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Synthesis of ZIF‐93/11 Hybrid Nanoparticles via Post‐Synthetic Modification of ZIF‐93 and Their Use for H 2 /CO 2 Separation
Author(s) -
SánchezLaínez Javier,
Zornoza Beatriz,
Orsi Angelica F.,
Łozińska Magdalena M.,
Dawson Daniel M.,
Ashbrook Sharon E.,
Francis Stephen M.,
Wright Paul A.,
Benoit Virginie,
Llewellyn Philip L.,
Téllez Carlos,
Coronas Joaquín
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201802124
Subject(s) - zeolitic imidazolate framework , adsorption , nanoparticle , chemical engineering , thermal stability , x ray photoelectron spectroscopy , surface modification , hybrid material , materials science , membrane , benzimidazole , selectivity , selective adsorption , imidazolate , chemistry , metal organic framework , organic chemistry , nanotechnology , catalysis , biochemistry , engineering
The present work shows the synthesis of nano‐sized hybrid zeolitic imidazolate frameworks (ZIFs) with the rho topology based on a mixture of the linkers benzimidazole (bIm) and 4‐methyl‐5‐imidazolecarboxaldehyde (4‐m‐5‐ica). The hybrid ZIF was obtained by post‐synthetic modification of ZIF‐93 in a bIm solution. The use of different solvents, MeOH and N , N ‐dimethylacetamide (DMAc), and reaction times led to differences in the quantity of bIm incorporated to the framework, from 7.4 to 23 % according to solution‐state NMR spectroscopy. XPS analysis showed that the mixture of linkers was also present at the surface of the particles. The inclusion of bIm to the ZIF‐93 nanoparticles improved the thermal stability of the framework and also increased the hydrophobicity according to water adsorption results. N 2 and CO 2 adsorption experiments revealed that the hybrid material has an intermediate adsorption capacity, between those of ZIF‐93 and ZIF‐11. Finally, ZIF‐93/11 hybrid materials were applied as fillers in polybenzimidazole (PBI) mixed matrix membranes (MMMs). These MMMs were used for H 2 /CO 2 separation (at 180 °C) reaching values of 207 Barrer of H 2 and a H 2 /CO 2 selectivity of 7.7 that clearly surpassed the Robeson upper bound (corrected for this temperature).