Tunichrome mimetic matrix, its perspective in abatement for carcinogenic hexavalent chromium and specific coordination behavior

•A newly designed nano-bio tool inspired by marine tunicate, a filter feeder.•Superior retention of CrVI by mimicking tunichrome matrix in remediation treatment.•Pyrogallol - a primary factor in increased efficiency as a proof-of-concept study.•First comprehensive report on tunichrome's chromium metal coordination chemistry.

Inspired by naturally occurring metal chelation strategy by pyrogallol moiety of tunichromes of marine tunicates, a strong retention of carcinogenic chromium (CrVI) is described by mimicking tunichrome matrix as a proof-of-concept investigation in water treatment applications. Harvesting tunichromes tailored with the pyrogallol moiety are extremely difficult owing to aerial sensitivity and purification difficulties, thus proving a challenging synthesis problem. Despite significant interest, knowledge of specific metal coordination in tunicate's matrix is still ambiguous, hindering study scope. We planned to fabricate a promising tunichrome matrix (TM) tailored with pyrogallol moieties from the Earth-abundant raw materials (gallic acid and chitin nanofiber) at mass scale without artificial aid. Specifically, we aimed at atomistic understanding of contaminant and pyrogallol moiety of TM by examining the structural parameters (redox change, geometrical distortion, coordination bond). Cr K-edge extended X-ray absorption fine structure (EXAFS) corresponds well to nontoxic CrIII (average four CrO bond lengths of 1.91 Å) and a small fraction of CrVI (average two CrO bond lengths of 1.62 Å). A coupled reductive complexation mechanism was identified by combining near edge X-ray absorption fine structure (NEXAFS) and linear combination fits. From the viewpoint of practical utility and effective performance (nearly 119 mg chromium per g weight of TM), the impacts of water chemistry conditions were investigated from a variety of contaminated waters, showing a distinct improvement compared to conventional popular materials. The gained knowledge would be beneficial for utilizing a pyrogallol moiety as an alternative greener and sustainable scavenger, specifically for toxic chromium.

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