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Title: | 釕鈀雙金屬錯合物的合成與光催化活性 Synthesis and Photocatalytic Activity of A Ruthenium-Palladium Bimetallic Complex |
Authors: | 高若晴 Jo-Ching Kao |
Advisor: | 劉緒宗 Shiuh-Tzung Liu |
Keyword: | 光催化,過度金屬催化, Photocatalysis,Transition metal catalysis, |
Publication Year : | 2024 |
Degree: | 碩士 |
Abstract: | 本篇論文以多牙氮配位基 5-phenyl-2,8-di-(2-pyridinyl)anthyridine (bppa),將帶有2,2''-聯吡啶配基的釕金屬光催化單元和鈀金屬串聯,合成異核雙金屬錯合物RuPd,探討其光催化反應活性。
在光催化鈴木耦合反應中,使用可見光照射室溫下即可進行,且擁有良好的官能基耐受性,若在此光催化系統中額外添加能幫助電子轉移的三乙胺,會造成反應產率降低,顯示反應機構應為能量轉移。 而在硝基苯還原反應中,雖然不具有期望的光催化活性,然而RuPd可藉由與氫氣反應會生成鈀奈米粒子來催化硝基苯還原反應,且利用與RuPd鈀金屬單元相似的Pd-ppy錯合物即可進行,此反應可以容忍鹵素、甲氧基、乙醯基等可能進行副反應的官能基。透過核磁共振光譜儀監控反應以及使用可能的中間體作為起始物進行反應,推測此硝基苯還原反應是經由直接路徑而非縮合路徑。 In this thesis, we used a 5-phenyl-2,8-di-(2-pyridinyl)anthyridine (bppa) as a bridging ligand to synthesize a bimetallic complex RuPd and investigated its photocatalytic activity. Suzuki–Miyaura coupling of arylbromides and arylboronic acids can proceed smoothly under irradiation of visible light at room temperature. The addition of triethylamine, which is used to promote the electron transfer process, suppressed the catalytic activity of complex RuPd, suggesting that this reaction proceeds through an energy transfer process. The reduction of nitroarenes cannot be catalyzed by complex RuPd under irradiation of visible light. However, we found that complex RuPd could generate palladium nanoparticles in situ under hydrogen atmosphere, which could catalyze the reduction of nitroarenes into the corresponding anilines. This reduction was also proceeded with the use of complex Pd-ppy as the catalyst under the similar conditions for the complex RuPd, indicating that Pd-ppy yielded the active nanoparticle species as well. Thus, reduction of anilines with various functional groups such as halogen, methoxy, and acetyl catalyzed by Pd-ppy under the atmosphere of hydrogen was studied. The mechanism was investigated by monitoring the reaction via nuclear magnetic resonance spectroscopy and using potential intermediates as starting materials. The results suggest that this reaction proceeds through a direct route rather than a condensation pathway. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/92229 |
DOI: | 10.6342/NTU202400745 |
Fulltext Rights: | 同意授權(限校園內公開) |
Appears in Collections: | 化學系 |
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ntu-112-1.pdf Restricted Access | 7.11 MB | Adobe PDF | View/Open |
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