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Studying the interactions between CO2 sorbents and electrocatalysts for the electrochemical CO2 reduction reaction (e-CO2RR) can offer viable strategies to advance the development of the Reactive Capture of CO2 (RCC). In this report we studied the effect of amines on the performance of the [Co(PDI-Py)] catalyst for the e-CO2RR. The presence of amines shifts the onset potential for the e-CO2RR more positive and increases the catalytic activity while maintaining the high Faradaic efficiency (≥90%) for CO production. [ABSTRACT FROM AUTHOR]

The electrocatalytic CO2 reduction reaction (CO2RR) is a promising strategy for converting CO2 to fuels and value-added chemicals using renewable energy sources. Molecular electrocatalysts show promise for the selective conversion of CO2 to single products with catalytic activity that can be tuned through synthetic structure modifications. However, for the CO2RR by traditional molecular catalysts, beneficial decreases in overpotentials are usually correlated with detrimental decreases in catalytic activity. This correlation is sometimes referred to as a "molecular scaling relationship". Overcoming this inverse correlation between activity and effective overpotential remains a challenge when designing new, efficient molecular catalyst systems. In this perspective, we discuss some of the concepts that give rise to the molecular scaling relationships in the CO2RR by molecular catalysts. We then provide an overview of some reported strategies from the last decade for breaking these scaling relationships. We end by discussing strategies and progress in our own research designing efficient molecular catalysts with redox-active ligands that show high activity at low effective overpotentials for the CO2RR. [ABSTRACT FROM AUTHOR]

Vanadium-doped cobalt oxide materials have emerged as a promising class of catalysts for the oxygen evolution reaction. Previous studies suggest vanadium doping in crystalline Co spinel materials tunes the electronic structure and stabilizes surface intermediates. We report a CoV2O4 material that shows good activity for the oxygen evolution reaction. However, postmortem characterization of the catalyst material shows dissolution of vanadium resulting in an amorphous CoOx material, suggesting that this vanadium-free material, and not CoV2O4, is the active catalyst. This study highlights the importance of postmortem characterization prior to mechanistic and computational analysis for this class of materials. [ABSTRACT FROM AUTHOR]

Encapsulating cobalt phthalocyanine (CoPc) within the coordinating polymer poly-4-vinylpyridine (P4VP) results in a catalyst–polymer composite (CoPc–P4VP) that selectively reduces CO2 to CO at fast rates at low overpotential. In previous studies, we postulated that the enhanced selectively for CO over H2 production within CoPc–P4VP compared to the parent CoPc complex is due to a combination of primary, secondary, and outer-coordination sphere effects imbued by the encapsulating polymer. In this work, we perform in situ electrochemical X-ray absorption spectroscopy measurements to study the oxidation state and coordination environment of Co as a function of applied potential for CoPc, CoPc–P4VP, and CoPc with an axially-coordinated py, CoPc(py). Using in situ X-ray absorption near edge structure (XANES) we provide experimental support for our previous hypothesis that Co changes from a 4-coordinate square-planar geometry in CoPc to a mostly 5-coordinate species in CoPc(py) and CoPc–P4VP. The coordination environment of CoPc–P4VP is potential-independent but pH-dependent, suggesting that the axial coordination of pyridyl groups in P4VP to CoPc is modulated by the protonation of the polymer. Finally, we show that at low potential the oxidation state of Co in the 4-coordinate CoPc is different from that in the 5-coordinate CoPc(py), suggesting that the primary coordination sphere modulates the site of reduction (metal-centered vs. ligand centered) under catalytically-relevant conditions. [ABSTRACT FROM AUTHOR]

A Co complex with a redox-active bis(pyridylmonoimine) ligand has been prepared and shows catalytic activity for electrochemical CO2 reduction in acetonitrile. Addition of a proton source such as water or trifluoroethanol dramatically improves the activity and stability of the molecular catalyst. The Co complex reduces CO2 to CO selectively at −1.95 V vs. Fc+/0 in the presence of high concentrations of water. The activity of the Co complex for CO2 reduction compares favorably to other molecular Co-based catalysts in acetonitrile solutions. [ABSTRACT FROM AUTHOR]