CO, CN- ,NO+ 配位基π-accepting能力之研究和 亞硝基鐵錯合物製造氫氣之應用

Investigation of π-accepting ability of CO, CN, NO ligands and application of Iron nitrosyl complexes for hydrogen production.

林鼎鈞(Ting-Chun Lin)

指導教授 ： 謝忠宏

淡江大學/理學院/化學學系碩士班/碩士(2018年)

https://doi.org/10.6846/TKU.2018.00390

摘要

雙原子配位基 ( CO、NO、CN ) 在生物體為重要的配位基，本論文乃透過中心金屬鈷合成類似三配位基在同一金屬上的四配位錯合物，當錯合物在接上配位基時，鈷化合物的雙原子分子改變環境產生π-acceptor 和
σ-donor 變化，並透過紅外線光譜儀探究其振動能量及 X-ray 單晶繞射儀鑑定鈷化合物結構。
化合物 [(NO)Fe(N2S2)Fe(NO)2]+ 化合物
(N2S2= N,N’-bis(2-mer- capt-oethyl)-1,4-diazacycloheptane) 在 2014 被發表，可當作還原質子 (H+) 產生氫氣 (H2) 的電催化劑，本篇論文以
P2S2= meso-1,3Bis[(mercaptoethyl)phenylphosphino] propane (H2meppp) 做為配位基，且比較P與N做配位時，特性與穩定度的不同以求改良並藉由紅外線光譜探討其配位方式。
嘗試對 [(NO)Fe(N2S2)Fe(NO)2]+ 化合物做改良與穩定催化性測試，將氧化石墨烯固定在自製的金電極表面上，用於電催化產氫實驗，跟直接加入氧化石墨烯液體在原系統中觀察催化反應時氧化石墨烯是否影響催化性。

關鍵字

亞硝基鐵化合物 ； π-accepting 能力 ； 氧化石墨烯 ； 氫氣

並列摘要

Diatomic ligand (CO, NO, CN) are very important lignds in coordination chemistry. All of them are common used in biological enzymes. They are binding on metal as a π-acceptor and a σ-donor. We design new complexes with three different diatom ligands in one cobalt coordinated center. It will provide a new point of view to explain π-acceptor and σ-donor when three diatomic ligands bind to one metal center.
The hydrogenases is a redox active enzyme for the interconversion of proton and hydrogen in a biological system. The chemical structure of [FeFe]-hydrogenase contains iron centers, bridging dithiolate and diatomic CO/CN- ligands on the iron centers. In 2014, we reported the cationic complex [(NO)Fe(N2S2)Fe(NO)2]+ and neutral [(NO)Fe(N2S2)Fe(NO)2]
( N2S2=N, N-bis(2-mercaptoethyl)-1,4-diazacycloheptane ) can be the biomimetic functional model for [FeFe]-hydrogenase. The conversion of strong (HBF4) and weak (CH3COOH) acid to the hydrogen can be achieved by one and two electron reduction, respectively. In this study, we will also synthesize the iron complexes analog and modify the N2S2 ligand to the
P2S2( meso-1,3 Bis[(mercaptoethyl)phenylphosphino] ) ligand.
We attempted to test [(NO)Fe(N2S2)Fe(NO)2]+ catalytic efficiency with graphene oxide. Firstly, we make a gold electrode adsorbed graphene oxide and it can be used to electrocatalytic hydrogen reaction. Secondly, we inject graphene oxide solution to original system and compare the differences of stability and properties.
Keywords: nitrosyl iron complexes, π-accepting, graphene oxide, hydrogenase

並列關鍵字

π-accepting ； graphene oxide ； [FeFe]-hydrogenase

參考文獻

參考文獻

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