The effects of power ultrasound (24 kHz) on the electrochemical reduction of CO(2) on polycrystalline copper electrodes

The electrochemical CO(2) reduction reaction (CO2RR) on polycrystalline copper (Cu) electrode was performed in a CO(2)-saturated 0.10 M Na(2)CO(3) aqueous solution at 278 K in the absence and presence of low-frequency high-power ultrasound (f = 24 kHz, P(T) ~ 1.23 kW/dm(3)) in a specially and well-characterized sonoelectrochemical reactor. It was found that in the presence of ultrasound, the cathodic current (I(c)) for CO(2) reduction increased significantly when compared to that in the absence of ultrasound (silent conditions). It was observed that ultrasound increased the faradaic efficiency of carbon monoxide (CO), methane (CH(4)) and ethylene (C(2)H(4)) formation and decreased the faradaic efficiency of molecular hydrogen (H(2)). Under ultrasonication, a ca. 40% increase in faradaic efficiency was obtained for methane formation through the CO2RR. In addition, and interestingly, water-soluble CO(2) reduction products such as formic acid and ethanol were found under ultrasonic conditions whereas under silent conditions, these expected electrochemical CO2RR products were absent. It was also found that power ultrasound increases the formation of smaller hydrocarbons through the CO2RR and may initiate new chemical reaction pathways through the sonolytic di-hydrogen splitting yielding other products, and simultaneously reducing the overall molecular hydrogen gas formation.