Hydrogen-bonding interface engineering enables efficient perchlorate removal via dual-site polarization and suppressed competitive hydration.

Perchlorate (ClO4⁻) contamination poses serious risks to ecosystems and human health due to its high mobility, persistence, and thyroid-disrupting toxicity. Current technologies struggle with the rapid, selective removal of ClO4⁻, particularly in complex water matrices. In this study, we addressed this challenge by developing a hydrogen-bond interface-engineered adsorbent, Mn/N-coordinated porous carbon modified with formic acid (Mn-NC···HCOOH), to achieve efficient and rapid ClO4⁻ removal. The novelty of this work lies in the engineering of dual active sites (Mn and N-coordinated C), coupled with the polarization of these sites via hydrogen-bonding interactions, which significantly enhances ClO4⁻ binding and suppress competitive hydration from water molecules. This adsorbent exhibited an ultrafast uptake rate of 1.2 × 104 μg/ (g· min) and a Langmuir maximum adsorption capacity of 79.17 mg/g (about 50% higher than the unmodified Mn-NC). The material retained > 80% removal efficiency in the presence of common coexisting ions and natural organic matter over a broad pH range of 3.5-9.0. Importantly, it achieved 98% ClO4⁻ removal within 5 min in real ClO4⁻-contaminated wastewater (62.9 mg/L) and showed stable operation over 10 h continuous-flow packed-bed treatment. This work recommends hydrogen-bonding interface engineering as a promising strategy for designing high-performance adsorbents, which can be extended to the removal of other oxyanions for environmental remediation.