Developing high performance electrocatalysts to improve the sluggish kinetics of oxygen reduction reaction (ORR) at the cathode is essential in expanding fuel cell applications. Metal organic frameworks (MOFs), given their high surface area, tunable pore size, and diverse metal choices, are promising candidates to catalyze such a reaction. Herein, we report a family of nine 2D-phthalocyanine MOF-based catalysts for alkaline ORR, where M = Co, Ni, Cu. Structurally, these bimetallic materials have two distinct metal sites, where M1 is a phthalocyanine moiety and M2 is a node, existing as M-N4 moiety. X-ray Diffraction (XRD) shows that all as-prepared MOFs have similar structures and inter-layer spacing. X-ray Photoelectron Spectroscopy (XPS) shows slight shifts in binding energy when the same element is placed in a M1 or M2 site, which indicates that the M1 and M2 sites are chemically distinct.

Through cyclic voltammetry we evaluate the role of the metal sites for ORR activity and selectivity in 0.1 M KOH. All materials are active for alkaline ORR, while Ni (M1) – Co (M2) has the best overall kinetic activity performance of - 5 mA cm^-2 at 0.7 V vs. RHE. Cu – Cu, on the other hand, is the least active combination under the same testing conditions. Within composition series where M2 = Co, the activity trend for M1 is Ni > Cu ~ Co. From a 2-electron selectivity perspective, M1 = Ni > Cu > Co. From these general trends we hypothesize that Co M2 and Ni M1 sites are essential in promoting 4- and 2-electron selectively, respectively. On average we find a nominal ORR performance trend where M2 = Co > Cu > Ni. Interestingly, we note that the M1 identity also plays a non-linear role in activity and selectivity modulation. Though we identify one of the metal sites (M1 or M2) as the dominating site for activity and/or selectivity, the other site also contributes to the total performance. The density functional theory (DFT) calculation supports our experimental results and finds out that Ni as M1 is highly selective for H₂O₂ formation whereas Co as M2 shows excellent activity for ORR. Our predicted volcano plot shows that MOF with Ni – Co and Cu – Co combinations at Co active site offering lowest ORR overpotential among all other combinations, which is also in good agreement with experimental findings.

By evaluating different metal sites performance through electrochemical testing, we can better understand the active species in the MOF catalytic system. By pairing theory with experiment, we gain active site insight to design new specific enhanced active motifs. We believe that these performance trends can assist in better designing efficient MOF-based ORR catalysts that can lead to advances in clean energy technology for sustainable development.