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

由共价连接到阴离子交换离子交换聚合物的金属有机框架制成的单组分催化电极

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Abstract

Anion-conducting organic-inorganic polymers (OIPs), constructed using metal-organic framework (MOF)-like structures with non-toxic, non-rare catalytic metals (Fe(3+), Zr(4+)), 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 m(2)/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.

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