Advancements in Mercury-Free Electrochemical Sensors for Iron Detection: A Decade of Progress in Electrode Materials and Modifications

Efforts to quantify iron ion concentrations across fields such as environmental, chemical, health, and food sciences have intensified over the past decade, which drives advancements in analytical methods, particularly electrochemical sensors known for their simplicity, portability, and reliability. The development of electrochemical methods using non-mercury electrodes is increasing as alternatives to environmentally unsafe mercury-based electrodes. However, detecting iron species such as Fe(II) and Fe(III) remains challenging due to their distinct chemical properties, continuous oxidation-state interconversion, presence of interfering species, and complex behavior in diverse environments and matrixes. Selective trace detection demands careful optimization of electrochemical methods, including proper electrode materials selection, electrode surface modifications, operating conditions, and sample pretreatments. This review critically evaluates advancements over the past decade in mercury-free electrode materials and surface modification strategies for iron detection. Strategies include incorporating a variety of nanomaterials, composites, conducting polymers, membranes, and iron-selective ligands to improve sensitivity, selectivity, and performance. Despite advancements, achieving ultra-low detection limits in real-world samples with minimal interference remains challenging and emphasizes the need for enhanced sample pretreatment. This review identifies challenges, knowledge gaps, and future directions and paves the way for advanced iron electrochemical sensors for environmental monitoring, health diagnostics, and analytical precision.