Identification and quantification of electron-generated atomic hydrogen through in-situ electron spin resonance and density functional theory

Abstract

Electro-generated atomic hydrogen (H*) plays a crucial role in the electrochemical reduction process, serving as the key species that mediates the electrocatalytic hydrogenation reduction of stubborn contaminants in wastewater treatment. However, precisely identifying and quantifying transient atomic H* presents a significant challenge due to its limited lifespan and its existence solely within the boundary layer at the electrode/solution interface. Herein, we developed the electrodeposition of palladium nanoparticles onto carbon cloth and assessed its effectiveness as a cathode for generating and stabilizing atomic H*. The environmental application of atomic H* was validated through the dechlorination of 2, 4-dichlorophenol wastewater and the reduction of antimonite wastewater. Additionally, the identification of atomic H* was verified by electrochemical measurements, high-resolution mass spectra, and density functional theory. Moreover, introducing an excess of a spin trapping agent (5,5-dimethyl-1-pyrroline-N-oxide) and fast in-situ spin trapping facilitated creating favorable conditions for efficient trapping of atomic H* and subsequent electron spin resonance (ESR) spectroscopy quantification analysis. Subsequently, the quantification of atomic H* was achieved by double integration of the ESR signal of spin adduct and comparison with the external standard agent (4-hydroxy-2,2,6,6-tetramethyl-1-piperidine 1-oxyl). This study introduces a novel method for in-situ spin trapping and quantification of atomic H*, facilitating the advancement of electrochemical reduction technology and its application in wastewater treatment.