Electrochemistry
P4VP makes CoPc a selective CO2-to-CO catalyst
Open access · cc by · source: Europe PMC
Axial pyridine plus a polyvinylpyridine film together raise CoPc’s CO2-to-CO rate and faradaic efficiency while suppressing hydrogen evolution.
Key findings
CoPc-P4VP averages 2.0 mA cm–2 with nearly 90% FE_CO, TOF 4.8 s–1, TON 34 000, and CO/H2 = 19:1, versus CoPc at 0.62 mA cm–2, TON 4500, CO/H2 = 0.9:1. Axial pyridine alone gives 68% FE_CO; P2VP alone gives 73% FE_CO but does not raise TOF. Both primary (axial) and outer-sphere polymer effects are required.
Methodology
They drop-cast CoPc on edge-plane graphite, then compared free CoPc, CoPc in P4VP, CoPc(pyridine), CoPc in non-coordinating P2VP, and CoPc(py)-P2VP. CPE at −1.25 V vs SCE in pH ~5 phosphate quantified CO, H2, charge, TON, and TOF.
Limitations
TON/TOF use total deposited Co (1.3×10–9 mol cm–2), so they are lower bounds. No liquid C2 products were detected to ~10 μM. Long-term electrolyzer tests and in situ spectroscopy of the Co–pyridine bond during catalysis are limited.
How this study connects
Role on claims
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Axial pyridine plus a polyvinylpyridine film together raise CoPc’s CO2-to-CO rate and faradaic efficiency while suppressing hydrogen evolution.
Evidence for the claim as stated.
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