MnCo2O4 Spinel Nanorods for Highly Sensitive Electrochemical Detection of Nitrite

Inorg Chem. 2024 May 27;63(21):9941-9952. doi: 10.1021/acs.inorgchem.4c01012. Epub 2024 May 13.

Abstract

The rational design of nitrite sensors has attracted significant research interest due to their widespread use and the associated risks of methemoglobinemia and carcinogenicity. The undisclosed nitrite-sensing performance of the spinel cobaltite MnCo2O4 (MCO) prepared by an oxalate-assisted coprecipitation method is reported in this study. Spectroscopy and microscopy investigations revealed the formation of uniform MCO nanorods with a high aspect ratio. The electrocatalytic nitrite oxidation at the MCO-coated glassy carbon electrode (MCO/GCE) indicated the promising performance of the synthesized material for nitrite sensing. MCO/GCE detects nitrite in a concentration range of 5 μM to 3 mM and has a limit of detection of 0.95 μM with a higher sensitivity of 857 μA mM-1 cm-2 in a response time of 4 s. In MCO, the mixed-valence states of Co2+/Co3+ confer a high electrical conductivity, and higher valent redox couples of Mn and Co impart remarkable electrocatalytic activity toward nitrite oxidation. MCO spinel undergoes facile and ultrafast faradaic reactions to mediate nitrite oxidation. Additionally, the mesopores of MCO nanorods facilitate the rapid diffusion of electrolyte and nitrite ions. Employing the electrode in sensing nitrite in milk, lake, and tap water samples further validates its potential application in real-life testing. MCO spinel nanorods showcase promising scope for utilization in the electrochemical sensing of nitrite and inspire further exploration of transition-metal oxide-based mixed-spinel materials.