Passive daytime radiative cooling (PDRC) is an emerging sustainable technology that can spontaneously radiate heat to outer space through an atmospheric transparency window to achieve self-cooling. PDRC has attracted considerable attention and shows great potential for personal thermal management (PTM). However, PDRC polymers are limited to polyethylene, polyvinylidene fluoride, and their derivatives. In this study, a series of polymer films based on thermoplastic polyurethane (TPU) and their composite films with silica aerogels (aerogel-functionalized TPU (AFTPU)) are prepared using a simple and scalable non-solvent-phase-separation strategy. The TPU and AFTPU films are freestanding, mechanically strong, show high solar reflection up to 94%, and emit strongly in the atmospheric transparency window, thereby achieving subambient cooling of 10.0 and 7.7 °C on a hot summer day for the TPU and AFTPU film (10 wt%), respectively. The AFTPU films can be used as waterproof and moisture permeable coatings for traditional textiles, such as cotton, polyester, and nylon, and the highest temperature drop of 17.6 °C is achieved with respect to pristine nylon fabric, in which both the cooling performance and waterproof properties are highly desirable for the PTM applications. This study opens up a promising route for designing common polymers for highly efficient PDRC.

Passive thermal regulation has attracted increasing interest owing to its zero-energy consumption capacity, which is expected to alleviate current crises in fossil energy and global warming. In this study, a biomimetic multilayer structure (BMS) comprising a silica aerogel, a photothermal conversion material (PTCM), and a phase change material (PCM) layer is designed inspired by the physiological skin structure of polar bears for passive heating with desirable temperature and endurance. The transparent silica aerogel functions as transparent hairs and allows solar entry and prevents heat dissipation; the PTCM, a glass plate coated with black paint, acts as the black skin to convert the incident sunlight into heat; and the PCM composed of n-octadecane microcapsules stores the heat, regulating temperature and increasing endurance. Impressively, outdoor and simulated experiments indicate efficient passive heating (increment of 60 °C) of the BMS in cold environments, and endurance of 157 and 92 min is achieved compared to a single aerogel and PTCM layer, respectively. The uses of the BMS for passive heating of model houses in winter show an increase of 12.1 °C. COMSOL simulation of the BMSs in high latitudes indicates robust heating and endurance performance in a −20 °C weather. The BMS developed in this study exhibits a smart thermal regulation behavior and paves the way for passive heating in remote areas where electricity and fossil energy are unavailable in cold seasons.

Silica aerogels, a type of porous material featuring extra low density and thermal conductivity, have drawn increasing interest from both academia and industry owing to their excellent thermal insulation performance. However, thermal insulation is always the single consideration when silica aerogels are used for thermal management. In this study, the on‐demand thermal management (ODTM) of silica aerogel with either passive thermal insulation, passive heating, or passive cooling in different environments is revealed. The ODTM behavior of silica aerogels can be simply fulfilled through their optical property variations such as solar light transparency and infrared emissivity, which are controllable via the microstructures of the building blocks and surface composition design. Robust solar heating of 25 °C higher than the ambient in the daytime and sub‐ambient cooling of 7 °C at night is achieved with the traditional transparent silica aerogel. Interestingly, sub‐ambient cooling of 5 °C in the daytime and a warmer state on cold nights is achieved by modifying its solar transmittance and infrared emissivity. This study guides a comprehensive understanding of the thermal management behavior of silica aerogels and leads to ODTM applications of silica aerogels by tailoring their optical and thermal conductivity properties.

Personal thermal management (PTM) materials have attracted increasing attention owing to their application for personal comfort in an energy-saving mode. However, they normally work in the same media such as in the air, and little is known about what will happen in other media like water. In this study, a system for cross-media thermal management (CMTM): passive cooling in air and thermal insulation underwater is proposed. Hybrid aerogels comprising thermoplastic polyurethane (TPU) matrix and superhydrophobic silica aerogel particle (SSAP) for CMTM are designed and synthesized using a thermally induced phase separation and self-templating strategy. The TPU matrix endows the aerogels with super stretchability (500%), shape memory, and outstanding healing recovery rate (89.9%), which are ideal characteristics for potential wearable usage. Additionally, the TPU and SSAP endow the aerogel with high solar reflectivity and infrared emissivity, thus achieving a sub-ambient cooling of 10.6 °C in air. Moreover, the SSAP endows the aerogels with low thermal conductivity (0.052 W m −1 •K −1 ) and high hydrophobicity (143°), enabling the aerogels for underwater thermal insulation. The CMTM performance of the aerogels makes them for potential uses in cross-media environments such as reefs and islands where cooling in air and thermal insulation in water are required.

Personal thermal management (PTM) has attracted extensive attention due to its convenience for both wearable cooling and warming in a person-to-person manner. However, challenges remain for PTM in harsh conditions, not only for the material's resistance to harsh conditions but also for the thermal regulation capacity in extreme environments. Herein, a conformal structured polypyrrole@Al 2 O 3 ceramic fiber fabric (CCF) has been designed and synthesized by an in situ conformal growth strategy. The polypyrrole shell induces robust photothermal conversion and joule heating capacities, while the Al 2 O 3 ceramic fiber matrix endows flame resistance up to 1300 °C, enabling the CCF to have dual-mode passive and positive heating in harsh conditions. Under a solar radiation intensity of 850 W•m −2 , the CCF can achieve a passive heating temperature of 65 °C. At a driving voltage of 5.5 V, the composite ceramic fiber fabric showed a rapid temperature response, and its surface temperature can be increased by 50.9 °C. This study provided a strategy for active and passive heating of functional fabrics targeted in harsh conditions.