臺灣博碩士論文加值系統

本研究利用固態燒結法(Solid-state reaction)製備六鈮酸鉀K4Nb6O17，再進行剝落反應，製備出奈米片結構NS-K4Nb6O17(NSK)，並加入Au或Rh以及Graphite oxide(GO) 作為產氫觸媒，利用商用WO3以初濕含浸法添加0.5wt% Pt作為產氧觸媒，並使用NaI水溶液當作I-/IO3-氧化還原媒介，光源使用400W中壓鹵素燈，並控制反應溶液在43 oC，進行Z-scheme光催化全水分解反應系統之研究。光觸媒性質鑑定藉由X-Ray繞射儀(XRD)、紫外-可見光分析儀、氣相層析儀(GC)、解析型穿透式電子顯微鏡(TEM)、光致激發光光譜儀(PL)、電化學工作站等。
首先我們以化學法檸檬酸鈉還原四氯金酸溶液合成出奈米金，改變檸檬酸鈉量能製備出不同大小的奈米金，分別為17 nm、33 nm、40 nm添加到NSK對於光催化活性的影響，以粒徑為33 nm的Au(m)/NSK產氫觸媒有最好的產氣活性(H2: 486 O2: 225 (μmol g-1 h-1))，接著以檸檬酸、PVP、抗壞血酸於三甘醇溶液還原六氯銠酸鈉，能合成出金字塔型Rh奈米顆粒，再藉由調控濃度與時間，能製備出不同大小的金字塔型Rh，分別為14 nm、25 nm、55 nm，其中以粒徑為25 nm的Rh(m)/NSK作為產氫觸媒有最好的產氣活性(H2: 759 O2: 415(μmol g-1 h-1)) ，Rh/NSK光觸媒製備藉由合成NSK時添加六氯銠酸鈉金屬鹽溶液，展現出很高的產氣活性(H2: 4240 O2: 1622 (μmol g-1 h-1))，再來添加GO於Rh/NSK提高產氣活性，合成時添加GO以3%GO/Rh/NSK最佳(H2: 5430 O2: 2226 (μmol g-1 h-1))，含浸法添加GO以IMP-5%GO/Rh/NSK有最高的產氫活性(H2: 7623 (μmol g-1 h-1))，但產氧活性(O2: 1913 (μmol g-1 h-1))不好，添加GO最好的方式是以反應中添加GO，以A-5%GO/Rh/NSK有最好的產氣活性(H2: 7039 O2: 3289 (μmol g-1 h-1))。

In this study, we used solid state reaction to prepare K4Nb6O17. Then, we used exfoliation method to prepare the nanosheets photocatalyst, NS-K4Nb6O17(NSK). Au, Rh, Graphite oxide(GO) were loaded to NSK as cocatalyst. The photocatalysis activity for H2 evolution in a Z-scheme on M/K4Nb6O17 (M= Au, Rh, GO) photocatalyst is studied. Pt/WO3 was used as O2 evolution photocatalyst. And NaI solution was used as shuttle redox mediator. The light source was a 400W medium-pressure Halogen lamp. The reaction of Z-scheme photocatalysis overall water splitting system was 43oC. The catalysts were characterized by X-ray diffraction(XRD), UV-visible, Gas Chromatography(GC), transmission electron microscopy(TEM), electrochemical analyzer.
First, Au nanoparticle was prepared by using C6H5O7Na3 to reduce HAuCl4.
Different amount of C6H5O7Na3 could prepare different size of Au nanoparticle,17 nm,
33 nm,40 nm . Au(m)/NSK with diameters of 33 nm Au nanoparticle had the best photoactivity (H2: 486 O2: 225 (μmol g-1 h-1)). Second, pyramid Rh nanoparticle was prepared by Na3RhCl6 reduced by L-ascorbic acid in triethylene glycol solution with PVP protector. By controlling concentration of Na3RhCl6, L-ascorbic acid and reaction time, different of size pyramid Rh nanoparticle,14 nm,25 nm,55 nm could be prepared. The highest of photoactivity H2 evolution photocatalyst is Rh(m)/NSK (H2: 759 O2: 415 (μmol g-1 h-1))with diameters of 25 nm pyramid Rh nanoparticle. The Rh/NSK photocatalyst was prepared by adding Na3RhCl6 to exfoliation solution of NSK. The Rh/NSK photocatalyst exhibited a vary high photoactivity (H2: 4240 O2: 1622 (μmol g-1 h-1)). Furthermore, GO was loading to Rh/NSK to improve photoactivity. The 3%GO/Rh/NSK photocatalyst was prepared by adding GO and Na3RhCl6 to exfoliation solution of NSK, and showed a higher photoactivity (H2: 5430 O2: 2226 (μmol g-1 h-1)). IMP-5%GO/Rh/NSK was prepared by Impregnation method showed the highest H2 evolution rate (H2: 7623 ) but O2 evolution rate was lower (O2: 1913 (μmol g-1 h-1)). The best way to load GO on NSK is to add GO in the NaI solution. A-5%GO/Rh/NSK exhibited a highest photoactivity (H2: 7039 O2: 3289 (μmol g-1 h-1)).

