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研究生： 蘇家陞
Su, Chia-Sheng
論文名稱： 對己二腈電合成反應具高活性與選擇性之電極材料開發
Development of electrode material with high activity and selectivity towards electrosynthesis of adiponitrile
指導教授： 林家裕
Lin, Chia-Yu
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2021
畢業學年度： 109
語文別： 中文
論文頁數： 78
中文關鍵詞： 丙烯腈 、己二腈 、電催化加氫二聚合 、電觸媒
外文關鍵詞： Acrylonitrile, Adiponitrile, Electro-hydrodimerization, Electro-catalyst
相關次數： 點閱：116  下載：0 
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    • 己二腈係為製備尼龍66的單體之一，因工業需求量大，因此開發一具高效能與具環境友善之生產程序方法極為重要。相較傳統須使用氫化氰有毒氣體的丁二烯氫氰化反應生產己二腈製程，丙烯腈電化學加氫二聚化反應生成己二腈因具可在常溫常壓進行，且僅利用水作為丙烯腈氫化的質子來源等優點，其近年的研究開發日益受到矚目。
    本研究利用定電流電化學沉積法製備鉍基電觸媒修飾電極，並且將其應用於電催化丙烯腈加氫二聚化合成己二腈。藉由修飾電極之電鍍條件(如電鍍電量、電鍍液組成)與丙烯腈電解條件(如四級銨鹽濃度、丙烯腈濃度效應、電解液之酸鹼值)之探討與優化，我們所製備的鉍基電觸媒修飾電極其性能可與目前商用的鉛修飾電極匹敵。例如，在施加電位為-1.60 V (vs. NHE)下，所製備之鉍基電觸媒修飾電極其法拉第效率、己二腈產生速率以及轉換頻率分別可達84.17 ± 1.11 %、0.48 ± 0.01 mmol cm-2 h-1與88.65 ± 2.47 h-1，而鉛修飾電極則為78.25 ± 1.88 %、0.61 ± 0.04 mmol cm-2 h-1與104.66 ± 7.16 h-1。為了進一步提高鉍基電觸媒之電催化活性，我們也利用製備具奈米片狀結構之碘氧化鉍並透過還原前處理來製備具奈米片狀結構之鉍基電觸媒。結果顯示，奈米結構化可進一步提高其電催化活性;所得法拉第效率、己二腈產生速率以及轉換頻率分別可高達79.80 ± 2.27 %、1.28 ± 0.20 mmol cm-2 h-1及546.47 ± 86.30 h-1。本研究成功開發出一種對環境友善、低毒性，且對丙烯腈電催化加氫二聚化生成己二腈之反應具有高的選擇率與高的法拉第效率的電觸媒材料。

    Adiponitrile (ADN) is one of the monomeric precursor for the synthesis of nylon 66. However, the traditional ADN synthesis mostly relies on the hydrocyanation process of 1,3-butadiene with hazardous hydrogen cyanide1-3. The electrohydrodimerization (EDH) of acrylonitrile into ADN serves a less energy-intensive and green synthetic alternative route to produce ADN4-7.
    In this work, we present the detailed studies on the effects of electrode materials and electrolysis conditions (e.g., applied potential, electrolyte composition, and electrolyte pH) on the electrohydrodimerization of acrylonitrile into adiponitrile at near neutral pH. Under optimal condition, the nanostructured bismuth modified electrode exhibited a turnover frequency of 546.47 ± 86.30 h-1, which is about 5.2 times higher than the nanostructured lead modified electrode (104.66 ± 7.16 h-1). In addition, the nanostructured bismuth modified electrode showed comparable selectivity, in terms of Faradaic efficiency, towards adiponitrile production with the lead modified one (79.80 ± 2.27 % vs 78.25 ± 1.88 %). These results suggest that bismuth can be a promising non-toxic alternative to lead that is commonly used in commercial EDH process for ADN production.

    摘要 I Extended Abstract II 致謝 XIII 總目錄 XIV 表目錄 XVI 圖目錄 XVII 第一章 緒論 1 1.1 前言 1 1.2 己二腈市場需求 3 1.3 己二腈化學合成法 4 1.3.1 丁二烯法 4 1.3.2 己二酸法 6 第二章 原理與文獻回顧 8 2.1 丙烯腈電化學加氫二聚合成反應機制 8 2.2 吸附模型與材料選擇 12 2.3 丙烯腈電解條件效應 16 2.4 鉍基電觸媒之電催化應用 22 2.4 研究動機 25 第三章 實驗方法 26 3.1 實驗藥品 26 3.2 實驗設備 28 3.3 溶液配製 29 3.4 工作電極之製備 30 3.4.1 鉍基電觸媒之製備 31 3.4.2 鉛基電觸媒之製備 31 3.4.3 奈米片狀結構之鉍基電觸媒之製備 32 3.5 電化學分析系統 33 3.6 氣相層析法 35 3.6.1 產物定量分析 36 3.6.2 定電位電解法合成己二腈之數值計算 38 第四章 結果與討論 39 4.1 直流電製備鉍基電觸媒修飾電極於電催化丙烯腈 39 4.1.1 形貌與相態分析 39 4.1.2 表面覆蓋率於電催化丙烯腈之影響 42 4.1.3 四丁基銨鹽濃度於電催化丙烯腈之影響 45 4.1.4 反應電位於電催化丙烯腈之影響 48 4.1.5 丙烯腈濃度於電催化丙烯腈之影響 53 4.1.6 溶液酸鹼值於電催化丙烯腈之影響 55 4.2 直流電製備鉛基電觸媒修飾電極於電催化丙烯腈 58 4.2.1 形貌與相態分析 58 4.2.2 鉛基電觸媒與鉍基電觸媒之比較 61 4.3 奈米片狀鉍基電觸媒修飾電極 63 4.3.1 形貌與相態分析 63 4.3.2 各類電觸媒性能之比較 66 第五章 結論與未來展望 70 5.1 結論 70 5.2 建議與未來展望 71 第六章 附錄 72 第七章 參考文獻 74

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