Polyacid-Protonated Covalent Organic Frameworks Enable Stable and Efficient Photothermal Textiles

Protonation is an effective strategy to enhance light trapping and photothermal conversion in covalent organic frameworks (COFs), yet conventional protonation sites are prone to environmental deactivation, leading to diminished stability and photothermal performance. Inspired by the stability of protein matrices, we developed polyacid-protonated COFs (PaCOFs) through in situ polymerization of dimercaptobutanesioic acid via dynamic disulfide bonds within COF pore channels. The resulting PaCOFs exhibit exceptional protonation stability and deliver a superior photothermal conversion efficiency of 77.8%, surpassing those of most conventional photothermal nanomaterials. Notably, PaCOFs can be readily processed by electrospinning into dual-mode thermal management textiles that achieve radiative cooling (∼7.2 °C) and solar heating (∼10.1 °C) under sunlight. These textiles outperform their commercial counterparts in wearable applications, establishing polyacid protonation as a robust strategy for stabilizing COFs and advancing their integration into photothermal energy conversion and personal thermal management.