Enzyme-like activity of cobalt-MOF nanosheets for hydrogen peroxide electrochemical sensing

Metal-organic frameworks (MOFs) are receiving increased attention as new functional nanomaterials for the development of electrochemical sensors. Herein, we develop an electrochemical platform for non-enzymatic hydrogen peroxide detection built with a composite of two-dimensional cobalt MOF nanosheets and Nafion (2D-Co-MOF@Nafion). The feasibility of the 2D-Co-MOF@Nafion composite as active material for high performance hydrogen peroxide sensor was investigated by using cyclic voltammetry and chronoamperometry. Its voltammetric response reveals an efficient charge transport through the MOF composite, and rapid electron exchange between MOF and electrode. Notably, these MOF nanosheets exhibit enzyme-like activity for the non-common catalytic oxidation of hydrogen peroxide, leading to an electrochemical sensor with rapid quantitative detection, outstanding sensitivity, selectivity, stability, and durability at the desirable neutral pH. In particular, for a cobalt metal loading of 1.2 nanomol, the sensor yields amperometric H2O2 detection with characteristic electrocatalytic parameters of imax= 5.7 mA cm−2 and KM = 13 mM. Moreover, linear ranges of up to either 1 mM or 10 mM are achieved, with sensitivities as high as 570 ± 5 A cm−2 mM−1 or 395 ± 10 A cm−2 mM−1 for the low and high concentration ranges, respectively. The particular coordination chemistry of the MOF consisting of a regular arrangement of multiple Co(II) redox metal sites connected by appropriate organic ligands can provide inherent enzyme-mimicking properties, thereby explaining the higher oxidase-like activity of the present MOF. This work raises the new idea of using two-dimensional cobalt-based MOFs as active nanozymes, offering exciting opportunities in the design of non-enzymatic electrochemical sensing devices. [Display omitted] •2D-Co-MOF nanosheets display “oxidase” activity for the non-common catalytic oxidation of hydrogen peroxide.•The current electrochemical sensor exhibits outstanding sensitivity, selectivity, stability, and durability at neutral pH.•The calibration curves follow a Michaelis -Menten dependence.•The particular coordination chemistry of the MOF is envisaged to play a key role.