金屬有機骨架（Metal－organic frameworks, MOFs）是一系列由金屬節點與有機連器所組成的奈米孔洞材料，具有極高比表面積、結構可調性與良好的後修飾潛力。相較於傳統孔洞材料，MOFs在單位體積中含有大量且高度分散的活性位點，使其廣泛應用於催化、感測、分離與儲存等。其中，鋯基金屬有機骨架（Zr-MOFs），其優異的水穩定性與結構多樣性，更適合用於水相中的各類反應與感測，成為近年來熱門研究與應用的材料之一。本研究以二維鋯基金屬有機骨架—ZrBTB（BTB = 1,3,5-tri(4-carboxyphenyl)benzene）作為平台，透過後修飾方式在Zr6節點上同時安裝不同比例的鑭系金屬—鋱（Tb3+）與銪（Eu3+）離子，並系統性探討含不同Eu/Tb比例之2D Zr-MOF的結晶性、形貌、孔洞性及光致發光特性，並進一步應用於水相中重水（D2O）的感測。
材料的發光機制主要是藉由BTB連接器吸收激發光後，將能量傳遞至Tb，再進一步由Tb將能量轉移至Eu，當材料中含有少量Eu而周圍有大量Tb時，可以得到最強的Eu發光強度，且此發光增強現象並無法在Tb-ZrBTB與Eu-ZrBTB以相同比例的物理混合物中觀察到。透過螢光量子效率（PLQY）的測定，也證實Tb可作為BTB與Eu之間能量傳遞的中間者，進而促進Eu的放光增強。最後，本文進一步將具可調性發光性質的材料應用於重水的螢光感測，以BTB的放光作為內部參考因子，而Eu的放光作為感測訊號，使得最佳材料Eu-Tb-ZrBTB(1:10)在感測表現上優於單金屬後修飾的Tb-ZrBTB、Eu-ZrBTB及兩者的物理混合物。

Metal–organic frameworks (MOFs) are composed of metal ions and organic linkers. With unique properties such as high structural tunability, regular and interconnected porosity, and adjustable chemical functionality, MOFs have been considered appealing nanoporous materials for a range of applications such as sensing, gas adsorption, separation, and catalysis. In this work, a two-dimensional zirconium-based metal–organic framework (2D Zr-MOF), ZrBTB (BTB = 1,3,5-tri(4- carboxyphenyl)benzene), is used as a platform to simultaneously immobilize terbium ions and europium ions with tunable ratios on its hexa-zirconium nodes by a post-synthetic modification. The crystallinity, morphology, porosity and photoluminescence (PL) properties of the obtained 2D Zr-MOFs with various europium-to-terbium ratios are investigated. With the energy transfer from the excited BTB linker to the installed terbium ions and the energy transfer from terbium ions to europium ions, a low loading of immobilized europium ions and a high loading of surrounding terbium ions in the 2D Zr-MOF result in the optimal PL emission intensities of europium; this phenomenon is not observable for the physical mixture of both terbium-installed ZrBTB and europium-installed ZrBTB. The role of installed terbium ions as efficient mediators for the energy transfer from the excited BTB linker to the installed europium ion is confirmed by quantifying PL quantum yields. As a demonstration, these materials with modulable PL characteristics are applied for the ratiometric detection of D2O in water, with the use of the stable emission from the BTB linker as the reference. With the strong emission of immobilized europium ions and the good dispersity in aqueous solutions, the optimal bimetal-installed ZrBTB, Eu-Tb-ZrBTB(1:10), can achieve the sensing performance outperforming those of the terbium-installed ZrBTB, europium-installed ZrBTB and the physical mixture of both.

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