Enhanced oxidoreductase activity of diatom frustule supported Fe3O4 for sensitive colorimetric detection of Cr(VI)

Abstract

Given Cr(VI) is a ubiquitous water pollutant posing significant public health risks, there is a need for an inexpensive and easy-to-use detection tool. Herein, a diatom frustule-supported Fe₃O₄ (DF-Fe₃O₄) with enhanced oxidoreductase mimetic activity is reported for direct colorimetric detection of Cr(VI). Unlike the peroxidase nanozymes which are often reported for colorimetric detection, DF-Fe₃O₄ triggered a chromogenic redox reaction between TMB and Cr(VI) without requiring H₂O_2. This enables direct redox reactions while circumventing potential interferences associated with the use of H₂O_2. DF-Fe₃O₄ was synthesized with a coprecipitation method and subsequently characterized by SEM, XRD, and XPS techniques, revealing the distribution of Fe₃O₄ NPs on the frustule matrix. The frustule obtained from Nitzschia sp. of a sediment sample rendered a robust catalytic support enhancing the oxidoreductase activity of pristine Fe₃O₄ NPs by 20.8 %. Further, the nanozyme maintains 73 % of its activity even at 95 °C while losing only 33 % of its activity after one month of storage. The oxidoreductase mimetic activity was evaluated using the chromogenic redox reaction between TMB and Cr(VI) which rapidly forms a blue color (${\lambda }_{\max }=$ 654 nm), where its intensity forms the basis of the colorimetric detection. With a K_m value of 0.058 mM, the nanozyme was able to selectively detect Cr(VI) down to 0.21 µM with a linear range between 0.1–500 µM. Recoveries from spiked wastewater samples were between 91.14–102.20 %. The obtained analytical figures of merits demonstrated the applicability of the developed sensor for Cr (VI) analysis devoid of complex instrumentation in the established analytical methods.