Rational Design of Hollow Nanostructures: Engineering the Cavity Microenvironment for Advanced Electrocatalysis

Hollow nanostructures have emerged as a pivotal class of nanomaterials in electrocatalysis, offering intrinsic advantages such as high surface-to-volume ratios, reduced density, and economical utilization of precious metals. However, the prevailing research paradigm has predominantly focused on the external shell characteristics while overlooking the decisive role of the interior cavity microenvironment. This review introduces a novel conceptual framework that positions the rational engineering of the cavity microenvironment—encompassing mass transport dynamics, localized electronic structure modulation, active site exposure, and structural stability—as a unified design principle for next-generation electrocatalysts. We systematically elucidate how precise control over cavity geometry, composition, and interfacial properties can optimize electrocatalytic performance for oxygen reduction (ORR), oxygen evolution (OER), and hydrogen evolution (HER) reactions. By correlating microenvironmental parameters with catalytic metrics, we establish structure–property–performance relationships and highlight recent breakthroughs. Finally, we outline future challenges in achieving atomic-level precision in cavity design, understanding dynamic evolution under operating conditions, and scaling up synthesis for industrial applications.