致謝 II
摘要 III
Abstract IV
目錄 VI
圖目錄 IX
表目錄 XIII
第一章 研究背景和文獻回顧 1
1.1前言 1
1.2研究目的 1
1.3文獻回顧 2
1.3.1光催化水分解 2
1.3.2 pH值的影響 6
1.3.3共觸媒影響 7
1.3.4 K4Nb6O17光觸媒 13
1.3.5剝落法/再離子交換製備奈米片光觸媒 14
1.3.6氧化石墨 17
1.3.7 Z-schene系統 18
第二章 實驗方法與步驟 28
2.1 實驗藥品與耗材 28
2.2實驗設備與儀器 28
2.3光觸媒製備 29
2.3.1製備SS-K4Nb6O17光觸媒 29
2.3.2製備SS-H3.1K0.9Nb6O17光觸媒 30
2.3.3製備NS-K4Nb6O17光觸媒 31
2.3.4製備金屬Rh添加於NS-K4Nb6O17光觸媒 32
2.3.5氧化石墨之製備 33
2.3.6奈米金之製備 33
2.3.7金字塔型Rh之製備 34
2.3.8添加GO於 NS-K4Nb6O17-1.5wt%Rh光觸媒 34
2.3.9添加奈米金於 NS-K4Nb6O17光觸媒 35
2.3.10添加金字塔型Rh於 NS-K4Nb6O17光觸媒 35
2.3.11製備金屬Pt添加於WO3光觸媒 35
2.3.12光觸媒命名 36
2.4 光觸媒性質分析 38
2.4.1 X-Ray繞射儀(XRD) 38
2.4.2 紫外-可見光(UV-visible)分析儀 38
2.4.3 氣相層析儀(Gas Chromatography)。 39
2.4.4 解析型穿透式電子顯微鏡(TEM) 40
2.4.5 光致激發光光譜儀(P.L) 41
2.5 GC檢量線製作 41
2.5.1 氫氣檢量線 42
2.5.2 氧氣檢量線 43
2.6 光催化水分解產氫實驗 44
2.7 光觸媒光電化學性質量測 45
第三章 實驗結果與討論 47
3.1 共觸媒鑑定 47
3.1.1氧化石墨鑑定 47
3.1.2奈米金鑑定 54
3.1.3金字塔型Rh鑑定 55
3.2添加奈米金於NSK之光催化全水分解效果影響 57
3.3添加Rh於NSK之光催化全水分解效果影響 66
3.4 添加GO於Rh/NSK之光催化全水分解效果影響 77
3.5 改變添加GO方式於Rh/NSK之光催化全水分解效果影響 85
第四章 結論 95
參考文獻 97

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