Promising Mercaptobenzoic Acid-Bridged Charge Transfer for Electrochemiluminescence from CuInS₂@ZnS Nanocrystals via Internal Cu⁺/Cu²⁺ Couple Cycling

Abstract

Screening novel electrochemiluminescence (ECL) systems with less inherent interference is strongly anticipated for ECL evolution. Herein, near-infrared ECL (∼730 nm) with an ultralow triggering potential of 0.45 V (vs Ag/AgCl) is achieved under physiological conditions with 4-mercaptobenzoic acid (MBA) and citrate capped CuInS₂@ZnS (CIS@ZnS) nanocrystals (NCs), which is promising for less autofluorescence and electrochemical interference. Cu⁺ species within the CIS@ZnS NCs can be electrochemically oxidized at 0.45 V to form internal Cu²⁺ defects, while the capping agent MBA can bridge a direct charge transfer between the oxidized NCs and the traditional coreactant tripropylamine (TPrA) for weak ECL at 0.45 V. When hydrazine hydrate is adopted as coreactant, CIS@ZnS NCs/hydrazine hydrate exhibits 8k-fold enhanced oxidative-reduction ECL via the internal Cu⁺/Cu²⁺ couple cycling at 0.45 V in comparison to CIS@ZnS NCs/TPrA. This work opens a way to enhance the radiative charge transfer of NCs.