Rational construction of a robust metal-organic framework nanozyme with dual-metal active sites for colorimetric detection of organophosphorus pesticides.

While nanomaterials with enzyme-mimicking activities are emerging as promising candidates in the colorimetric detection of organophosphorus pesticides (OPs), the catalytic activities and recognition ability to analyte of most nanozymes are inherently deficient. In this work, we introduced manganese ions into a typical iron based MOF (Fe-MIL(53)) via a one-pot hydrothermal reaction strategy, which brought out a catalytically favorable bimetallic Mn/Fe-MIL(53) MOF nanozyme. The catalytic performance of Mn/Fe-MIL(53) is superior to that of pure Fe-MIL (53) and the mechanism for superior catalytic activity of material is revealed by active species scavenging experiments and X-ray photoelectron spectroscopy (XPS). Besides, the introduction of manganese endows the material with the characteristic of being specially destroyed by choline, which motivates the establishment of a simple, selective and sensitive colorimetric strategy for OPs detection. The proposed colorimetric strategy could quantify the methyl parathion and chlorpyrifos in the concentration range of 10-120 nM and 5-50 nM, respectively. The low detection limit of 2.8 nM for methyl parathion and 0.95 nM (3 S/N) for chlorpyrifos were achieved. Good recoveries were obtained when applied in the real sample detection. Our work paves the way to boost catalytic performance of MOF nanozymes, which will be useful in biosensing.