Zirconium-Based Metal-Organic Frameworks for Oxygen Sensing

doi:10.6023/A24110333

Abstract

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

Cite this article

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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Fig. & Tab. 7

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

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)

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)

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

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

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

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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