研究生: |
黃詠勝 |
---|---|
論文名稱: |
鋅鐵氧化物修飾硒硫化鎘奈米棒光觸媒於 可見光驅動光催化分解水產氫之研究 ZnFe2O4 Decorated CdS1-xSex Nanorods in Visible-light Driven Photocatalytic Water Splitting for Hydrogen Production |
指導教授: | 呂世源 |
口試委員: |
吳紀聖
李岱洲 |
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: | 2014 |
畢業學年度: | 102 |
語文別: | 中文 |
論文頁數: | 99 |
中文關鍵詞: | 硒硫化鎘 、分解水 、產氫 、異質結構 、鋅鐵氧化物 、能隙控制 |
相關次數: | 點閱:2 下載:0 |
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以光觸媒催化產氫,有三個重要的步驟,第一是吸收入射光的能量產生電子電洞對,第二是電子電洞遷移至光觸媒表面,最後分別產生還原與氧化反應。其中重要的關鍵有二:光觸媒具有適合的能帶結構吸收入射光,和電子電洞對的分離效率。此兩者將影響光觸媒的效能甚鉅。
本研究以製備硒硫化鎘奈米棒(CdS1-xSex nanorods)為主體材料,再搭配附在奈米棒外部的鋅鐵氧化物ZnFe2O4形成異質結構複合材料。最核心的構想是希望能藉由硒元素的摻入調控光觸媒的能隙,再加上鋅鐵氧化物自身磁性可回收的特性,而這樣的異質結構且能帶位置匹配使得產氫效率提升、減少光腐蝕,使產氫長效性穩定。之後的檢測再利用UV-visible、XRD、BET、XPS、SEM、PL、TEM分別檢測光觸媒之光吸收特性、觸媒晶相、比表面積、元素比例、形貌、放光特性以及粒徑大小,藉以進一步分析討論。
光觸媒使用熱溶劑法製備,以丙二胺為溶劑攝氏190度持溫24小時反應,成功合成出硒硫化鎘奈米棒,根據XRD和UV-visible吸收光譜的檢測,可以證實硒元素成功摻入硒硫化鎘奈米棒內,得以調控光觸媒半導體的能隙。在複合之後的樣品也通過磁性的檢測,能順利用磁鐵將分散在水中的樣品蒐集起來。
固體懸浮法產氫的研究設備為內照式反應系統,使用的犧牲試劑是亞硫酸鈉搭配硫化鈉,反應器的外部以1M的亞硝酸鈉溶液,過濾紫外光,於400W 高壓汞燈照射下,將0.05克光觸媒分散於500毫升犧牲試劑溶液進行反應。硒硫化鎘奈米棒的產氫效果隨著硒元素的增加而上升,但在硒的元素比例到達30%之後產氫速率增加的現象消失甚至有下降。在複合之後的材料,目前最佳的產氫速率是20wt%鋅鐵氧化物複合10%硒硫化鎘奈米棒,其產氫速率在複合前後由40.63(μ mol hr-1)升至99.73(μ mol hr-1)。
這是由於鋅鐵氧化物和硒硫化鎘能帶結構匹配,光生電子會從鋅鐵氧化物傳導至硒硫化鎘的導帶位置進行還原反應,電洞則從硒硫化鎘的價帶傳導至鋅鐵氧化物的價帶,再與水溶液或是犧牲試劑發生氧化反應,因而達到增進電子電洞分離的效果,使產氫速率提升。在產氫的長效穩定性測試,20wt%鋅鐵氧化物複合10%硒硫化鎘奈米棒經歷35小時長效產氫共七次的循環測試,平均產氫速率維持在99.67(μ mol hr-1)的數值,第七次的產氫效率依然保有103(μ mol hr-1),可見其具備長效產氫穩定性。
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