Donor-π-acceptor cobalt porphyrins for electrocatalytic oxygen reduction reaction in acidic medium.

Donor-π bridge-acceptor (D-π-A) design principle has been widely employed to build functionalized materials with excellent optical properties, whereas its feasibility in electrocatalytic reactions is seldom investigated. We demonstrate the primary study of D-π-A rule in constructing electrocatalysts for oxygen reduction reaction (ORR) purpose by rationally designing three cobalt porphyrins EGZ1–3 with 9H-carbazole, triphenylamine and N,N-diphenyl-[1,1′-biphenyl]-4-amine as the donor substituents, respectively, cobalt porphyrin as the π bridge, and cyanoacrylic acid as the acceptor unit. The electronic properties of the molecules are calculated using the density functional theory and the composite catalysts EGZs/C are characterized by a series of spectroscopic approaches. The electrochemical measurements show that EGZ3/C attains a more positive reduction potential and a greater response current density than EGZ1/C and EGZ2/C, which is possibly due to the optimized electronic structure and the substituent effect. The electron transfer number as well as hydrogen peroxide generation yield values suggest slightly better selectivity of EGZ3/C and EGZ2/C than those of EGZ1/C (i.e., ~ 2.9, ~ 2.9 vs. ~ 2.7 and ~ 54%, ~ 53% vs. ~ 62%, respectively) towards full oxygen reduction. Our result reveals the feasibility of the D-π-A design rule and the importance of molecular electronic state and the substituent feature in constructing ORR electrocatalysts. [Display omitted] • Three donor-π-acceptor cobalt porphyrins are synthesized. • The electronic structure of porphyrins is calculated by density functional theory. • Porphyrin-carbon black composites are studied in oxygen reduction reaction. • The electrocatalyst EGZ3/C attains the best ORR performance. • Both electronic structure and substituents affect the electrocatalytic activity. [ABSTRACT FROM AUTHOR]