Surface-decorated porphyrinic zirconium-based metal-organic frameworks (MOFs) using post-synthetic self-assembly for photodegradation of methyl orange dye

Ahmed M Kobaisy; Marwa F Elkady; Ahmed A Abdel-Moneim; Mohamed E El-Khouly

doi:10.1039/d3ra02656f

Surface-decorated porphyrinic zirconium-based metal-organic frameworks (MOFs) using post-synthetic self-assembly for photodegradation of methyl orange dye

RSC Adv. 2023 Jul 31;13(33):23050-23060. doi: 10.1039/d3ra02656f. eCollection 2023 Jul 26.

Authors

Ahmed M Kobaisy¹, Marwa F Elkady², Ahmed A Abdel-Moneim¹, Mohamed E El-Khouly¹

Affiliations

¹ Nanoscience Program, Institute of Basic and Applied Science, Egypt-Japan University of Science and Technology (E-JUST) New Borg El-Arab City Alexandria Egypt mohamed.elkhouly@ejust.edu.eg.
² Chemical and Petrochemicals Engineering Department, Egypt-Japan University of Science and Technology (E-JUST) New Borg El-Arab City Alexandria Egypt.

Abstract

We report herein the surface decoration of a water-soluble free-base porphyrin, namely, 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin-tetra(p-toluenesulfonate) (H₂TMPyP), over three different zirconium-based metal-organic frameworks of different linker structure and functionality; namely UiO66, UiO66-NH₂, and MIP-202, via self-assembly. The synthesized MOFs along with the resulting complexes have been characterized via spectroscopic and analytical techniques (XRD, FT-IR, TEM, N₂ adsorption/desorption, and laser scanning confocal microscopy). The self-assembly of H₂TMPyP with the examined three MOFs was observed by using the steady-state absorption and fluorescence, as well as the fluorescence lifetime studies. It was evident that the highest complex interaction was recorded between porphyrin and UiO-66-NH₂ compared with the lowest interactions between porphyrin and MIP-202. This is in good agreement with the high surface area and pore volume of UiO-66 (1100 m² g^-1 and 0.68 cm³ g^-1) and compared to that of MIP-202 (94 m² g^-1 and 0.26 cm³ g^-1). The photocatalytic activities of the three porphyrin entities immobilized zirconium-based MOFs were compared toward methyl orange dye degradation from aqueous solution under visible light irradiation (λ_ex = 430 nm). The photocatalytic studies render the fabrication of the self-assembled H₂TMPyP@UiO-66-NH₂ composite as a promising material for dye degradation from polluted wastewater.