The electrochemical sensing applications of a series of water-stable 2D metal-organic framework (MOF)-modified screen-printed carbon electrodes (SPCEs) are reported. The MOF materials in this study are [M(bipy)(C4O4)(H2O)2]·3H2O, in which bipy = 4,4'-bipyridine and M = Mn, Fe, Co and Zn. The MOF materials are characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), showing that the MOFs have a layer-by-layer rod structure with a smooth surface. We use the nitrofurazone molecule as a probe to investigate the influence of the metal ions of MOFs on electrochemical sensing ability. Cyclic voltammetry demonstrated that the Mn-MOF electrode of interest delivered stronger signals than that of other electrodes. Through first-principles calculations, we also revealed that the change in the spin polarization of divalent metal ions passing from the free ion state to the MOF environment appeared to be significantly correlated with the enhancement in the peak response current. The theoretical and experimental results consistently indicate that Mn-MOF has the smallest bandgap and good sensitivity among these MOF materials. Accordingly, we proposed a simple model to illustrate this observation and disclosed the importance of the electron configuration of the transition metal constructing the MOF materials used in improving electrochemical sensing applications.
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