Valence-State-Engineered Electrochemiluminescence from Au Nanoclusters

To determine the intrinsic effects of body elements on the electrochemiluminescence (ECL) of metal nanoclusters (NCs), herein, a valence-state engineering strategy is developed to adjust the NCs' ECL with bovine serum albumin (BSA)-stabilized AuNCs as a model, in which engineering the valence state of the Au body element, i.e., Au(0) and Au(I), is performed via successively reducing the precursor AuCl4– to Au(I) and Au(0) with BSA. The obtained BSA-AuNCs/N2H4 system leads to three anodic ECL processes at 0.37 (ECL-1), 0.85 (ECL-2), and 1.45 V (ECL-3). ECL-1 is generated from the BSA-Au(0) section of BSA-AuNCs in a surface-defect-involved route and is much stronger and red-shifted compared to ECL-2 and ECL-3, which are generated from the BSA-Au(I) section of BSA-AuNCs in the band-gap-engineered route. Each of the anodic ECL processes can be selectively generated and/or suppressed via adjusting the Au(I)/Au(0) ratio of BSA-AuNCs, tunable ECL generation route, and triggering potential, and the emission intensity and waveband of metal NCs are conveniently achieved in body-element-involved valence-state engineering.