Robust Self‐Catalytic Reactor for CO₂ Methanation Fabricated by Metal 3D Printing and Selective Electrochemical Dissolution

Abstract

The methanation of CO2 has been actively pursued as a practical approach to mitigating global climate change. However, the complexity of the catalyst development process has hindered the development of new catalysts for CO2 methanation; as a result, few catalysts are commercially available. Herein, a multifunctional self‐catalytic reactor (SCR) is prepared via metal 3D printing and selective electrochemical dissolution as a method to not only simplify the catalyst development process but also fabricate active catalysts for CO2 methanation. The combination of metal 3D printing and selective electrochemical dissolution is demonstrated as a feasible method to prepare active catalysts for the methanation of CO2 in a short time. In addition, the use of an electrochemical method enables the formation of galvanic cells on the SCR; these cells continuously generate active sites via self‐dissolution during a simple refresh process, resulting in high reusability of the SCR. The proposed method represents a new facile technique to fabricate highly reusable catalysts that exhibit superior performance for CO2 methanation, and the results provide a guideline for preparing metal 3D‐printed catalysts that will satisfy industrial demand.

Hollow carbon-based materials for electrocatalytic and thermocatalytic CO2 conversion

“…Methane synthesis from CO 2 hydrogenation (CO 2 + 4H 2 / CH 4 + 2H 2 O, DH°= −165 kJ mol −1 ), known as the Sabatier reaction, is an exothermic process that is more thermodynamically favorable than many other hydrogenation routes. 21,171 However, it still suffers from signicant kinetic limitations due to the intrinsical inertness of linear CO 2 and the involvement of an eight-electron transfer process. 165,172,173 Several metal-containing catalysts have been demonstrated as effective candidates for this reaction, typically based on Ru, Rh, Pd, and Ni NPs on supported materials, with Ni-based catalysts being the most popular one because of the low cost and rich reserves.…”

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

“…The catalytic active sites in an SCR are generated within the reactor itself through self-oxidation or dissolution, simplifying post-treatment processes and enhancing reusability. [7,9] This integrated approach not only optimizes reactor capacity utilization but also streamlines catalyst development, potentially accelerating the development of new commercial catalysts. Wei et al utilized selective laser sintering (SLS) to fabricate an SCR with Fe, Co, and Ni for harsh catalytic reactions such as Fisher-Tropsch (FT) reactions, CO 2 hydrogenation, and methane dry reforming, demonstrating high performance and reusability (Figure 4a and b).…”

“…[8] Kim et al created Ni-SCRs with four different pattern shapes using SLM for CO 2 methanation and applied electrochemical methods to expose active Ni sites (Figure 4c and d). [9] After the appropriate electrochemical treatment, the Ni-SCR was transformed into a highly active catalyst, achieving 80 % CO 2 conversion in the P4 pattern with high stability and reusability. [5] b) Repeating micromixer reactor prepared by STS 316 for benzaldehyde and furfural reduction.…”

“…[4][5][6] Moreover, the new concept of integration of catalyst and reactor functions, covered by the term self-catalytic reactor (SCR), has been recently proposed and opened a new way of optimizing the usage of metal 3D printing in the catalytic field (Figure 1). [7][8][9] However, the successful integration of metal 3D printing technology into the design and manufacturing process of catalytic reactors hinges on solving unique challenges, including materials selection, printer resolution, post-surface treatment requirements, and durability under harsh reaction conditions. In spite of these challenges, the potential benefits, such as improved catalyst performance, reactor design efficiency, and environmental sustainability, require thorough investigation and discussion.…”

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

“…More recently, metal 3D-printing methods, such as selective laser melting (SLM), − selective laser sintering (SLS), − and direct metal printing, , have been extended into the catalysis field because they can be used to integrate a catalyst and reactor into a single system . We have demonstrated that metal 3D printing is a feasible method to prepare a multifunctional self-catalytic reactor (SCR) using Hastelloy X powder as a starting material . Selective electrochemical dissolution of the SCR successfully transformed the original inert surface, which consisted of a Cr- and Fe-based passivation layer, into a Ni-enriched surface that is active as a robust catalyst for CO 2 methanation.…”