锆基金属有机框架材料在氧传感器上的应用

doi:10.6023/A24110333

摘要/Abstract

氧气传感在环境监测、医疗保健、工业生产和应用安全等各领域都发挥着至关重要的作用, 而金属有机框架(MOFs)由于具有较强的氧吸附能力, 有望应用于氧气传感并提高其响应性能. 本工作选取4个常见的锆基MOF材料并比较了其与配体的荧光发射和荧光寿命, 阐述了其发光机理. 4种锆基MOF均表现出对氧气的荧光淬灭性能, 证明了氧气是有效淬灭锆基MOF的荧光的主要空气组分. 其中, MOF-808和UiO-66具有良好的稳定性, 有望成为氧气传感器的候选材料. 在探究Zr基MOF中导致荧光淬灭的组成时, 通过对比具有相同配体的铬MOF, 证明了Zr⁴⁺是引发荧光淬灭的主要因素, 理论计算以及氧气吸附测试辅助验证了锆基MOF在氧气传感中的优势. 另外, UiO-66较短的恢复响应时间证明了MOF中孔道的作用, MOF荧光寿命的降低揭示了氧气对MOF荧光路径的抑制. 这些发现预计将为开发敏感的氧气传感器提供理论指导.

关键词: 金属有机框架材料, 氧气传感, 多孔材料, 荧光淬灭

Oxygen sensing plays a vital role in a variety of fields, including environmental monitoring, healthcare, industrial processes, and safety management. Metal-organic frameworks (MOFs), owing to their robust oxygen adsorption capacity and tunable structure, are anticipated to be applied in oxygen sensing to enhance response performance. In this work, we synthesized four common Zr-MOFs (MOF-808, UiO-66, NU-1000, NH₂-UiO-66) using the solvothermal method and validated the interaction between the ligands and zirconium clusters by comparing their fluorescence emission and lifetime. Then, the fluorescence of these four MOFs were tested under vacuum, air, and oxygen atmospheres. The experiments demonstrate that oxygen is the main air component that effectively quenches the fluorescence of zirconium-based MOFs. Recirculation experiments and powder X-ray diffraction of MOFs before and after fluorescence quenching indicate that zirconium-based MOFs exhibit high photo-stability. Under vacuum and pure oxygen conditions, UiO-66 can quench 88% of its fluorescence, with response and recovery times as low as 13 s and 15 s, respectively. This rapid detection of O₂ over multiple cycles suggests that UiO-66 possesses a high level of sensitivity. In contrast, the fluorescence of chromium-based MOFs with the same ligands is hardly affected. This may be related to the electronic structure of tetravalent zirconium being able to match the electronic structure of paramagnetic oxygen, allowing the fluorescence process of the MOF to be quenched under the action of oxygen. To explore the advantages of zirconium-based MOFs in oxygen sensing, density functional theory calculations are adopted to determine the adsorption energy of oxygen with MIL-100(Cr) and MOF-808(Zr), which have the same ligands, confirming that one of the reasons for the special sensitivity of zirconium-based MOFs to oxygen is the shorter collision radius between Zr metal clusters and O₂ molecules. The reduction in fluorescence lifetime confirmed the interaction between oxygen and the MOF. These findings are expected to provide theoretical guidance for the development of sensitive oxygen sensors.

Key words: metal-organic framework materials, oxygen sensing, porous materials, fluorescence quenching

引用此文

王跃, 邹莹, 张元, 郑舒婕, 王恒宇, 刘天赋, 李仁富. 锆基金属有机框架材料在氧传感器上的应用[J]. 化学学报, 2025, 83(1): 45-51.

Yue Wang, Ying Zou, Yuan Zhang, Shujie Zheng, Hengyu Wang, Tianfu Liu, Renfu Li. Zirconium-Based Metal-Organic Frameworks for Oxygen Sensing[J]. Acta Chimica Sinica, 2025, 83(1): 45-51.

