Optimization of 3D Metal‐Based Assemblies for Efficient Electrocatalysis: Structural and Mechanistic Studies

Abstract The commercial utilization of low‐dimensional catalysts has been hindered by their propensity for agglomeration and stacking, greatly minimizing their utilization of active sites. To circumvent this problem, low‐dimensional materials can be assembled into systematic 3D architectures to synergistically retain the benefits of their constituent low‐dimensional nanomaterials, with value‐added bulk properties such as increased active surface area, improved charge transport pathways, and enhanced mass transfer, leading to higher catalytic activity and durability compared to their constituents. The hierarchical organization of low‐dimensional building blocks within 3D structures also enables precise control over the catalyst's morphology, composition, and surface chemistry, facilitating tailored design for specific electrochemical applications. Despite the surge in 3D metal‐based assemblies, there are no reviews encompassing the different types of metal‐based 3D assemblies from low‐dimensional nanomaterials for electrocatalysis. Herein, this review addresses this gap by investigating the various types of self‐supported 3D assemblies and exploring how their electrocatalytic performance can be elevated through structural modifications and mechanistic studies to tailor them for various electrochemical reactions.