Co₃O₄/NiCo₂O₄ heterojunction as oxygen evolution reaction catalyst for efficient luminol anode electrochemiluminescence

Luminol has garnered significant attention from analysts as one of the most effective and commonly used electrochemiluminescence (ECL) reagents. However, the efficient luminescence of luminol anode is limited by the excitation of various reactive oxygen species (ROS). Typically, ROS are generated through co-reactive reagents and dissolved oxygen. Unfortunately, the former suffers from two drawbacks, namely biotoxicity and instability, while the latter cannot offer sufficient oxygen due to its limited solubility in aqueous solutions. Consequently, a low decomposition rate is usually obtained, leading to insufficient ROS. Therefore, there is an urgent need to develop efficient luminol anode systems. This study focuses on the use of zeolitic imidazolate framework-67 (ZIF-67) as a template, employing a controlled chemical etching method to create a ZIF-67/Ni-Co-layered double hydroxide (LDH). The intermediate composite is then annealed in air, resulting in the formation of a Co₃O₄/NiCo₂O₄ double-shelled nanobox (DSNB) heterostructure. Due to its structural advantages, the DSNB exhibits excellent electrocatalytic performance in the oxygen evolution reaction (OER). Furthermore, it was found that both the intermediates and products of OER can directly participate in the luminol chemiluminescence process, ultimately resulting in a 700-fold increase in the electrochemiluminescence (ECL) signal compared to an equal molar concentration of luminol solution. This work not only establishes the OER-mediated ECL system but also deepens the understanding of the relationship between ROS and luminol, providing a new pathway to study the luminol anodic ECL luminescence system.