Ultrasensitive detection of Hg(II) by small-sized Mn3O4 loaded on g-C3N4 nanosheets: Heterojunction facilitates electron transfer and Mn(II)/Mn(III)/Mn(IV) cycle

Transition metal oxides are widely used in electrochemical detection because of the promotion of redox of heavy metal ions (HMIs) by valence change behavior. However, it is challenging to favorably promote the valence change to achieve the improvement of detection sensitivity. Herein, a Mn3O4/g-C3N4 composite (named as MO-CN) with small-sized of Mn3O4 and high proportion of Mn(II) and Mn(III) was prepared, which reveals an excellent performance on detecting mercury ion (Hg(II)). It is discovered that Mn3O4 becomes small in size and well disperses on g-C3N4, which solves the adverse effect of agglomeration and also lead to a good conductivity. And g-C3N4 can provide more adsorption sites to enhance the adsorption on Hg(II). Heterojunction is proved to form in MO-CN and thus accelerates electrons to flow from g-C3N4 to Mn3O4. This results in transforming Mn(IV) to Mn(II) and Mn(III) in Mn3O4, thereby promoting the cycle of Mn(II)/Mn(III)/Mn(IV) and furthermore facilitating the redox of Hg(II). Simultaneously, the obtained sensitivity (473.43 μA μM-1 cm-2) and limit of detection (LOD, 0.003 μM) are as expected. The nanocomposites and heterojunction based on transition metal oxide and 2D nanomaterials is promising to boost the detection of HMIs.