Understanding the factors governing the water oxidation reaction pathway of mononuclear and binuclear cobalt phthalocyanine catalysts.

ABSTRACT

The rational design of efficient catalysts for electrochemical water oxidation highly depends on the understanding of reaction pathways, which still remains a challenge. Herein, mononuclear and binuclear cobalt phthalocyanine (mono-CoPc and bi-CoPc) with a well-defined molecular structure are selected as model electrocatalysts to study the water oxidation mechanism. We found that bi-CoPc on a carbon support (bi-CoPc/carbon) shows an overpotential of 357 mV at 10 mA cm-2, much lower than that of mono-CoPc/carbon (>450 mV). Kinetic analysis reveals that the rate-determining step (RDS) of the oxygen evolution reaction (OER) over both electrocatalysts is a nucleophilic attack process involving a hydroxy anion (OH-). However, the substrate nucleophilically attacked by OH- for bi-CoPc is the phthalocyanine cation-radical species (CoII-Pc-Pc˙+-CoII-OH) that is formed from the oxidation of the phthalocyanine ring, while cobalt oxidized species (Pc-CoIII-OH) is involved in mono-CoPc as evidenced by the operando UV-vis spectroelectrochemistry technique. DFT calculations show that the reaction barrier for the nucleophilic attack of OH- on CoII-Pc-Pc˙+-CoII-OH is 1.67 eV, lower than that of mono-CoPc with Pc-CoIII-OH nucleophilically attacked by OH- (1.78 eV). The good agreement between the experimental and theoretical results suggests that bi-CoPc can effectively stabilize the accumulated oxidative charges in the phthalocyanine ring, and is thus bestowed with a higher OER performance.