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图/表 7

图1. (a) NU-1000, (b) MOF-808, (c) NH2-UiO-66和(d) UiO-66的结构图、分子式及其粉末X射线衍射图

Figure 1. Structural diagrams, molecular formulas, and powder X-ray diffraction patterns of (a) NU-1000, (b) MOF-808, (c) NH2-UiO-66, and (d) UiO-66

图2. (a) MOF-808 (λEx=320 nm)及其配体BTC (λEx=272 nm)的光致发光光谱; (b) NU-1000 (λEx=360 nm)及其配体H4TBAPy (λEx=375 nm)的光致发光光谱; (c) UiO-66 (λEx=290 nm)及其配体BDC (λEx=290 nm)的光致发光光谱和(d) NH2-UiO-66 (λEx=290 nm)及其配体NH2-BDC (λEx=365 nm)的光致发光光谱; (e) MOF-808 (λEm=390 nm)及其配体BTC (λEm=320 nm)的瞬态荧光光谱; (f) NU-1000 (λEm=500 nm)及其配体H4TBAPy (λEm=544 nm)的瞬态荧光光谱; (g) UiO-66 (λEm=380 nm)及其配体BDC (λEm=380 nm)的瞬态荧光光谱; (h) NH2-UiO-66 (λEm=460 nm)及其配体NH2-BDC (λEm=590 nm)的瞬态荧光光谱

Figure 2. (a) The luminescence spectra of MOF-808 (λEx=320 nm) and BTC (λEx=272 nm); (b) the luminescence spectra of NU-1000 (λEx=360 nm) and H4TBAPy (λEx=375 nm); (c) the luminescence spectra of UiO-66 (λEx=290 nm) and BDC (λEx=290 nm); (d) the luminescence spectra of NH2-UiO-66 (λEx=290 nm) and NH2-BDC (λEx=365 nm); (e) the transient fluorescence spectra of MOF-808 (λEm=390 nm) and BTC (λEm=320 nm); (f) the transient fluorescence spectra of NU-1000 (λEm=500 nm) and H4TBAPy (λEm=544 nm); (g) the transient fluorescence spectra of UiO-66 (λEm=380 nm) and BDC (λEm=380 nm); (h) the transient fluorescence spectra of NH2-UiO-66 (λEm=460 nm) and NH2-BDC (λEm=590 nm)

图3. 真空与空气(21% O2)氛围下(a) MOF-808, (b) UiO-66, (c) NU-1000和(d) NH2-UiO-66的可逆的发光响应-恢复曲线(圆圈所示为背景信号)

Figure 3. The reversible luminescence response-recovery curves of (a) MOF-808, (b) UiO-66, (c) NU-1000, and (d) NH2-UiO-66 between vacuum and air (21% O2) (The circle indicates the background signal of the detector)

图4. (a) O2或N2氛围下UiO-66的PL发射光谱(λEx=290 nm); 在(b)真空与纯O2或空气、(c)真空与纯O2或N2和水混合气氛下UiO-66的可逆的发光响应-恢复曲线

Figure 4. (a) The PL emission spectra of UiO-66 under O2 or N2 (λEx=290 nm); The reversible luminescence response-recovery curves of UiO-66 between (b) vacuum and pure O2 or air, (c) vacuum and pure O2 or the mixed gas of N2 and H2O

图5. 在真空和空气(21% O2)氛围下(a) MIL-100(Cr)和(b) MIL-53(Cr)的可逆的发光响应-恢复曲线

Figure 5. The reversible luminescence response-recovery curves of (a) MIL-100(Cr) and (b) MIL-53(Cr) between vacuum and air (21% O2)

图6. UiO-66的响应和恢复时间(由290 nm激发, 在375 nm处检测)

Figure 6. The response and recovery time of UiO-66 (excited by 290 nm, detected at 375 nm)

图7. (a) NU-1000 (λEm=500 nm)和(b) NH2-UiO-66 (λEm=460 nm)在空气和真空条件下的瞬态荧光

Figure 7. The transient fluorescence of (a) NU-1000 (λEm=500 nm) and (b) NH2-UiO-66 (λEm=460 nm) under air and vacuum conditions

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