3D-Printed Metal–Organic Framework Monoliths for Gas Adsorption Processes

Abstract

Metal-organic frameworks (MOFs) have shown promising performance in separation, adsorption, reaction, and storage of various industrial gases; however, their large-scale applications have been hampered by the lack of a proper strategy to formulate them into scalable gas-solid contactors. Herein, we report the fabrication of MOF monoliths using the 3D printing technique and evaluation of their adsorptive performance in CO removal from air. The 3D-printed MOF-74(Ni) and UTSA-16(Co) monoliths with MOF loadings as high as 80 and 85 wt %, respectively, were developed, and their physical and structural properties were characterized and compared with those of MOF powders. Our adsorption experiments showed that, upon exposure to 5000 ppm (0.5%) CO at 25 °C, the MOF-74(Ni) and UTSA-16(Co) monoliths can adsorb CO with uptake capacities of 1.35 and 1.31 mmol/g, respectively, which are 79% and 87% of the capacities of their MOF analogues under the same conditions. Furthermore, a stable performance was obtained for self-standing 3D-printed monolithic structures with relatively good adsorption kinetics. The preliminary findings reported in this investigation highlight the advantage of the robocasting (3D printing) technique for shaping MOF materials into practical configurations that are suitable for various gas separation applications.

Hierarchical Metal–Organic Frameworks with Macroporosity: Synthesis, Achievements, and Challenges

“…Reprinted with permission from Ref. [146]. Copyright 2017 American Chemical Society novel one-pot room temperature approach using water as a solvent was carried out by Sultan et al [149].…”

CelloMOF: Nanocellulose Enabled 3D Printing of Metal–Organic Frameworks

“…As compared to these techniques, 3D printing offers valuable advantages, such as high reproducibility, fabrication of complex geometries, controlled pore structures, tailored directionality, low cost, time effectiveness, and up‐scalability. However, 3D printing of MOFs usually requires additive materials, such as bentonite clay (as a binder) and polyvinyl alcohol (as a plasticizer) in ethanol, acrylonitrile butadiene styrene, poly(lactic acid), thermoplastic polyurethane matrices, and photopolymers, while demanding high processing temperature of up to 230 °C or ultraviolet curing. 3D printing of a composite containing MOFs has only been investigated to a limited extent.…”

Synthesis through 3D printing: formation of 3D coordination polymers

“…14 In the past two years, there have been several reports of functional 3D-printed structures that contained coordination polymers. Thakkar et al reported the 3D-printing of MOF, embedded in an organic-inorganic binder for removal of CO 2 from air, 15 as well as the 3D-printing of ZIF-7 embedded within organic monoliths for ethane/ethylene separation processes. 16 Our group reported the 3D-printing of Cu-BTC MOF for the adsorption of organic dyes from solutions, 17 and Lyu et al reported a 3D-printed cobalt-based MOF embedded within an organic binder for energy storage applications.…”