Hierarchical Microspheres‐Based Composite Materials with TiO₂‐Coated SiO₂ Combined with BaSO₄ or PNIPAM for Radiative Cooling

Abstract Microspheres dispersed in composites exhibit excellent infrared emissivity for radiative cooling applications, which reflect sunlight and passively dissipate heat into space without electricity. In this study, hierarchical microspheres (HMs) with a two‐tier structure, composed of SiO₂, TiO₂‐coated SiO₂, BaSO₄, or PNIPAM, are incorporated into PDMS‐based composites. These microspheres feature larger spheres assembled from submicrometer‐scale nanoparticles and are fabricated via microfluidics to enhance radiative cooling performance. SiO₂ HMs not only boost visible light reflection and exhibit structural color through a photonic stop band but also achieve an average emissivity of 97.55% in the atmospheric window. Both experimental and simulated results show that HMs enhance the emissivity performance of the composite material compared with solid SiO₂ microspheres of the same diameter. Additionally, applying TiO₂ coating to SiO₂ HMs further increases the overall emissivity to 98.05%. Incorporating BaSO₄ HMs also increased the average visible reflectivity to 96.56%, while maintaining superior infrared emissivity at 97.58%. The inclusion of PNIPAM spheres enabled temperature‐responsive transmissivity, with the composite materials containing PNIPAM and SiO₂ HMs preserving high infrared emissivity in the atmospheric window. These HM structures exhibit excellent solar reflectivity and thermal emission, making them effective for radiative cooling.