Surface Chemical Engineering of a Metal 3D-Printed Flow Reactor Using a Metal-Organic Framework for Liquid-Phase Catalytic H2 Production from Hydrogen Storage Materials

ACS Appl Mater Interfaces. 2023 Nov 8;15(44):51079-51088. doi: 10.1021/acsami.3c10945. Epub 2023 Oct 25.

Abstract

The accurate positioning of metal-organic frameworks (MOFs) on the surface of other materials has opened up new possibilities for the development of multifunctional devices. We propose here a postfunctionalization approach for three-dimensional (3D)-printed metallic catalytic flow reactors based on MOFs. The Cu-based reactors were immersed into an acid solution containing an organic linker for the synthesis of MOFs, where Cu2+ ions dissolved in situ were assembled to form MOF crystals on the surface of the reactor. The resultant MOF layer served as a promising interface that enabled the deposition of catalytically active metal nanoparticles (NPs). It also acted as an efficient platform to provide carbonous layers via simple pyrolysis under inert gas conditions, which further enabled functionalization with organic modifiers and metal NPs. Cylindrical-shaped catalytic flow reactors with four different cell densities were used to investigate the effect of the structure of the reactors on the catalytic production of H2 from a liquid-phase hydrogen storage material. The activity increased with an increasing internal surface area but decreased in the reactor with the smallest cell size despite its high internal surface area. The results of fluid dynamics studies indicated that the effect of pressure loss becomes more pronounced as the pore size decreases.

Keywords: flow reactor; hydrogen; metal 3D printing; metal−organic framework; postfunctionalization.