One-Component Catalytic Electrodes from Metal–Organic Frameworks Covalently Linked to an Anion Exchange Ionomer

Anion-conducting organic–inorganic polymers (OIPs), constructed using metal–organic framework (MOF)-like structures with non-toxic, non-rare catalytic metals (Fe3+, Zr4+), have been developed. The incorporation of MOF-like structures imparts porosity to the polymers, classifying them as porous organic polymers (POPs). The combination between catalytic activity, ion conduction, and porosity allows the material to act as one-component catalytic electrodes. A high catalytic activity is expected since the entire surface area contributes to electrocatalysis, rather than being restricted to triple-phase boundaries. The synthesis involved anchoring a synthon onto a commercial polymer, assembling organo-metallic moieties, and functionalizing with quaternary ammonium (QA) groups. Two hybrid materials, Zr-POP-QA and Fe-POP-QA, were thoroughly characterized by NMR, FTIR, XPS, BET surface area (≈200 m2/g), and TGA. The resulting electrodes demonstrated a high electrochemically active surface area and a high efficiency for the oxygen reduction reaction (ORR), a critical process for energy storage and conversion technologies. The performance was characterized by a 4-electron reduction pathway, a high onset potential (≈0.9 V vs. RHE), and a low Tafel slope (≈0.06 V). We attribute this efficiency to the high active surface area, which results from the simultaneous presence of catalytic transition metal ions (Zr or Fe) and ion conducting groups.