Photoliquefiable Azobenzene Surfactants toward Solar Thermal Fuels that Upgrade Photon Energy Storage via Molecular Design

Photoresponsive phase change materials (PPCMs) are capable of storing photon and heat energy simultaneously and releasing the stored energy as heat in a controllable way. While, the azobenzene‐based PPCMs exhibit a contradiction between gravimetric energy storage density and photoinduced phase change. Here, a type of azobenzene surfactants with balance between molecular free volume and intermolecular interaction is designed in molecular level, which can address the coharvest of photon energy and low‐grade heat energy at room temperature. Such PPCMs gain the total gravimetric energy density up to 131.18 J g−1 by charging solid sample and 160.50 J g−1 by charging solution. Notably, the molar isomerization enthalpy upgrades by a factor of up to 2.4 compared to azobenzene. The working mechanism is explained by the computational studies. All the stored energy can release out as heat under Vis light, causing a fast surface temperature rise. This study demonstrates a new molecular designing strategy for developing azobenzene‐based PPCMs with high gravimetric energy density by improving the photon energy storage. A good balance between molecular free volume and intermolecular interaction for azobenzene‐containing surfactants is realized in molecular level, which leads to solar thermal fuels addressing the coharvest of photon energy and low‐grade heat energy at room temperature. This study provides a molecular designing strategy for developing solar thermal fuels with high gravimetric energy density by improving the photon energy storage.