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Experiments were carried out in a glovebox as described in references 14 and 18. The PGE electrode (0.03 cm2) was sanded with P800 emery paper then CODH (0.5 μL, 0.6 mM) was applied. The pH was measured with a pH probe placed in the electrochemical cell. Experiments under 100% CO2 (Figure 2) and KM experiments (for CO and CO2) were conducted at pH 6, 200 mM MES, since the pH of this solution remained stable upon CO2 saturation. Other experiments employed mixed buffer, as in ref 18. Gas flow controllers were used to give accurate mixtures of CO and CO2. The electrode was rotated rapidly (4000 rpm) to supply substrate at the electrode and remove product. A saturated calomel electrode (SCE) was used as reference. E(SHE, ESCE, 0.242 V at 25°C
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