Bioinspired hierarchical nanofibers enable molecular discrimination for environment-adaptive functionality integration.

The trade-off between permeation flux and removal efficiency has long hindered membranes for multiphase pollutant purification. Herein, we fabricate hierarchical interface-armored poly(lactic acid) (HIA-PLA) nanofibrous membranes featuring a biomimetic protective architecture with cross-scale micro-nano structures that enable simultaneous high-efficiency and high-flux separation. Bimetallic metal-organic frameworks (BMOF) are in-situ polymerized at polydopamine-modified PLA nanofibers, yielding ultrahigh nanocrystal loading (73.6%), abundant Lewis basic sites, and accessible open metal centers. The bioinspired membranes enable high electrical output (21.8 V), outstanding PM0.3 filtration efficiency (98.7% at 90% RH), high CO2 uptake (3.1 mmol·g-1), and exceptional separation selectivity (CO2/N2 = 278; CO2/CH4 = 54). It exhibits excellent regenerability with nearly 100% performance retention even after 10 cycles. This exceptional functionality integration arises from synergistic size exclusion, electrostatic adsorption, and hierarchical pore confinement. Notably, the HIA-PLA membranes also demonstrate promising self-regulating sensing capabilities, in need for real-time respiratory monitoring applications. This work establishes a useful platform empowering efficient air purification with wearable health monitoring for extreme environments.