Superior Singlet Oxygen Electrosynthesis via Neighboring Dual Molecular Oxygen Coactivation for Selective Tetracycline Detoxification.

ABSTRACT

Oxygen (O2) electroreduction offers a green approach for singlet oxygen (1O2) synthesis in wastewater contaminants detoxification. However, traditional single O2 activation on single-metal catalytic sites seriously suffers from the kinetically-unfavorable desorption of adsorbed superoxide species (•O2 -*/•OOH*). Here, we demonstrate a novel dual O2 coactivation pathway on shortened Fe1-OV-Ti sites for superior 1O2 electrosynthesis through a rapid disproportionate process between surface-confined •O2 -*/•OOH*. Theoretical calculations combined with in situ electrochemical spectroscopies demonstrated that the shortened distance between Fe single atom and adjacent unsaturated Ti atom facilitates the direct recombination of surface-confined Fe-•OOH and Ti-•OO- to yield 1O2, bypassing the formidable •O2 -*/•OOH* desorption process. Impressively, Fe1-OV-Ti could realize an excellent 1O2 electrosynthesis rate of 54.5 µmol L-1 min-1 with an outstanding 1O2 selectivity of 97.6 % under neutral condition, surpassing that of Fe1-O-Ti (27.1 µmol L-1 min-1, 91.7 %). Using tetracycline (TC) as a model pollutant, the resulting Fe1-OV-Ti electrode achieved nearly 100 % degradation in 120 min at -0.6 V, meanwhile preventing the generation of toxic intermediates. This study provides a new 1O2 electrosynthesis strategy by controlling the distance of adjacent catalytic sites for the coactivation of dual molecular oxygen.