NiCo‐LDH Hollow Nanocage Oxygen Evolution Reaction Promotes Luminol Electrochemiluminescence

Abstract Conventional luminol co‐reactant electrochemiluminescence (ECL) systems suffer from low stability and accuracy due to factors such as the ease of decomposition of hydrogen peroxide and inefficient generation of reactive oxygen species (ROS) from dissolved oxygen. Inspired by the luminol ECL mechanism mediated by oxygen evolution reaction (OER), the nickel‐cobalt layered double hydroxide (NiCo‐LDH) hollow nanocages with hollow structure and defect state are used as co‐reaction promoters to enhance the ECL emission from the luminol‐H 2 O system. Thanks to the hollow structure and defect state, NiCo‐LDH hollow nanocages show excellent OER catalytic activity, which can stabilize and efficiently produce ROS and enhance the ECL emission. Additionally, mechanistic exploration suggests that the ROS involved in the co‐reaction of the luminol‐H 2 O system are derived from the OER reaction process, and there is a positive correlation between ECL intensity and the OER catalytic activity of the co‐reaction promoter. The selection of catalysts with excellent OER catalytic activity is a key factor in improving ECL emission. Finally, a dual‐mode immunosensor is constructed for the detection and analysis of alpha‐fetoprotein (AFP) based on the promoting effect of NiCo‐LDH hollow nanocages on the luminol‐H 2 O ECL system.