Constructing Randomly Lamellar HKUST–1@Clinoptilolite through Polyethylene Glycol—Assisted Hydrothermal Method and Coordinated Complexation for Enhanced Adsorptive Separation for CO2 and CH4

Abstract

Clinoptilolite (CP) was successfully synthesized via a hydrothermal route in the presence of polyethylene glycol (PEG), and it was then delaminated by washing using Zn2+ containing acid. HKUST-1, as one kind of the Cu-based MOFs, showed a high CO2 adsorption capacity owing to its large pore volume and specific surface area. In the present work, we selected one of the most efficient ways for preparing the HKUST-1@CP compounds via coordination between exchanged Cu2+ and ligand (trimesic acid). Their structural and textural properties were characterized by XRD, SAXS, N2 sorption isotherms, SEM, and TG-DSC profiles. Particularly, the effect of the additive PEG (average molecular weight of 600) on the induction (nucleation) periods and growth behaviors were detailed and investigated in the hydrothermal crystallization procedures of synthetic CPs. The corresponding activation energies of induction (En) and growth (Eg) periods during crystallization intervals were calculated. Meanwhile, the pore size of the inter-particles of HKUST-1@CP was 14.16 nm, and the BET specific area and pore volume were 55.2 m2/g and 0.20 cm3/g, respectively. Their CO2 and CH4 adsorption capacities and selectivity were preliminarily explored, showing 0.93 mmol/g for HKUST-1@CP at 298 K with the highest selective factor of 5.87 for CO2/CH4, and the dynamic separation performance was evaluated in column breakthrough experiments. These results suggested an efficient way of preparing zeolites and MOFs composites that is conducive to being a promising adsorbent for applications in gas separation.