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The mechanism of alcohol oxidation by surface-bound oxoammonium (yellow) is an EC mechanism described by the MichaelisMenten model, with k cat and K M accessible from operando FEEPR through the quantitative detection of the key STEMPO catalytic intermediate. k s (also obtainable from electrochemistry alone) is slow, and the exact value is dependent on the electrode and experimental conditions, leading to n app < 1 (Extended Data Fig. 7). The [CatalystSubstrate] = [TEMPO + RCH 2 OH] adduct formation is characterized by the MichaelisMenten constant K M . Regeneration of the STEMPO catalyst in the steps following the ratedetermining step ( k cat ) occurs via PCET and/or comproportionation (main text and equations ( 1 ) to ( 6 )). Rate constants and K M are given for the substrate MBA at pH 8.0 (Extended Data Figs. 8 and 9 present values for glycerol at pH 8.0 and MBA at pH 7.3, respectively).

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