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

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.

Advances in Metal 3D Printing Technology for Tailored Self‐Catalytic Reactor Design

“…The CFD study indicated that a decrease in pore size from 2.0 mm to 1.5 mm caused a pressure drop (Δp) approximately 3 times greater, resulting in a negative effect on the catalytic activity by reducing the surface velocity. [15] Moreover, Li et al designed an optimum CuNi alloy monolithic catalyst for a reverse water-gas shift (RWGS) reaction combined with CFD method. Two different unit cell sizes of triply periodic minimal surface (TPMS) structure and honeycomb monolith were designed to investigate the effect of the geometric structure on the catalytic performance.…”

“…recently proposed the utilization of metal organic frameworks (MOFs) as a modifier. The Cu‐based 3D‐printed reactors were immersed into an acid solution containing an organic linker for the synthesis of MOFs, where Cu 2+ ions dissolved in situ were assembled to form MOF crystals on the surface of the reactor [15] . This further allows carbonization, deposition of metal nanoparticles, and modification with organic molecules, enabling H 2 production from liquid‐phase hydrogen storage materials.…”

“…utilized CFD to elucidate the effect of pore size in a MOF‐functionalized Cu‐SCR on liquid‐phase catalytic H 2 production. The CFD study indicated that a decrease in pore size from 2.0 mm to 1.5 mm caused a pressure drop (Δp) approximately 3 times greater, resulting in a negative effect on the catalytic activity by reducing the surface velocity [15] . Moreover, Li et al.…”

Confined Space Nanoarchitectonics for Dynamic Functions and Molecular Machines

“…Such spaces include environments that are surrounded by nanopore structures, as well as surface spaces that are strongly bounded from the surface. The design of such spaces involves the use of mesoporous materials [215][216][217][218], metal-organic frameworks (MOFs) [219][220][221][222], covalent organic frameworks (COFs) [223][224][225][226], self-assembled monolayers (SAM) [227][228][229][230], Langmuir-Blodgett (LB) film [231][232][233][234], layer-by-layer (LbL) assembly [235][236][237][238], etc.…”