Voltammetric Detection of Singlet Oxygen Enabled by Nanogap Scanning Electrochemical Microscopy

Despite the significance of singlet oxygen (1O2) in several biological, chemical, and energy storage systems, its voltammetric reduction at an electrode remains unreported. We address this issue using nanogap scanning electrochemical microscopy (SECM) in substrate-generation/tip-collection mode. Our investigation reveals a reductive process on the SECM tip at −1.0 V (vs Fc+/Fc) during the breakdown of the Li2CO3 substrate in deuterated acetonitrile. Notably, this value is approximately 0.9 V more positive than the reduction potential of triplet oxygen (3O2), consistent with thermodynamic estimates for the energy of the formation of 1O2. This finding holds significant implications for understanding the reaction mechanisms involving 1O2 in nonaqueous media.