有機無機複合金屬磷酸鹽材料之綠色合成與功能性研究

Green Syntheses and Functionalities of Organic-Inorganic Hybrid Metal Phosphates

黃玉廷(Yu-Ting Huang)

指導教授 ： 王素蘭

國立清華大學/理學院/化學系/博士(2011年)

https://doi.org/10.6843/NTHU.2011.00222

摘要

本研究使用有機胺為模板，在中溫中壓水熱反應中得到18個化合物，分屬三個不同的系統。系統A 著重於縮短能源與廢棄物再生的議題，以微波代替傳統加熱方式，將合成時間縮短至原有的1%即能成功得到產物-A1、A2與A3的單相；並發現扮演配基的對苯二甲酸在”看似”相同的結構中，可作不同程度的轉動。此結果顯示微波方式所得到的產物其實與傳統加熱法結果並非全然相等， 顛覆了已往使用微波合成作為已知相量產的認知；另一方面我們成功將寶特瓶(PET)的碎片當作起始反應試劑，運用於兩個極具效率的反應得到了新穎結構A5與A6，後者擁有有趣的光致發光性質，可成為螢光粉材料應用於白光LED，為回收廢棄保特瓶的利用提供一嶄新的視野。
系統B含有六個含有機超分子的層狀鋅磷酸鹽，獨特而有彈性的擬中性層(H3tren)2[Zn3(PO4)4]上具有錯綜的氫鍵分佈，控制著非掌性單體客分子在層間形成掌性超分子無限鏈，導引出B1-B4掌性結構；擬中性層間距也隨不同客分子大小擴張，最高可至20 Å；層上的鋅可以部分用過渡金屬取代，不僅發現摻雜鈷金屬的層可導致有機酸分子客體在層間形成兩種不同排列的超分子鏈 (B4與B4a)、摻雜錳金屬後可導致光致發光性質，由有機酸超分子客體扮演光敏化劑的角色而帶來高亮度的橘色(B1-Mn)或粉紅色 (B4-Mn)螢光。
系統C為運用仿生材料中重要的bola界面活性劑的長碳鏈有機胺DADD為模板，並加入有機酸大分子BPDA與磷酸鹽所建構出的六個層狀化合物，其中一個鎵磷酸鹽C3不僅具有22 Å超大層間距，還展現罕見的餘輝發光性質。
在此三個研究系統中，我們藉由單晶X光繞射方法，瞭解各個新物質詳細的結構，從結構的觀點探討合成、熱穩定性質、有機超分子的自組裝與各種光致發光機制，在有機/無機複合金屬磷酸鹽領域提供多項重要的創新觀點與突破。

關鍵字

金屬磷酸鹽 ； 綠色合成 ； 餘暉發光 ； 層狀材料 ； 寶特瓶回收 ； 超分子組裝

並列摘要

In this research, 18 compounds were synthesized by employing organic amine as template under hydrothermal conditions. They were classified into three systems:
System A put emphasis on reduction of energy consumption and chemical recycling of waste PET. Reactions with the use of microwave as an energy source largely cut down the reaction time to 1% as compared to conventional heating time and successfully yielded three single-phased products of A1, A2 and A3. The compounds A2,A3 and A5 displayed 3D structures “seemingly the same “ but they are not exactly identical due to the common organic linkers of BDC moiety adopting different orientations with respect to the same inorganic framework. The results should overturn our conventional cognition on scaling up product by microwave synthesis. On the other hand, scraps of waste PET bottle were successfully employed in two reactions as potent reagents to produce new compound A5 and high-valued phosphor materials A6 with potential application to white-light LEDs, providing a brand new perspective to chemical recovery of waste PET.
System B contains six layered zinc phosphates encapsulating organic supra molecules as guest species. Bearing intricate hydrogen-bonding patterns within each layer, the pseudo-neutral (H3tren)2[Zn3(PO4)4] sheets are highly adaptable to varied achiral organic monomers, making them transformed into different chiral supramolecular chains. As a result, the entire structures of B1-B4 were turned into chiral as well. Depending on the molecular size of guest monomers, the layer gap was able to pop up the most to 2.01 nm (B4). Furthermore, the zinc center could be doped with homo-valence transition metal ions. Incorporation of Co2+ ions into layers exerted strong influence on supramolecular guests’ arrangements while doping of Mn2+ ions created novel photoluminescence property-the inter-layer supramolecular guest became a good sensitizer for the emission of bright orange- (from B1-Mn) or pink- (from B4-Mn) light under UV excitation.
System C involved the use of bola-type surfactant, the long chain amine-DADD, as organic template. In the synthesis additional bulky organic acid-BPDA was included together with (metal) phosphate to generate six layered materials. The compound of C3 is highly interesting as it not only was observed ultra-large inter layer gap of 2.2nm but also revealed intriguing green afterglow property.
In the three systems, every structure was well-characterized and extended to the discussion on their syntheses, thermal properties, self-assembly of supramolecular guests and the mechanisms of luminescence. The study generated significant results with substantial novelty and made conceptual breakthroughs to the field of organic/inorganic hybrid metal phosphate materials.

並列關鍵字

Metal phoshphate ； Green Syntheses ； Afterglow ； Layer materials ； PET Bottle Recycle ； Supramolecular Assembly

參考文獻

1. (a) Breck, D. W. Zeolite Molecular Sieves: Structure,

(b) Venuto, P. B. Microporous Mater., 1994, 2, 297.(c)

Corma, A. Chem. Rev., 1995, 95, 559.

2. Barrer, R. M.; Denny, P. J. J. Chem. Soc.1961, 971.

Taspatsis, M.; Davis, M. E. Chem. Comm. 1997, 2179.