Stable Operation of Paired CO₂ Reduction/Glycerol Oxidation at High Current Density

Despite the considerable efforts made by the community, the high operation cell voltage of CO₂ electrolyzers is still to be decreased to move toward commercialization. This is mostly due to the high energy need of the oxygen evolution reaction (OER), which is the most often used anodic pair for CO₂ reduction. In this study, OER was replaced by the electrocatalytic oxidation of glycerol using carbon-supported Pt nanoparticles as an anode catalyst. In parallel, the reduction of CO₂ to CO was performed at the Ag cathode catalyst using a membraneless microfluidic flow electrolyzer cell. Several parameters were optimized, starting from the catalyst layer composition (ionomer quality and quantity), through operating conditions (glycerol concentration, applied electrolyte flow rate, etc.), to the applied electrochemical protocol. By identifying the optimal conditions, a 75-85% Faradaic efficiency (FE) toward glycerol oxidation products (oxalate, glycerate, tartronate, lactate, glycolate, and formate) was achieved at 200 mA cm total current density while the cathodic CO formation proceeded with close to 100% FE. With static protocols (potentio- or galvanostatic), a rapid loss of glycerol oxidation activity was observed during the long-term measurements. The anode catalyst was reactivated by applying a dynamic potential step protocol. This allowed the periodic reduction, hence, refreshing of Pt, ensuring stable, continuous operation for 5 h.