taken into a platinum dish, and acid was added and decomposed by heating. The heated decomposition product was subjected to constant volume and diluted by quantitative analysis by ICP-MS. 3. BET specific surface area A sample of 0.15 g was collected, and the specific surface area was measured by a fully automatic BET specific surface area measuring apparatus Macsorb (manufactured by Mountech Co., Ltd.). The pretreatment time and the pretreatment temperature were set to 30 minutes and 200 °C, respectively. [Example 1] 1. Preparation of a catalyst 18.24 g of a 30% titanium sulfate solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to distilled water to prepare a solution of 1 〇〇ml. The prepared solution was dropped into a mixed solution of -25-201143194 2 8 % ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.) 1 〇 〇 m 1 and distilled water 2 〇 〇 m 1 to obtain a precipitate of titanium hydroxide. The reaction liquid containing the obtained titanium hydroxide was centrifuged to obtain colloidal titanium hydroxide. 2.008 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., average polymerization degree: 1000) was dissolved in 50 ml of distilled water and mixed with 6.5 g of the obtained colloidal titanium hydroxide, and then the solvent was removed. In the tubular furnace, the obtained mixed powder was heat-treated in a nitrogen atmosphere for 3 hours to obtain an electrode catalyst for a fuel cell (hereinafter also referred to as "catalyst (1)"). Figure 1 shows the powder X-ray diffraction spectrum of the catalyst (1). A ray peak having a cubic crystal structure and a ruthenium oxide having a rutile structure was observed. Further, the first table indicates the result of elemental analysis of the catalyst (1). The presence of carbon, nitrogen and oxygen was confirmed, and it was confirmed that nitrogen reacted at a heat treatment temperature of 1 〇〇〇 °c to enter the crystal lattice. The catalyst (1) had a BET specific surface area of 2 13 m 2 /g. 2. Preparation of Electrode for Fuel Cell The catalyst (1) 〇. 95g and carbon (XC-72 manufactured by Cabot Co., Ltd.) 0.005g were mixed in a mass ratio of isopropyl alcohol: pure water = 2:1. The solution was 1 Og, stirred with an ultrasonic wave to suspend and mix. 30 μl of the mixture was applied to a glassy carbon electrode (manufactured by Tokai Carbon Co., Ltd., diameter: 5.2 mm), and dried at 120 ° C for 1 hour, and a fuel cell contact of 1.0 mg or more was formed on the surface of the carbon electrode. Media layer. Further, NAFION (registered trademark) (manufactured by DuPont, 5% NAFION (registered trademark) solution (DE521)) was diluted 10-fold with isopropyl alcohol, and this dilution was applied -26-201143194 1〇μ1 at 120 Drying was carried out for 1 hour at ° C to obtain an electrode (1) for a fuel cell. 3. Evaluation of oxygen reduction energy The electrode (1) for the fuel cell produced was placed at 30 in an aqueous solution of sulfuric acid of 5 mol/L in an oxygen atmosphere and a nitrogen atmosphere. The arm was polarized at a potential scanning speed of 5 mV/sec, and the current-potential curve was measured. At this time, the reversible hydrogen electrode in the same concentration of aqueous sulfuric acid solution was set as the reference electrode. From the above measurement results, a potential of a difference of p2 pA/cm2 or more was started between the reduction current in the oxygen atmosphere and the reduction current in the nitrogen atmosphere, and the oxygen reduction onset potential was set. In addition, the difference between the reduction current in an oxygen environment at 0.65 V (vs. RHE) and the reduction current in a nitrogen atmosphere was calculated. Then, the enthalpy after dividing the calculated electrode area by the calculated area is set to the oxygen reduction current density (mA/cm2). The catalytic energy of the electrode (1) for fuel cell produced was evaluated by the oxygen reduction onset potential and the oxygen reduction current density. That is, the higher the