Metal–Organic Framework-Derived High-Entropy Oxides as Coreaction Accelerators for an Efficient Luminol/Dissolved Oxygen Electrochemiluminescence System for Ultrasensitive Mercury Detection

Abstract

The development of luminol-dissolved O₂ (luminol-DO) electrochemiluminescence (ECL) systems is crucial for real-world applications. Despite its stability and low biotoxicity, luminol-DO ECL systems struggle with low ECL performance due to their low reactivity. Investigating new materials like coreactant accelerators increases reactive oxygen species (ROS) formation and enhances luminol-DO ECL intensity. Motivated by the ROS-mediated ECL process, for the first time, we designed oxygen vacancy (O_V)-rich high-entropy oxides (HEO) with five metal components [(FeCoNiCuZn)O] derived from metal-organic frameworks (MOFs) as coreaction accelerators to establish efficient luminol-DO ECL systems. High entropy (HE) MOFs were annealed at four different temperatures (600, 700, 800, and 900 °C). Indeed, the HE MOFs annealed at 800 °C (HEO-800) showed a 120-fold stronger ECL intensity compared to the bare glassy carbon electrode in the luminol-DO ECL system. The enhanced ECL performance can be attributed to the porous structure, unique morphology, heterostructures, high-density active sites, rich O_V, unsaturated metals, and synergistic impact, which act as catalysts to accelerate the conversion of DO to ROS. The developed HEO-800-based luminol-DO ECL system can be effectively used for the high-sensitivity detection of mercury ions (Hg²⁺). The system detected Hg²⁺ over a wide concentration range from 0.1 nM to 100 μM, with a detection limit of 0.02 nM. The sensing mechanism relied on high-affinity metallophilic Hg²⁺-HEO-800 interactions, effectively quenching the ECL intensity of the luminol-DO/HEO-800 ECL system. The ECL sensing platform, developed without H₂O₂, offers a novel method for detecting substances, demonstrating significant potential for clinical diagnosis and biomarker analysis.