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 selec-tivity 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 pre-cipitation-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.s4Ru0.46 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 fa-vorable,thus realizing the near 100％EG selectivity.This work provides a new understanding for the high-selectivity electrosynthesis of high-value-added oxides.
NETL
NSTL
万方数据
