Polyoxometalate-based peroxidase-mimicking sensors for colorimetric detection and discrimination of phenolic pollutants

Abstract

Phenol and its derivatives represent a kind of significant hazards to both human health and the integrity of ecological systems. Exploring an efficient detection and discrimination approach for them is urgent. Herein, a kind of polyoxometalate-based peroxidase-mimicking crystalline colorimetric sensors were developed by integrating dual active sites of Keggin-type polyoxoanions and coordination unsaturated copper centers, for which the formulas are [Cu(dppeo)3]2[Cu(dppeo)2(H2O)](dppeo)0.75[PMo12O40]2·9H2O (1), [Cu(dppeo)2(H2O)]2 [SiW12O40]·6H2O (2), [Cu(dppeo)2]3[PW12O40]2·12H2O (3), (dppeo = 1,2-bis(diphenylphosphino)ethane dioxide). Structural analysis revealed that these compounds exhibit 0-D supramolecular architecture formed through the interplay of electrostatic forces and hydrogen bonding interactions between Keggin-type polyoxoanions and dppeo-chelated copper-organic cationic fragments. Sensors 1–3 exhibit favorable peroxidase-mimicking catalytic activities, which expedite the reaction involving phenol, 4-aminoantipyrine and hydrogen peroxide (H2O2), resulting in a pronounced color change for indicating the target concentration levels. These crystalline sensors responded linearly to phenol concentration within 0.01–1.0 mM, affording low detection limits of 1.19, 1.59 and 3.78 μM for 1–3. These sensors demonstrate exceptional anti-interference capabilities and exhibit excellent applicability in real water samples, ensuring high recovery rates. By incorporating a colorimetric array with principal component analysis, the sensors effectively discriminate between common phenolic compounds. This research presents an innovative methodology for the design of crystalline sensor materials, paving the way for the detection and differentiation of phenolic pollutants within environmental applications.