Synergistic solar-thermal icephobic armor: Ultrasmall-bandgap MOFs drive efficient anti-/de-icing via superhydrophobic photothermal cooperation

Metal–organic frameworks (MOFs) have been positioned as promising candidates for fabricating photothermal superhydrophobic surfaces, due to their gas-trapping porosity, tunable nanoarchitectures, and notable solar-thermal conversion. Breaking the photon barrier of conventional MOFs, we engineer an ultrasmall-bandgap MOF ( E g = 0.33 eV) into laser-carved hierarchical microarmor, creating sunlight-driven icephobic surfaces with molecular-level warfare capabilities. The bioinspired architecture—featuring in situ grown MOF nanoneedles on laser-etched honeycomb scaffolds—achieves a record-high solar-thermal conversion efficiency (STCE) of 94.79% through ultrafast vibrational relaxation ( τ ≈ 1.25 ps) and bandgap-modulated electron–phonon coupling, as resolved by transient absorption spectroscopy and atomistic simulations. This synergy of multiscale textures and engineered carrier dynamics achieves record-breaking anti-/de-icing at −15 °C: 4,633 s icing delay, 6.0 kPa ice adhesion, and 277 s de-icing speed, all while surviving harsh mechanical ablation and freeze-thaw cycles. Remarkably, after 1,200 mechanical flexion cycles, the ice adhesion strength maintains ultralow values (< 30.0 kPa) compatible with gravity-driven shedding, enabled by stress-dissipative microarchitected interfaces, which is further validated in anti-/de-icing demonstrations on steel-cored aluminum stranded wire and wind turbine blades. This bandgap engineering paradigm pioneers ultrasmall-bandgap MOFs as photothermal icephobic sentinels, integrating semiconductor physics with phonon-engineered energy dissipation for climate-resilient infrastructure. • Ultrasmall-bandgap MOFs (0.33 eV) enable record 94.79% solar-thermal conversion via tailored electron-phonon coupling. • Bioinspired microarmor achieves extreme anti-/de-icing: 4633 s delay, 6.0 kPa adhesion, and 277 s de-icing at −15 °C. • Stress-dissipative interfaces sustain ultralow ice adhesion (