Zhao Wei, Obeso Juan L, López-Cervantes Valeria B, Bahri Mounib, Sánchez-González Elí, Amador-Sánchez Yoarhy A, Ren Junyu, Browning Nigel D, Peralta Ricardo A, Barcaro Giovanni, Monti Susanna, Solis-Ibarra Diego, Ibarra Ilich A, Zhao Dan
Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore, 117585, Singapore.
Laboratorio de Fisicoquímica y Reactividad de Superficies (LaFReS), Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Circuito Exterior s/n, CU, Coyoacán, 04510, Ciudad de México, Mexico.
Angew Chem Int Ed Engl. 2025 Jan 15;64(3):e202415088. doi: 10.1002/anie.202415088. Epub 2024 Nov 6.
We report the inaugural experimental investigation of covalent organic frameworks (COFs) to address the formidable challenge of SO detection. Specifically, an imine-functionalized COF (SonoCOF-9) demonstrated a modest and reversible SO sorption of 3.5 mmol g at 1 bar and 298 K. At 0.1 bar (and 298 K), the total SO uptake reached 0.91 mmol g with excellent reversibility for at least 50 adsorption-desorption cycles. An isosteric enthalpy of adsorption (ΔH) for SO equaled -42.3 kJ mol, indicating a relatively strong interaction of SO molecules with the COF material. Also, molecular dynamics simulations and Møller-Plesset perturbation theory calculations showed the interaction of SO with π density of the rings and lone pairs of the N atoms of SonoCOF-9. The combination of experimental data and theoretical calculations corroborated the potential use of this COF for the selective detection and sensing of SO at the sub-ppm level (0.0064 ppm of SO).
我们报告了关于共价有机框架（COF）用于应对二氧化硫（SO）检测这一艰巨挑战的首次实验研究。具体而言，一种亚胺功能化的COF（SonoCOF - 9）在1巴和298 K条件下表现出适度且可逆的SO吸附量，为3.5 mmol g。在0.1巴（298 K）时，SO的总吸附量达到0.91 mmol g，并且在至少50次吸附 - 解吸循环中具有出色的可逆性。SO的等量吸附焓（ΔH）为 - 42.3 kJ mol，表明SO分子与COF材料之间存在相对较强的相互作用。此外，分子动力学模拟和Møller - Plesset微扰理论计算显示了SO与SonoCOF - 9环的π电子密度以及N原子孤对电子之间的相互作用。实验数据与理论计算相结合，证实了这种COF在亚ppm水平（0.0064 ppm的SO）下对SO进行选择性检测和传感的潜在用途。
