A Phthalocyanine‐Based Layered Two‐Dimensional Conjugated Metal–Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction

Layered two‐dimensional (2D) conjugated metal–organic frameworks (MOFs) represent a family of rising electrocatalysts for the oxygen reduction reaction (ORR), due to the controllable architectures, excellent electrical conductivity, and highly exposed well‐defined molecular active sites. Herein, we report a copper phthalocyanine based 2D conjugated MOF with square‐planar cobalt bis(dihydroxy) complexes (Co‐O₄) as linkages (PcCu‐O₈‐Co) and layer‐stacked structures prepared via solvothermal synthesis. PcCu‐O₈‐Co 2D MOF mixed with carbon nanotubes exhibits excellent electrocatalytic ORR activity (E_1/2=0.83 V vs. RHE, n=3.93, and j_L=5.3 mA cm^?2) in alkaline media, which is the record value among the reported intrinsic MOF electrocatalysts. Supported by in situ Raman spectro‐electrochemistry and theoretical modeling as well as contrast catalytic tests, we identified the cobalt nodes as ORR active sites. Furthermore, when employed as a cathode electrocatalyst for zinc–air batteries, PcCu‐O₈‐Co delivers a maximum power density of 94 mW cm^?2, outperforming the state‐of‐the‐art Pt/C electrocatalysts (78.3 mW cm^?2).