Unary Au Nanocrystal with Prestored Electrons and Intrinsic Low Hole-Injected Potential for Low-Triggering Potential Electrochemiluminescence

Screening a novel electrochemiluminescence (ECL) system and lowering the ECL triggering potential are essential to ECL evolution. Herein, the near-infrared (NIR) ECL system with low-triggering potential ECL was constructed with weakly reductive <i>tert</i>-butylamine borane as coreactant and mercaptosuccinic acid/citrate (MSA/Cit)-capped Au (MSA/Cit@AuNCs) as luminophores. Toxic-element-free and dual-ligand MSA/Cit@AuNCs were prepared via ligand exchange and utilized as a model for developing unary metal NCs-based luminophores with more enhanced ECL performance than monoligand Au nanocrystals (AuNCs), which exhibited a two hole-injected process at around 0.48 and 0.80 V, respectively. Beneficial to the intrinsic low hole-injected potential of AuNCs, MSA/Cit@AuNCs exhibited similar low-triggering ECL potential at around 0.57 V with the participation of series coreactants or not, originating from the recombination of an internal prestored electron within the conduction band (CB) and electroinjected holes at around 0.25 V. Furthermore, the enhanced low-triggering potential around 0.57 V and NIR ECL around 835 nm of MSA/Cit@AuNCs was eventually obtained with the reductive <i>tert</i>-butylamine borane or N₂H₄·H₂O containing a -C-N single-bond structure merely as coreactant. The low-triggering potential ECL of MSA/Cit@AuNCs/<i>tert</i>-butylamine borane system at 0.57 V can be harnessed to selectively determine a carcinoembryonic antigen (CEA) with one linear range spanning from 2 to 20000 fg/mL and a limit of detection of 0.33 fg/mL (S/N = 3). This study will contribute to a more comprehensive understanding of the ECL mechanism in terms of both regulating NCs and selecting coreactants.