Water Based Synthesis of ZIF-8 Assisted by Hydrogen Bond Acceptors and Enhancement of CO₂ Uptake by Solvent Assisted Ligand Exchange

The aim of this work was to synthesize zeolitic imidazolate framework-8 (ZIF-8) by an alternative method and then modify the surface properties for enhancing the CO₂ adsorption performance. The ZIF-8 was synthesized by a water based synthesis method using 2-methyl imidazole (2-MeIM) as a hydrogen bond donor and quaternary ammonium salts (QAS) as a hydrogen bond acceptor. The optimal synthesis conditions were investigated by varying (i) the order of precursor mixing during the synthesis process (ii) different QAS (tetrabutyl ammonium bromide (TBAB), tetraethyl ammonium bromide (TEAB) and trimethyl phenyl ammonium bromide (TMPAB)) and (iii) the ratio between 2-MeIM and QAS. The results show that the optimal synthesis condition was using TMPAB as the hydrogen bond acceptor with the ratio between 2-MeIM and TMPAB of 8:2 and in the order of first mixing both hydrogen bond donor and acceptor before adding Zn(NO₃)₂⋅6H₂O solution. TMPAB can provide uniform size distribution with the smallest particle sizes of ZIF-8. This can be explained by the higher hydrogen bond strength between hydrogen bond donor (2-MeIM) and hydrogen bond acceptor (TMPAB) when compared with that of the rest of two QAS. The synthesized ZIF-8 was modified by solvent-assisted ligand exchange methods. The organic linker of ZIF-8 (2-MeIM) was exchanged by 2-aminobenzimidazole (2-NH₂bZIM) and 2-phenylimidazole (2-PhIM). The CO₂ uptake of modified ZIF-8 was enhanced upon exchanging with 2-NH₂bZIM. The increase in CO₂ uptake was due to an additional interaction between CO₂ and exchanged imidazole linker and an increase in surface properties (higher surface area, pore size and pore volume).