Electron-Accelerator-Induced Fast Electron Transfer for Enhancing Electrochemiluminescence of Gold Nanoclusters and...

Herein, the gold nanoclusters/CaFe₂O₄ nanospheres (Au NCs/CaFe₂O₄) heterostructure as a novel electrochemiluminescence (ECL) emitter was developed. Excitingly, Au NCs/CaFe₂O₄ displayed highly efficient and greatly stable ECL based on the newly defined electron-accelerator p-type semiconductor CaFe₂O₄ NS-induced fast electron transfer; it solved one key obstacle of metal NC-based ECL emitters: sluggish through-covalent bond electron transport kinetics-caused inferior ECL performance. Specifically, on account of the energy level matching between emitter Au NCs and electron-accelerator CaFe₂O₄ NSs, the valence band (VB) of the electron-accelerator could provide abundant holes for rapidly transporting the electrogenerated electron from the highest occupied molecular orbital (HOMO) of Au NCs to the electrode, generating massive excited species of Au NCs for strong ECL emission. Notably, Au NCs/CaFe₂O₄ emerged 5.4-fold higher ECL efficiency with 3.5-fold higher electrochemical oxidation current in comparison with pure Au NCs, exhibiting great prospects in extensive lighting installations, ultrasensitive biosensing, and high-resolution ECL imagery. As applications, an ECL bioassay platform was constructed with Au NCs/CaFe₂O₄ as an emitter and U-like structure-fueled catalytic hairpin assembly (U-CHA) as a signal amplifier for fast and trace analysis of aflatoxin B1 (AFB1) with the detection limit (LOD) down to 2.45 fg/mL, which was 3 orders of magnitude higher than that of the previous ECL biosensors with much better stability. This study developed an entirely new avenue for enlarging the ECL performance of metal NCs, and it is a very attractive orientation for directing the reasonable design of prominent metal NC-based ECL emitters and broadening the practical application of metal NCs.