超微孔有機柱鋅磷酸鹽結構的有序化以及金屬化並應用於二氧化碳分離與質子傳導

Abstract

近年來，多孔材料因吸附性質而備受矚目，但其結晶性 (Crystallinity)在有序化(Ordering)過程中的機制尚待釐清。本研究中以 [Zn2(VOH2O)(PO4)2(bpy)]·4H2O (VZn-bpy-w，又稱NTHU-16)為研究主軸，是一種以金屬化 (Metalation)策略將釩嵌入至鋅磷酸鹽無機層中所合成，具孔洞性的有機無機複合磷酸鹽 (Organic-Linked Metal Phosphate, OMPO)。本文除了針對其在熱穩定性、沸水穩定性、空氣穩定性與化學穩定性做詳細探討，也測試各項合成條件，並將合成系統由中溫中壓溶劑熱法更改為回流法，以雙溶劑置換 (Two Solvent Exchange, TOSE)與加熱抽真空 (Heat Under Vacuum, HEVA)的策略成功放大合成規模，更節省超過90%的反應時間。得益於回流法系統的開放性，本文將合成過程拆解成各個步驟，並以PXRD與結晶度指數 (Crystallinity Index, CI)的計算來描述HEVA與TOSE策略在有序化過程的影響。高穩定性的VZn-bpy-w在298K有二氧化碳的氣體吸附，同時不會吸附氮氣，有在煙道氣中進行二氧化碳分離的潛力。又因結構中的結晶水與配位水的存在，使其具有質子傳導的特性，期望能應用於燃料電池。

Recently, porous materials have been attracted by their adsorption properties. However, the detailed formation mechanism of its crystallinity during “Ordering” is still inconclusive. This research features [Zn2(VOH2O)(PO4)2(bpy)]4H2O (VZn-bpy-w, also denoted NTHU-16; bpy=4,4’-bipyridine). This porous Organic-Linked Metal Phosphate (OMPO) was synthesized by Metalation strategy inserting Vanadium into inorganic Zincophosphate layers. The identification of thermal, boiling water, air, and chemical stability were described. Moreover, the synthesized conditions were explored, and the synthesis system was changed to reflux from solvothermal. Two solvent exchange (TOSE) and Heat Under Vacuum (HEVA) strategies enable synthesized scale-up and reduced reaction time by more than 90%. Benefits of the open system, the synthesis progress was separated into several steps. PXRD and Crystallinity Index (CI) described the effects of TOSE and HEVA during ordering. Highly stable VZn-bpy-w showed CO2 gas adsorption while the N2 exclusion, with CO2 separation potential in the flue gas. Furthermore, crystal waters and coordinated waters in the structure triggered proton conductivity, expected to apply in fuel cell.