金屬有機骨架（Metal－organic frameworks, MOFs）是由金屬節點（Node）與小分子有機連接器（Organic linker）所組成的一類多孔奈米材料，相較於傳統孔洞材料，MOF具有高比表面積、規律孔洞結構與結構可修飾性等優點，因此被廣泛應用於吸附、催化、分離與感測等領域。而在光致發光感測之應用中，此類特性可將作為發光中心的鑭系金屬離子均勻且分散地修飾於MOF的骨架中，然而，多數MOF的水穩定性並不好，限制了水相感測的應用。因此，本研究使用二維鋯基金屬有機骨架—ZrBTB（BTB = 1,3,5-tri(4-carboxyphenyl)benzene）作為修飾平台，ZrBTB不僅具有高水穩定性，二維結構也使其在溶液中能分散成層狀，最大化地暴露表面的活性位點於環境中，使目標感測物迅速擴散至材料表面的活性位點而提升靈敏度與縮短反應時間。
由於 ZrBTB 的 BTB linker 已被證實可作為鑭系金屬離子—鋱（Tb3+）的高效光敏劑，能吸收入射光之能量並透過天線效應將能量傳遞至 Tb，進而增強 Tb的特徵放光。此外，在水相環境中，發光材料表面的電荷可能會有助於吸引溶液中帶相反電性的離子，透過靜電吸引作用使待測分析物更容易接觸材料表面的活性位點。因此，本研究將以此為基礎，除了Tb之外，也將帶電配體（正電配體：betaine hydrochloride, TMA、負電配體：4-sulfobenzoic acid potassium salt, SO3）共同修飾於ZrBTB 的Zr6節點上，並在帶電配體與Tb之附載量皆相似的情況下，比較Tb-ZrBTB、Tb-SO3-ZrBTB與Tb-TMA-ZrBTB三種發光材料分別在亞硝酸根離子與鐵離子中的感測成果，是否的確因帶電配體的靜電吸引作用而進一步地提升其光致發光感測之表現。

In this study, a two-dimensional and water-stable zirconium-based metal–organic framework with six pairs of terminal –OH/–OH₂ groups on its hexa-zirconium nodes, ZrBTB (BTB = 1,3,5-tris(4-carboxyphenyl)benzene), was employed as an ideal platform for dual post-synthetic modifications (PSM) to install both terbium ions and charged functional ligands (4-sulfobenzoic acid potassium salt, SO3 or betaine hydrochloride, TMA). The crystallinity, morphology, porosity, chemical states, and loadings of both terbium ions and charged ligands were characterized for each material. To investigate whether charged ligands can attract oppositely charged analytes in aqueous solutions and improve sensing performance, the photoluminescence (PL) properties of Tb-ZrBTB, Tb-TMA-ZrBTB, and Tb-SO3-ZrBTB were then examined. Since the excited BTB linker can serve as an antenna to efficiently transfer energy to terbium ions, and Tb emission is known to be sensitive to nitrite and ferric ions, these three materials were subjected to PL tests in aqueous solutions containing different concentrations of nitrite and Fe³⁺. The sensitivities toward nitrite and Fe³⁺ were evaluated using the Stern–Volmer equation, along with the corresponding limits of detection (LOD). The results show that the positively charged Tb-TMA-ZrBTB exhibited the best performance for nitrite sensing, with a Stern–Volmer constant (KSV) of 498,570 M⁻¹ and an LOD of 40.03 nM, while the negatively charged Tb-SO3-ZrBTB achieved the highest response for Fe³⁺ sensing (KSV = 10,800 M⁻¹; LOD = 1.49 µM). These findings demonstrate that incorporating charged ligands into Tb-modified MOFs facilitates electrostatic interactions with oppositely charged analytes and effectively enhances their photoluminescent sensing capability.

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