Engineering Bipolar Covalent Organic Framework Membranes for Selective Acid Extraction

Nitric acid (HNO3) is a vital industrial chemical, and its recovery from complex waste streams is essential for sustainability and resource optimization. This study demonstrates the effectiveness of bipolar covalent organic framework (COF) membranes with tunable ionic site distributions as a solution for this challenge. The membranes are fabricated by layering anionic COF nanosheets on cationic COF layers, supported by a porous substrate. The resulting membranes exhibit significant rectifying behavior, driven by the asymmetric charge polarity and the intrinsic electric field, which enhances HNO3 transport. The transmembrane diffusion coefficient of 2.74 × 10–5 cm2 s–1 exceeds the self‐diffusion rate of NO3–, leading to increased HNO3 flux and selectivity compared to the individual anionic and cationic COF membranes. The optimized bipolar membrane configuration achieves remarkable separation factors, ranging from 22 to 242,000 for HNO3, in comparison to other solutes such as HCl, H2SO4, H3PO4, and various metal salts in an eight‐component mixed waste stream. This results in a substantial increase in HNO3 purity, from 12.5% to 94.1% after a single membrane separation. With the broad range of COF materials and the versatility of the proposed membrane design, this work represents a significant advancement in chemical separation technologies.