Manipulating the electronic state of ruthenium to boost highly selective electrooxidation of ethylene to ethylene glycol in acid

Electrochemical oxidation of ethylene is a novel approach to manufacture valuable ethylene glycol (EG), which is an important raw material in organic chemical industry. However, the poor EG selectivity and expensive additional purification costs hinder this method from being practically used. In this work, ultrafine iridium-ruthenium (IrRu) alloy nanoparticles are synthesized through the precipitation-reduction method and their electrocatalytic performance towards ethylene oxidation to EG has been comprehensively studied. Near 100% selectivity is achieved with a EG yield of 60.62 mmol gRu−1 h−1 at 1.475 V on an optimal Ir0.54Ru0.46 catalyst. OH-stripping, in-situ electrochemical attenuated total internal reflectance Fourier transform infrared spectra and DFT calculation reveal that the introduction of Ir can modulate the electronic structure and d-band center so as to endow the Ru with the mild binding energy with the key intermediates and small energy barrier for *HOCH2CH2OH desorption, thereby enhancing the EG generation. Simultaneously, the high energy barrier for the overoxidation of the *CH2CH2OH renders the EG formation thermodynamically favorable, thus realizing the near 100% EG selectivity. This work provides a new understanding for the high-selectivity electrosynthesis of high-value-added oxides.