However, approaches to elucidate local conditions on nanostructured electrodes and optimize their structures require experimental results or parametrized Tafel terms for reactivity as boundary condition. At the atomic scale close to the electrode, the local role of cations in eCO 2 R was directly addressed via ab initio molecular dynamics (AIMD) by explicitly adding cations in the electrolyte. Partially desolvated cations stabilize CO 2 through direct coordination and slow growth AIMD simulations show that inner sphere mechanisms reduce barriers for CO 2 adsorption . Moreover, MD simulations at extended time-scales show that cation coordination affects mostly the polarizable adsorbates (CO 2 -, COOH, COCO) .