The protonic ceramic electrochemical cell (PCEC) is an emerging and attractive technology that converts energy between power and hydrogen using solid oxide proton conductors at intermediate temperatures. To achieve efficient electrochemical hydrogen and power production with stable operation, highly robust and durable electrodes are urgently desired to facilitate water oxidation and oxygen reduction reactions, which are the critical steps for both electrolysis and fuel cell operation, especially at reduced temperatures. In this study, a triple conducting oxide of PrNi_0.5Co_0.5O_3-δ perovskite is developed as an oxygen electrode, presenting superior electrochemical performance at 400~600 °C. More importantly, the self-sustainable and reversible operation is successfully demonstrated by converting the generated hydrogen in electrolysis mode to electricity without any hydrogen addition. The excellent electrocatalytic activity is attributed to the considerable proton conduction, as confirmed by hydrogen permeation experiment, remarkable hydration behavior and computations.

The oversupply of ethane, a major component of natural gas liquids, has stimulated the wide applications of ethylene since the shale gas revolution. However, ethylene production is energy-intensive and represents the most energy-consuming single process in the chemical industry. In this communication, we report, for the first time, a novel low-thermal-budget process for the co-production of ethylene and pure hydrogen using a proton-conducting electrochemical deprotonation cell. At a constant current density of 1 A cm⁻², corresponding to a hydrogen production rate of 0.448 mol cm⁻² per day, and 400 °C, a close to 100% ethylene selectivity was achieved under an electrochemical overpotential of 140 mV. Compared to an industrial ethane steam cracker, the electrochemical deprotonation process can achieve a 65% saving in process energy and reduce the carbon footprint by as much as 72% or even more if renewable electricity and heat are used. If the heating value of produced hydrogen is taken into account, the electrochemical deprotonation process actually has a net gain in processing energy. The electrochemical deprotonation process at reduced temperatures in the present study provides a disruptive approach for petrochemical manufacturing, shifting the paradigm from thermal chemical practice to a clean energy regime.