oxygen reduction onset potential and the higher the oxygen reduction current density, the higher the catalyst energy of the catalyst in the fuel cell electrode. Figure 9 shows the current-potential curve obtained by the above measurement. The catalyst (1) prepared in Example 1 had an oxygen reduction onset potential of 0.83 V (v. RHE) and an oxygen reduction current density of 〇·1 8 mA/cm 2 » [Example 2] 1. Catalyst Modulation -27- 201143194 18.24 g of a 30% titanium sulfate solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to distilled water to prepare a 100 ml solution. The prepared solution was dropped into a mixed solution of 100 ml of 28% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) and 200 ml of distilled water to obtain a precipitate of titanium hydroxide. The reaction liquid containing the obtained titanium hydroxide was centrifuged to obtain colloidal titanium hydroxide. 2.008 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., average polymerization degree: 1000) was dissolved in 50 ml of distilled water, and mixed with 6.5 g of the obtained colloidal titanium hydroxide. Then remove the solvent. In the tubular furnace, the obtained mixed powder was heat-treated at 800 ° C for 3 hours in a nitrogen atmosphere to obtain an electrode catalyst for a fuel cell (hereinafter also referred to as "catalyst (2 )"). Figure 2 shows the powder X-ray diffraction spectrum of the catalyst (2). It is observed that a titanium compound having a cubic crystal structure, a titanium oxide having an anatase structure, and a ruthenium peak of a titanium oxide having a rutile structure. Further, the first watch system indicates elemental analysis of the catalyst (2). result. The presence of carbon, nitrogen and oxygen was confirmed, and it was confirmed that nitrogen reacted at a heat treatment temperature of 800 ° C to enter the crystal lattice. The catalyst (2) had a BET specific surface area of 243 m 2 /g. 2. Production of Fuel Cell Electrode The fuel cell electrode (2) was obtained in the same manner as in Example 1 except that the above-mentioned catalyst (2) was used. 3. Evaluation of oxygen reduction energy The catalyst energy was evaluated in the same manner as in Example 1 except that the fuel cell electrode (2) described above was used. The first graph shows the current-potential curve obtained by the above measurement. -28- 201143194 The catalyst (2) produced in Example 2 had an oxygen reduction onset potential of 0.78 V (v. RHE) and an oxygen reduction current density of 0 〇 8 mA/cm 2 . [Example 3] 1. Preparation of a catalyst 18.24 g of a 30% titanium sulfate solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to distilled water to prepare a solution of 10 ml. The prepared solution was dropped into a solution of 100 ml of 28% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) and 200 ml of distilled water to obtain a precipitate of titanium hydroxide. The reaction liquid containing the obtained titanium hydroxide was centrifuged to obtain colloidal titanium hydroxide. 1.3 96 g of glucose (manufactured by Junsei Chemical Co., Ltd.) was dissolved in 50 ml of distilled water, and mixed with 6.5 g of the obtained colloidal titanium hydroxide. The solvent is then removed. In the tubular furnace, the obtained mixed powder was heat-treated at 1000 ° C for 3 hours in a nitrogen atmosphere to obtain an electrode catalyst for a fuel cell (hereinafter also referred to as "catalyst (3 )"). Figure 3 shows the powder X-ray diffraction spectrum of the catalyst (3). A ray peak having a cubic crystal structure and a ruthenium oxide having a rutile structure was observed. Further, the first table indicates the result of elemental analysis of the catalyst (3). The presence of carbon, nitrogen and oxygen was confirmed, and it was confirmed that nitrogen reacted at a heat treatment temperature of 1 〇 〇 c °c to enter the crystal lattice. The catalyst (3) had a BET specific surface area of 223 m 2 /g. 2. Production of Fuel Cell Electrode The fuel cell electrode (3) was obtained in the same manner as in Example 1 except that the above-mentioned catalyst (3) was used. 3. Evaluation of oxygen reduction energy The catalyst energy was evaluated in the same manner as in Example 1 except that the fuel cell electrode (3) described above was used. Figure 11 shows the current-potential curve obtained by the above measurement. The catalyst (3) produced in Example 3 had an oxygen reduction onset potential of 0.86 V (v. RHE) and an oxygen reduction current density of 0.5 9 m A/cm 2 . [Example 4] Preparation of 1-catalyst 18.24 g of a 30% titanium sulfate solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.823 g of iron acetate (manufactured by Aldrich Co., Ltd.) were added to distilled water to prepare a 100 ml solution. The prepared solution was dropped into a mixed solution of 20% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 ml of distilled water to obtain a precipitate of titanium hydroxide. The reaction liquid containing the obtained titanium hydroxide was centrifuged to obtain colloidal titanium hydroxide. 2.008 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., average polymerization degree: 1000) was dissolved in 50 ml of distilled water, and mixed with 6.5 g of the obtained colloidal titanium hydroxide. The solvent is then removed. The obtained mixed powder was heat-treated in a tubular furnace at 1 000 ° C for 3 hours in a nitrogen atmosphere to obtain an electrode catalyst for a fuel cell (hereinafter also referred to as "catalyst (4)"). The figure 4 shows the powder X-ray diffraction spectrum of the non-catalyst (4). A radiant peak of a titanium compound having a cubic crystal structure and an oxidant having a rutile structure was observed. -30- 201143194 In addition, the '1st watch shows the elemental analysis result of the catalyst (4). The presence of carbon, nitrogen and oxygen was confirmed and the nitrogen was confirmed to be at the heat treatment temperature 丨〇 〇 . The underlying reaction enters the crystalline crystal lattice. The catalyst (4) had a BET specific surface area of 210 m 2 /g. 2. Production of fuel cell electrode The fuel cell electrode (4) was obtained in the same manner as in Example 1 except that the catalyst (4) was used. 3. Evaluation of oxygen reduction energy The catalyst energy was evaluated in the same manner as in Example 1 except that the fuel cell electrode (4) described above was used. Fig. 12 shows the current-potential curve obtained by the above measurement. The catalyst (4) prepared in Example 4 had an oxygen reduction onset potential of 0.83 V (v. RHE). The oxygen reduction current density was 0.39 m A/cm 2 » [Comparative Example 1] 1. Catalyst modulation 18.24 g of a 30% titanium sulfate solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to distilled water to prepare a 100 ml solution. The prepared solution was dropped into a mixed solution of 100 ml of 28% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) and 200 ml of distilled water to obtain a precipitate of titanium hydroxide. The reaction liquid containing the obtained titanium hydroxide was centrifuged to obtain colloidal titanium hydroxide. 2.008 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., average polymerization degree: 10 〇〇) was dissolved in 50 ml of distilled water, and mixed with 6.5 g of the obtained colloidal titanium hydroxide. Then remove the solvent. In the tubular furnace, the obtained mixed-31 - 201143194 powder was heat-treated in a argon atmosphere for 3 hours to obtain an electrode catalyst for a fuel cell (hereinafter also referred to as "touch". Media (5)"). Figure 5 shows the powder X-ray diffraction spectrum of the catalyst (5). Only the ray peaks of the titanium oxide having a rutile structure were observed. Further, the first table indicates the result of elemental analysis of the catalyst (5). The presence of carbon and oxygen is confirmed. When the heat treatment ambient gas was set to argon gas, it was confirmed that nitrogen did not enter the crystal lattice