Hollow-structured materials exhibit breakthrough potential in energy storage and conversion, leveraging unique advantages including high specific surface area, controllable cavity architecture, and short-range mass transfer pathways, alongside tunable functional properties. This review synthesizes recent progress, emphasizing the constitutive relationships governing material synthesis, structural engineering, and resultant performance. Key synthesis strategies including encompassing hard-templating, soft-templating, and template-free approaches are delineated with respect to their mechanisms and characteristics. Subsequently, cutting-edge applications in energy storage systems (e.g., lithium-ion batteries, supercapacitors), conversion systems (e.g., photoelectrocatalysis) and the application of partial in-situ testing technology for exploring the reaction mechanism are highlighted. The review concludes by outlining critical challenges and opportunities pertaining to scalable fabrication, structural stability, and device integration, providing a roadmap for the precise design and performance optimization of these materials.

The development of efficient and affordable electrode materials is key to the construction of clean energy storage systems. Transition-metal chalcogenophosphates (TMPX₃, where TM represents Ni, Fe, Zn, V, Mn, Co, etc., and X denotes S, Se, or Te) are a promising class of two-dimensional (2D) layered materials with great potential for energy storage, photoelectrocatalysis, and electronic devices due to their unique electronic structure and tunable bandgap. In this review, we systematically summarise the latest research progress on TMPX₃ materials, adopting a pioneering multidimensional analysis framework to overcome the limitations of a unified single perspective. Firstly, we reveal the mechanisms of P–S bond anisotropy and TM coordination on the energy band structure from the atomic scale; secondly, through the comparative analysis of the existing preparation methods and regulation strategies, the optimised pathways for precise control of the number of layers and large-scale production are proposed. On this basis, we focus on the applications of TMPX₃ in photoelectrocatalysis and metal batteries, and elucidate the cross-scale correlation mechanism between its electronic/interfacial properties and macroscopic performance. Finally, the challenges and future opportunities of the material are presented, with the aim of providing valuable insights into the multi-field, precisely coupled design and energy storage applications of TMPX₃ materials.