Origin of alkali cation effects in electrochemical $\mathrm{CO_2}$ reduction
In plain words
On copper and gold electrodes, $\mathrm{CO_2}$ reduction barely works without metal cations in the solution, and larger cations such as cesium work better than lithium. Why the cation matters so much is unsettled.
Precise statement
For $\mathrm{CO_2}$ reduction on Cu and Au electrodes in aqueous MHCO3 ($M = \mathrm{Li}, \mathrm{Na}, \mathrm{K}, \mathrm{Cs}$), identify the mechanism by which the cation controls the rate of the first $\mathrm{CO_2}$ activation step and the product selectivity: interfacial field stabilization of adsorbed $\mathrm{CO2}-$, direct coordination, local buffering of pH, or modification of the hydrogen-bond network. An answer is a model predicting partial current densities versus cation identity and concentration.
What would settle it
Spectroscopic detection of cation-adsorbate interactions combined with explicit-cation constant-potential simulations that reproduce the measured trends.
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