because there was no nitrogen gas source. The catalyst (5) had a BET specific surface area of 187 m 2 /g. 2. Production of Electrode for Fuel Cell In addition to the use of the above-mentioned catalyst (5), the electrode for fuel cell (5) was obtained in the same manner as in Example 1. The evaluation of the oxygen reduction energy was carried out except that the electrode for the fuel cell described above was used ( Other than Example 5, the catalyst energy was evaluated in the same manner as in Example 1. Fig. 13 shows the current-potential curve obtained by the above measurement. The catalyst (5) prepared in Comparative Example 1 had an oxygen reduction onset potential of 0.75 V (VS.RHE) and an oxygen reduction current density of 〇.〇4 m A/cm 2 'heat treatment in an argon atmosphere, It is known that the catalyst energy is lower than that of the heat treatment under a nitrogen atmosphere. [Comparative Example 2] 1. Preparation of a catalyst A 30% titanium sulfate solution (manufactured by Wako Pure Chemical Industries, Ltd.) H24g was added to distilled water to prepare a solution of 10 ml. The prepared solution was dropped into a mixed solution of -200-201143194 28% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.) of 100 ml and distilled water (200 ml) to obtain a precipitate of titanium hydroxide. The reaction solution containing the obtained titanium hydroxide was subjected to centrifugation, whereby colloidal titanium hydroxide was obtained. The obtained colloidal titanium hydroxide 6.5 g was not mixed with an organic compound, and vacuum dried at 80 °C. In the tubular furnace, the obtained powder was heat-treated at 1 000 ° C for 3 hours in a nitrogen atmosphere to obtain an electrode catalyst for a fuel cell (hereinafter also referred to as "catalyst (6 )"). Figure 6 shows the powder X-ray diffraction spectrum of the catalyst (6). Only the ray peaks of the titanium oxide having a rutile structure were observed. Further, the first table indicates the result of elemental analysis of the catalyst (6). Only the presence of oxygen is confirmed. Therefore, when the organic compound is not used, even if the heat treatment atmosphere is nitrogen, it does not react with nitrogen, and it is confirmed that nitrogen does not enter the crystal lattice. The catalyst (6) has a BET specific surface area of 12 m 2 /g. 2. Production of fuel cell electrode The fuel cell electrode (6) was obtained in the same manner as in Example 1 except that the above-mentioned catalyst (6) was used. 3. Evaluation of oxygen reduction energy The catalyst energy was evaluated in the same manner as in Example 1 except that the fuel cell electrode (6) described above was used. Fig. 14 shows the current-potential curve obtained by the above measurement. The catalyst (6) prepared in Comparative Example 2 had an oxygen reduction onset potential of 0.60 V (v. RHE) and an oxygen reduction current density of 0 m/cm 2 , and an organic compound was not used, compared with those using an organic compound. It can be seen that the catalyst can be -33- 201143194 extremely low. [Comparative Example 3] 1. Preparation of a catalyst 18.24 g of a 30% titanium sulfate solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to distilled water to prepare a solution of 10 ml. The prepared solution was dropped into a mixed solution of 100 ml of 28% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) and 200 ml of distilled water to obtain a precipitate of titanium hydroxide. The reaction liquid containing the obtained titanium hydroxide was centrifuged to obtain colloidal titanium hydroxide. 