The Regulation of O2 Spin State and Direct Oxidation of CO at Room Temperature Using Triboelectric Plasma by Harvesting Mechanical Energy.

Abstract

Oxidation reactions play a critical role in processes involving energy utilization, chemical conversion, and pollutant elimination. However, due to its spin-forbidden nature, the reaction of molecular dioxygen (O2) with a substrate is difficult under mild conditions. Herein, we describe a system that activates O2 via the direct modulation of its spin state by mechanical energy-induced triboelectric corona plasma, enabling the CO oxidation reaction under normal temperature and pressure. Under optimized reaction conditions, the activity was 7.2 μmol h−1, and the energy consumption per mole CO was 4.2 MJ. The results of kinetic isotope effect, colorimetry, and density functional theory calculation studies demonstrated that electrons generated in the triboelectric plasma were directly injected into the antibonding orbital of O2 to form highly reactive negative ions O2−, which effectively promoted the rate-limiting step of O2 dissociation. The barrier of the reaction of O2− ions and CO molecular was 3.4 eV lower than that of O2 and CO molecular. This work provides an effective strategy for using renewable and green mechanical energy to realize spin-forbidden reactions of small molecules.