Immobilization of porphyrin complexes into crystalline metal-organic frameworks (MOFs) enables high exposure of porphyrin active sites for CO electroreduction. Herein, well-dispersed iron-porphyrin-based MOF (PCN-222(Fe)) on carbon-based electrodes revealed optimal turnover frequencies for CO electroreduction to CO at 1 wt.% catalyst loading, beyond which the intrinsic catalyst activity declined due to CO mass transport limitations. In situ Raman suggested that PCN-222(Fe) maintained its structure under electrochemical bias, permitting mechanistic investigations. These revealed a stepwise electron transfer-proton transfer mechanism for CO electroreduction on PCN-222(Fe) electrodes, which followed a shift from a rate-limiting electron transfer to CO mass transfer as the potential increased from -0.6 V to -1.0 V vs. RHE. Our results demonstrate how intrinsic catalytic investigations and in situ spectroscopy are needed to elucidate CO electroreduction mechanisms on PCN-222(Fe) MOFs.
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