2.008 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., average polymerization degree: 1000) was dissolved in 50 ml of distilled water, and mixed with 6.5 g of the obtained colloidal titanium hydroxide. Then remove the solvent. The obtained mixed powder was heat-treated in a tubular furnace at 1,200 ° C for 3 hours in a nitrogen atmosphere to obtain an electrode catalyst for a fuel cell (hereinafter also referred to as "catalyst (7)"). . Fig. 7 shows the powder X-ray diffraction spectrum of the catalyst (7) "No ray peaks of titanium oxide having a rutile structure were observed, and only a titanium carbon oxynitride having a cubic crystal structure was observed. Ray peaks. Further, the first table indicates the result of elemental analysis of the catalyst (7). The presence of carbon, nitrogen and oxygen was confirmed and confirmed to be 丨2 热处理 at the heat treatment temperature. (The lower part reacts more with nitrogen, so that nitrogen enters the structure in a large amount and the oxygen tends to decrease. The catalyst (7) has a BET specific surface area of 162 m 2 /g. 2. Manufacturing of fuel cell electrodes is used. Other than the above-mentioned catalyst (7), the other electrode of the fuel cell (7) was obtained in the same manner as in the first embodiment. -34-201143194. 3. Evaluation of oxygen reduction energy In addition to the use of the fuel cell electrode (7) described above, The catalyst energy was evaluated in the same manner as in Example 1. Fig. 15 shows the current-potential curve obtained by the above measurement. The catalyst (7) prepared in Comparative Example 3 had an oxygen reduction onset potential of 0.73 V ( Vs. RHE), the oxygen reduction current density is 0 mA/cm 2 , and when the heat treatment temperature is increased from l 〇〇〇 ° C to 120 (TC, it is known that the catalyst energy is lowered. [Comparative Example 4] 1. Catalyst modulation 3.52 g of titanium oxide (Super Titania F6, manufactured by Showa Denko Co., Ltd.) and 1.32 g of carbon (Vulcan 72, manufactured by Cabot Co., Ltd.) were sufficiently pulverized and mixed in a tubular furnace at 1 000 ° C under a nitrogen atmosphere. After the heat treatment of the mixed powder for 3 hours, in a tubular furnace, at 1〇〇 °C, the obtained powder l.Og was heat-treated for 3 hours in a nitrogen-containing atmosphere composed of 2% by volume of oxygen, 4% by volume of hydrogen, and 94% by volume of nitrogen gas, thereby preparing an electrode contact for a fuel cell. The medium (hereinafter also referred to as "catalyst (8)j) ° Fig. 8 shows the powder X-ray diffraction spectrum of the catalyst (8). Only the ray peak of the titanium oxide having the rutile structure was observed. Further, the first table shows the result of elemental analysis of the catalyst (8). Only the presence of oxygen was confirmed. Therefore, it was found that under the synthesis conditions, carbon does not react with titanium oxide, and nitrogen in the heat treatment environment does not enter. In the structure. -35- 201143194 The BET specific surface area of the catalyst (8) is 8 m2/g» 2. The fuel cell electrode is produced in the same manner as in the first embodiment except that the above-mentioned catalyst (8) is used. Battery electrode (8) 3. Evaluation of oxygen reduction energy The catalyst energy was evaluated in the same manner as in Example 1 except that the fuel cell electrode (8) was used. Fig. 16 shows the measurement obtained by the above measurement. Current-potential curve. Catalyst prepared in Comparative Example 4 ( 8), the oxygen reduction onset potential is 0.66V (v. RHE), and the oxygen reduction current density is 0.02 mA/cm2. It can be seen that under the synthesis conditions, the oxygen reduction energy as a catalyst is extremely low. The oxygen reduction onset potential and the oxygen reduction current density of the electrode catalyst for a fuel cell obtained in the above-mentioned Examples and Comparative Examples are summarized. [Table 1] Elemental analysis results of electrode catalysts for each fuel cell (% by mass) )
