Palladium nanoparticles supported on different arrangements of MOF-808. Effect on their catalytic performance

GONZALO F. FERNÁNDEZ; IRINA DELLA CAGNOLETTA; ALEJANDRO M. GRANADOS; MELINA S. ARCIDIÁCONO; FEDERICO D. LÓPEZ; MATÍAS RAFTI; DORIS E. GRUMELLI; PAULA M. UBERMAN ; ALEJANDRO M. FRACAROLI

Cancún

Congreso; 32nd International Materials Research Congress (IMRC 2024); 2024

IMRC

Metal-organic frameworks (MOFs) are porous crystalline solids constructed with inorganic clusters and polyfunctional organic ligands, as building units. Among their attractive properties MOFs feature permanent porosity, adjustable pore size, and the possibility of modifying its pore environments with crystallographic precision1. Therefore, MOFs had shown potential in different applications of various fields, such as gas storage, drug transport in biological systems, separation processes, and heterogeneous catalysis among others. In recent years, palladium nanoparticles (Pd-NPs) were successfully introduced into MOFs obtaining highly active catalytic systems in cross-coupling reactions2.We present here, a thermally and chemically stable Zr-based MOF, prepared as octahedral white crystals with side-sizes between 600 and 1000 nm (MOF-808)3, nanometer sizes, 60-70 nm (nMOF-808)4, and the same 600 nm scale MOF but supported on gold surfaces (sMOF-808). We introduce Pd-NPs, with an average size of ≈10 nm, post-synthetically in all of them and evaluate their activity as heterogeneous catalytic systems.The synthesized materials were comprehensively characterized using various techniques, including PXRD, TEM, SEM, AFM, N2 adsorption, and ellipsometry. We compared the amount of incorporate metal within each MOF support, and finally, the catalytic activity of these heterogeneous catalysts was evaluated in Suzuki-Miyaura cross-coupling reactions for C-C bond formation. All materials demonstrated excellent performance (up to 92 % of biphenyl product) under mild reactions conditions (methanol at 65 °C for 4 h-18 h). We believe this is probably due to the affected diffusion phenomena (in and out of the pores, for both reactants and products).