Issue 22, 2022

Pd(/Fe3O4)-on-ZIFs: nanoparticle deposition on (nano-)MOFs from ionic liquids

Abstract

Well-defined spherical Pd-NPs (∼6–12 nm size, 4–17% wt content) were efficiently deposited on nano- or micro- (∼100–2500 nm) crystals of zeolite imidazolate frameworks (ZIFs) from different ionic liquids (ILs, typically 1-butyl-3-methylimidazolium bistriflimidate, [BMIm]NTf2) at 180–230 °C under microwave (MW) heating for 1–10 min. The firm, nearly exclusive on-surface deposition, proven by systematic analysis of TEM micrographs, is achieved via size-exclusion of the IL-solvated PdCl2 precursor. The one-pot high-quality NP deposition from partially stabilizing IL media leads to particularly well-defined metal nanoparticles-on-metal–organic frameworks, MNP-on-MOF(NP)s. They are contraposed to MNP@MOFs or non-specified MNP/MOFs, and are viewed as an extension of MNPs from ionic liquids, securing MNP-agglomeration protection after removal of the IL and reversible redispersion, and offering the functionality of the porous support. Pd-on-ZIF-8-NP (R = Me substituent of the azole ligand) demonstrated the highest stability and morphological quality, while the ZIF-90 analogues with the same sod topology (R = COOH, CHO, CH2CH2NH2) or the triazolate MAF-66 (R = NH2) with dia topology showed lesser stability (particularly for R = COOH and CHO). Ferromagnetic Pd/Fe3O4- and Fe3O4/Pd-on-ZIF-8-NP, ZIF-90-NH2(-NP), and MAF-66 composites with nanoparticulated Fe3O4 (5–13 nm size, 5–22%wt content) demonstrate the feasibility of sequential NP deposition of varied nature. The Pd-on-ZIF composites demonstrated high catalytic activity in the reduction of 4-nitrophenol to 4-aminophenol by NaBH4 in water (TOF 0.38–4.10 vs. 0.088 s−1 for 10%wt Pd/C; amino-functionalization and the presence of Fe3O4 are a major and a minor factor, respectively). The reduction of the same substrate with H2 in apolar media was much slower for the composite catalysts compared to Pd/C (10%wt) due to possible poisoning by the residual IL.

Graphical abstract: Pd(/Fe3O4)-on-ZIFs: nanoparticle deposition on (nano-)MOFs from ionic liquids

Supplementary files

Article information

Article type
Paper
Submitted
01 Feb 2022
Accepted
15 Mar 2022
First published
15 Mar 2022
This article is Open Access
Creative Commons BY-NC license

J. Mater. Chem. A, 2022,10, 11955-11970

Pd(/Fe3O4)-on-ZIFs: nanoparticle deposition on (nano-)MOFs from ionic liquids

O. Koikolainen, L. Sondermann, S. Roitsch, I. Simon, D. Dietrich, V. Gvilava, J. Barthel, J. Thomas, C. Janiak and I. Boldog, J. Mater. Chem. A, 2022, 10, 11955 DOI: 10.1039/D2TA00883A

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