Intercalation of Porphyrin‐Based SURMOF in Layered Eu(III) Hydroxide: An Approach Toward Symbimetic Hybrid Materials

• Published in: Advanced functional materials Vol. 30; no. 27
• Main Authors: Sokolov, Maksim R., Enakieva, Yulia Yu, Yapryntsev, Alexey D., Shiryaev, Andrey A., Zvyagina, Alexandra I., Kalinina, Maria A.
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc 01.07.2020
• Subjects: Catalytic activity; Coordination; Europium; hybrid materials; Hybrid systems; Intercalation; layered rare‐earth hydroxides; Materials science; Metal-organic frameworks; porphyrins; Raman spectroscopy; Spectrum analysis; Stabilization; Substrates; SURMOFs; Zinc acetate
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202000681

A strategy for rational design of synergetic hybrid materials exploiting stabilization of intercalated layered matrices via coordination bonding is described. A new hybrid material is assembled through subsequent intercalation of the surface‐anchored metal–organic framework (SURMOF) components, zinc acetate and 5,10,15,20‐tetrakis(4‐carboxyphenyl)‐porphyrin‐zinc(II) (ZnTCPP), into the layered europium(III) hydroxychloride (LEuH). The formation of the SURMOF clusters intercalated in LEuH is confirmed by X‐ray diffraction, FTIR and Raman spectroscopy, and BET nitrogen absorption methods. The catalytic function of the SURMOF/LEuH hybrid and its components in the model reaction of hydrolysis of bis(4‐nitrophenyl) phosphate in the acidic solution is studied by UV–vis and MALDI‐TOF spectroscopy. Both the non‐intercalated matrix and the MOF powder are inactive and unstable in the substrate solution. Unlike its components, the SURMOF/LEuH hybrid exhibits synergetic catalytic activity increasing with the amount of the intercalated compounds because of the mutual stabilization of the components through coordination interactions. The results provide a basis for symbimetic (mimicking the symbiotic behavior in biological systems) hybrid materials, in which stabilization of functional units in the intercalated structure translates into a synergy of useful properties. A novel approach to create functional intercalated materials exploits stabilizing coordination bonding between porphyrin‐based surface‐anchored metal–organic framework and layered Eu(III) hydroxide. Due to this mutual protection, the layered symbimetic hybrid mimics the behavior of biological symbiotic organisms capable of catalytic “digesting” of potentially harmful organic substrates and surviving in aggressive acidic environments.