Simultaneous Anodic and Cathodic Formate Production in a Paired Electrolyzer by CO2 Reduction and Glycerol Oxidation

Electrochemical CO₂ conversion is a key technology to promote the production of carbon-containing molecules, alongside reducing CO₂ emissions leading to a closed carbon cycle economy. Over the past decade, the interest to develop selective and active electrochemical devices for electrochemical CO₂ reduction emerged. However, most reports employ oxygen evolution reaction as an anodic half-cell reaction causing the system to suffer from sluggish kinetics with no production of value-added chemicals. Therefore, this study reports a conceptualized paired electrolyzer for simultaneous anodic and cathodic formate production at high currents. To achieve this, CO₂ reduction was coupled with glycerol oxidation: a BiOBr-modified gas-diffusion cathode and a Ni_xB on Ni foam anode keep their selectivity for formate in the paired electrolyzer compared to the half-cell measurements. The paired reactor here reaches a combined Faradaic efficiency for formate of 141 % (45 % anode and 96 % cathode) at a current density of 200 mA cm⁻².