(Hf)PCN-224(Co) as an efficient ppm-level sensor for toxic SO2

(Hf)PCN-224(Co) as an efficient ppm-level sensor for toxic SO2

Herein, we report the first experimental investigation, supported with theoretical calculations, of a porphyrin-based metal organic framework (PMOF) to address the difficult challenge of SO2 detection and sensing. Specifically, the highly porous hafnium cobalt-porphyrin tetracarboxylate named (Hf)PC...

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Main Authors: Sergio Carrasco, Marco L. Martínez, Yoarhy A. Amador-Sánchez, Valeria B. López Cervantes, Elí Sánchez-González, Nora S. Portillo-Vélez, Ricardo A. Peralta, Christian A. Celaya, Ariel Guzmán-Vargas, Patricia Horcajada, Diego Solis-Ibarra, Ilich A. Ibarra
Format: Article
Language:English
Published: Elsevier 2025-06-01
Series:Materials Today Advances
Subjects:
SO2 capture
Adsorption-desorption isotherm
SO2 detection
Porphyrin
MOFs
Fluorescence
Online Access:http://www.sciencedirect.com/science/article/pii/S2590049825000244
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Summary:Herein, we report the first experimental investigation, supported with theoretical calculations, of a porphyrin-based metal organic framework (PMOF) to address the difficult challenge of SO2 detection and sensing. Specifically, the highly porous hafnium cobalt-porphyrin tetracarboxylate named (Hf)PCN-224(Co) was used as probe material. (Hf)PCN-224(Co) demonstrated a moderate SO2 sorption of 1.0 mmol g−1 at 0.1 bar and 298 K, and a limit of detection of 175.5 ppm, obtained by photoluminescent experiments. Furthermore, clear, different emission responses are observed for (Hf)PCN-224(Co) after the exposure to CO2 and water vapor, compared to SO2. Remarkably, (Hf)PCN-224(Co) shows crystalline retention after exposure to SO2 at low concentrations (i.e., 0.1 bar). The use of Hf4+, as well as microwave-assisted solvothermal synthesis, lead to crystalline defects in the form of missing linkers, providing additional Hf(IV) open metal sites, able to interact with SO2 molecules. Based on UV–Vis and X-ray photoelectron spectroscopies, we suggest ligand to metal charge transfer as primal emission mechanisms, and the coordination of SO2 with Hf6(OH)8 coordinatively unsaturated clusters as the most plausible origin for the emission response in SO2 detection/sensing. The tendency of this behavior is verified from the density functional theory calculations.
ISSN:2590-0498

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