In Situ Generated CO Enables High-Current CO 2 Reduction to Methanol in a Molecular Catalyst Layer.

Molecular catalysts such as cobalt phthalocyanine (CoPc) exhibit remarkable electrochemical activity in methanol production from CO 2 or CO, but fast conversion with a high current density is still yet to be realized. While adopting flow cells with gas diffusion electrodes is a common approach to enhanced reaction rates, the current scientific and engineering knowledge primarily centers on metal particle-based catalysts like Cu. This focus overlooks the emerging heterogenized molecular catalysts with distinct physical and chemical properties. In this work, we observe that the partial current density of CO reduction to methanol catalyzed by tetraamine-substituted CoPc (CoPc-NH 2 ) supported on carbon nanotubes (CNTs) remains below 30 mA cm -2 , even with systematic optimization of structural and operational parameters of the flow cell. A comparative analysis with a Cu metal catalyst reveals that the porous and electrolyte-philic nature of CoPc-NH 2 /CNT leaves a large fraction of active sites deprived of CO under reaction conditions. To address this microenvironmental challenge, we directly use CO 2 as the reactant, leveraging its faster diffusion rate in water compared to CO. Effective CO 2 reduction generates CO in situ to feed the catalytic sites, achieving an unprecedently high partial current density for methanol of 129 mA cm -2 . This research underscores the necessity for new insights and approaches in the development of molecular catalyst-based electrodes.