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Why the cation matters so much is unsettled.","posed_since":"","precise":"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.","problem_ref":"286fc96215ae2713eafcdda3b71aa7484b9baf085e8c3e22ddc419707ae185a1","references":"","settled_by":"Spectroscopic detection of cation-adsorbate interactions combined with explicit-cation constant-potential simulations that reproduce the measured trends.","status_note":"","title":"Origin of alkali cation effects in electrochemical $\\mathrm{CO_2}$ 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