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We discovered using SECM of the electro-reduction of CO2 on a Au substrate in CO2-saturated KHCO3 solutions that (i) formate comes solely from the direct reduction of bicarbonate; and (ii) CO forms only from CO2 reduction (under low pH conditions) and at higher applied potentials. The results point to the possibility of the selective reduction of CO2 to the formate product.
Narayanaru et al. (Wed,) studied this question.