Dynamic Micelle‐Hydrogels for 3D‐Architected Transition Metal Sulfides

Abstract Additive manufacturing of transition metal sulfides (TMS) enables the creation of complex 3D structures, significantly expanding their applications. However, preparing 3D‐structured TMS remains challenging due to difficulties in developing suitable inks. In this study, a supramolecular micelle hydrogel as the ink to fabricate 3D‐structured TMS is utilized. Initially, the hydrogels are printed and infused with metal salt solutions to stabilize the structures, which are then calcined to convert into miniaturized 3D‐TMS replicas. The micellar hydrogels crosslink via hydrophobic interactions, with sodium dodecyl sulfonate (SDS) micelles providing both a hydrophobic environment and sulfur sources. During calcination, the decomposed sulfur precursors coordinate with metal ions to form various TMS, including FeS 2 , Cu 2 S, Ni 3 S 2 , and Co 9 S 8 , along with several metal sulfides like PbS and SnS. Additionally, the method also allows for the preparation of transition metal dichalcogenides such as MoS 2 and WS 2 . The formation mechanism is demonstrated using Ni 3 S 2 as an example which exhibits notable catalytic activity in oxygen evolution reactions (OER) and hydrogen evolution reactions (HER). Given its simplicity and versatility, this dynamic micellar hydrogel‐derived strategy offers a promising pathway for creating advanced TMS materials.