Heterointerfacial and Architectural Engineering in MOF‐Templated Corn‐Like FePS 3 ‐ZnPS 3 ‐C@NC Anode for Durable Sodium Storage

2D layered transition metal thiophosphites (MPS₃) are promising high-capacity anodes for sodium-ion batteries (SIBs) but are plagued by poor conductivity and severe volume changes. To address these challenges, we report a corn-like multi-MPS₃ heterostructure engineered via a sophisticated MOF-on-MOF templating strategy. This unique architecture, comprising a FePS₃/ZnPS₃ heterojunction and a conformal N-doped carbon (NC) coating, establishes an interfacial field and spatial confinement synergy that facilitates rapid ion/electron transport and ensures exceptional structural integrity. The designed FePS₃-ZnPS₃-C@NC anode delivers remarkable sodium storage performance: a high initial discharge capacity of 1294.5 mAh g^-1 at 0.1 A g^-1 and long cycling stability with 87.6% capacity retention after 1200 cycles at 2 A g^-1. Such superior performance is attributed to: (i) the elastic carbon coating, which effectively buffers mechanical strain and preserves structural stability; and (ii) the heterointerfacial synergy, which enhances charge carrier mobility and reaction kinetics. Ex situ characterizations unravel a multi-mechanistic sodium storage process, accounting for the high capacity. Density functional theory (DFT) calculations confirm that the built-in electric field at the FePS₃/ZnPS₃ interface optimizes Na⁺ adsorption energy and interfacial charge transfer. This study provides a generalizable design paradigm for high-performance anodes through the rational integration of architectural control and interfacial engineering.