有機化合物 熱處理條件 Ti Fe C N 0 誠 實施例1 聚乙烯醇 N：' 1000°C 64.3 — 14 1.7 20 a施例2 聚乙烯醇 N：« 800°C 67.1 — 12 0.9 20 TlC〇7iN〇〇4〇〇89 K施例3 葡葡糖 N2、1000°C 66.3 — 23 2.4 9.3 Tie 丨.4〇N〇13〇〇.43 Η施例4 聚乙烯醇 N2 1000°C 66.1 2.7 16 2.3 13 〇4〇〇.89 比較例1 聚乙烯醇 Ar、1000t 64.0 — 15 0 21 TiC〇93〇〇98 比較例2 無 N2 > lOOOt 61.9 — 0 0 38 TiO,», 比較例3 聚乙烯醇 N2 > 1200〇C 72.2 — 13 2.8 12 TiC〇77N〇 n〇n sn 比較例4 無 N2、1000°C 59.0 — 0 0 41 Ti〇2.08 2%02/4%H2/94%N2' 1000°C -36- 201143194 L第2表〕各燃料電池用電極觸媒之氧還原能的評估結^ 氧還原起始電位 〔V vs.RHE〕 w- ^ · · · ， 一〆 氧還原電流密度@〇.65V ~~~' (mA/cm2) 實施例1 0.83 * — — 0.18 實施例2 0.78 0.08 實施例3 0.86 0.59 實施例4 0.83 0.39 比較例1 0.75 〜 一 0.04 比較例2 0.60 0 比較例3 0.73 0 比較例4 0.66 0.02 產業上之可利用性： 本發明之製造方法’可在較以往更低的反應溫度下進 行氮化反應’故可降低燃料電池用電極觸媒的製造成本。 【圖式簡單說明】 第1圖爲實施例1之觸媒（1 )的粉末X射線繞射光譜》 第2圖爲實施例2之觸媒（2 )的粉末X射線繞射光譜。 第3圖爲實施例3之觸媒（3 )的粉末X射線繞射光譜。 第4圖爲實施例4之觸媒（4 )的粉末X射線繞射光譜。 第5圖爲比較例1之觸媒（5)的粉末X射線繞射光譜。 第6圖爲比較例2之觸媒（6)的粉末X射線繞射光譜。 第7圖爲比較例3之觸媒（7)的粉末X射線繞射光譜。 第8圖爲比較例4之觸媒（8)的粉末X射線繞射光譜。 第9圖爲評估實施例1之燃料電池用電極（1)的氧還 •37- 201143194 原能之電流-電位曲線。 第10圖爲評估實施例2之燃料電池用電極（2)的氧還 原能之電流-電位曲線。 第1 1圖爲評估實施例3之燃料電池用電極（3 )的氧還 原能之電流-電位曲線。 第12圖爲評估實施例4之燃料電池用電極（4)的氧還 原能之電流-電位曲線。 第1 3圖爲評估比較例1之燃料電池用電極（5 )的氧還 原能之電流一電位曲線。 第1 4圖爲評估比較例2之燃料電池用電極（6 )的氧還 原能之電流一電位曲線。 第15圖爲評估比較例3之燃料電池用電極（7)的氧還 原能之電流-電位曲線。 第16圖爲評估比較例4之燃料電池用電極（8 )的氧還 原能之電流一電位曲線。 -38-Organic compound heat treatment conditions Ti Fe CN 0 Example 1 Polyvinyl alcohol N: '1000 ° C 64.3 — 14 1.7 20 a Example 2 Polyvinyl alcohol N: « 800 ° C 67.1 — 12 0.9 20 TlC〇7iN〇〇4 〇〇89 K Example 3 Glucose N2, 1000 ° C 66.3 — 23 2.4 9.3 Tie 丨.4〇N〇13〇〇.43 ΗExample 4 Polyvinyl alcohol N2 1000°C 66.1 2.7 16 2.3 13 〇4 〇〇.89 Comparative Example 1 Polyvinyl alcohol Ar, 1000t 64.0 - 15 0 21 TiC〇93〇〇98 Comparative Example 2 No N2 > lOOOT 61.9 - 0 0 38 TiO,», Comparative Example 3 Polyvinyl alcohol N2 > 1200〇C 72.2 — 13 2.8 12 TiC〇77N〇n〇n sn Comparative Example 4 No N2, 1000°C 59.0 — 0 0 41 Ti〇2.08 2%02/4%H2/94%N2' 1000°C -36 - 201143194 L No. 2] Evaluation of the oxygen reduction energy of the electrode catalyst for each fuel cell. Oxygen reduction onset potential [V vs. RHE] w- ^ · · · , an oxygen reduction current density @〇.65V ~~~' (mA/cm2) Example 1 0.83 * - - 0.18 Example 2 0.78 0.08 Example 3 0.86 0.59 Example 4 0.83 0.39 Comparative Example 1 0.75 ~ a 0.04 Comparative Example 2 0.60 0 Comparative Example 3 0.73 0 Comparison Example 4 0.66 0.02 INDUSTRIAL APPLICABILITY The production method of the present invention can be subjected to a nitridation reaction at a lower reaction temperature than in the prior art, so that the production cost of the electrode catalyst for a fuel cell can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a powder X-ray diffraction spectrum of a catalyst (1) of Example 1, and Fig. 2 is a powder X-ray diffraction spectrum of a catalyst (2) of Example 2. Fig. 3 is a powder X-ray diffraction spectrum of the catalyst (3) of Example 3. Fig. 4 is a powder X-ray diffraction spectrum of the catalyst (4) of Example 4. Fig. 5 is a powder X-ray diffraction spectrum of the catalyst (5) of Comparative Example 1. Fig. 6 is a powder X-ray diffraction spectrum of the catalyst (6) of Comparative Example 2. Fig. 7 is a powder X-ray diffraction spectrum of the catalyst (7) of Comparative Example 3. Fig. 8 is a powder X-ray diffraction spectrum of the catalyst (8) of Comparative Example 4. Fig. 9 is a graph showing the current-potential curve of the original energy of the oxygen electrode (1) of the fuel cell electrode (1) of Example 1. Fig. 10 is a graph showing the current-potential curve of the oxygen reduction energy of the fuel cell electrode (2) of Example 2. Fig. 1 is a graph showing the current-potential curve of the oxygen reduction energy of the fuel cell electrode (3) of Example 3. Fig. 12 is a graph showing the current-potential curve of the oxygen reduction energy of the fuel cell electrode (4) of Example 4. Fig. 13 is a graph showing the current-potential curve of the oxygen reduction energy of the fuel cell electrode (5) of Comparative Example 1. Fig. 14 is a graph showing the current-potential curve of the oxygen reduction energy of the fuel cell electrode (6) of Comparative Example 2. Fig. 15 is a graph showing the current-potential curve of the oxygen reduction energy of the fuel cell electrode (7) of Comparative Example 3. Fig. 16 is a graph showing the current-potential curve of the oxygen reduction energy of the fuel cell electrode (8) of Comparative Example 4. -38-