Mitigating Cobalt Phthalocyanine Aggregation in Electrocatalyst Films through Codeposition with an Axially Coordinating Polymer

Abstract Cobalt phthalocyanine (CoPc) is a promising molecular catalyst for aqueous electroreduction of CO₂, but its catalytic activity is limited by aggregation at high loadings. Codeposition of CoPc onto electrode surfaces with the coordinating polymer poly(4‐vinylpyridine) (P4VP) mitigates aggregation in addition to providing other catalytic enhancements. Transmission and diffuse reflectance UV–vis measurements demonstrate that a combination of axial coordination and π‐stacking effects from pyridyl moieties in P4VP serve to disperse cobalt phthalocyanine in deposition solutions and help prevent reaggregation in deposited films. Polymers lacking axial coordination, such as Nafion, are significantly less effective at cobalt phthalocyanine dispersion in both the deposition solution and in the deposited films. SEM images corroborate these findings through particle counts and morphological analysis. Electrochemical measurements show that CoPc codeposited with P4VPonto carbon electrode surfaces reduces CO₂ with higher activity and selectivity compared to the catalyst codeposited with Nafion.