Fabricating Mechanically Robust Binder-Free Structured Zeolites by 3D Printing Coupled with Zeolite Soldering: A Superior Configuration for CO Capture.

Abstract

3D-printing technology is a promising approach for rapidly and precisely manufacturing zeolite adsorbents with desirable configurations. However, the trade-off among mechanical stability, adsorption capacity, and diffusion kinetics remains an elusive challenge for the practical application of 3D-printed zeolites. Herein, a facile "3D printing and zeolite soldering" strategy is developed to construct mechanically robust binder-free zeolite monoliths (ZM-BF) with hierarchical structures, which can act as a superior configuration for CO capture. Halloysite nanotubes are employed as printing ink additives, which serve as both reinforcing materials and precursor materials for integrating ZM-BF by ultrastrong interfacial "zeolite-bonds" subjected to hydrothermal treatment. ZM-BF exhibits outstanding mechanical properties with robust compressive strength up to 5.24 MPa, higher than most of the reported structured zeolites with binders. The equilibrium CO uptake of ZM-BF reaches up to 5.58 mmol g (298 K, 1 bar), which is the highest among all reported 3D-printed CO adsorbents. Strikingly, the dynamic adsorption breakthrough tests demonstrate the superiority of ZM-BF over commercial benchmark zeolites for flue gas purification and natural gas and biogas upgrading. This work introduces a facile strategy for designing and fabricating high-performance hierarchically structured zeolite adsorbents and even catalysts for practical applications.