Narducci Riccardo, Sgreccia Emanuela, Montella Alessio Vincenzo, Ercolani Gianfranco, Kaciulis Saulius, Syahputra Suanto, Bloch Emily, Pasquini Luca, Knauth Philippe, Di Vona Maria Luisa
Tor Vergata University of Rome, Department Industrial Engineering and International Laboratory-Ionomer Materials for Energy, 00133 Roma, Italy.
Chemistry Department, Tor Vergata University of Rome, Via della Ricerca Scientifica, 00133 Roma, Italy.
Molecules. 2025 Mar 10;30(6):1230. doi: 10.3390/molecules30061230.
Anion-conducting organic-inorganic polymers (OIPs), constructed using metal-organic framework (MOF)-like structures with non-toxic, non-rare catalytic metals (Fe, Zr), 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/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.
已经开发出了一种阴离子传导性有机-无机聚合物（OIPs），它采用具有无毒、非稀有催化金属（铁、锆）的类金属有机框架（MOF）结构构建而成。类MOF结构的引入赋予了聚合物孔隙率，使其被归类为多孔有机聚合物（POPs）。催化活性、离子传导性和孔隙率之间的结合使该材料能够作为单组分催化电极发挥作用。由于整个表面积都有助于电催化，而不是局限于三相边界，因此有望具有高催化活性。合成过程包括将一个合成子锚定到一种商业聚合物上，组装有机金属部分，并使用季铵（QA）基团进行功能化。通过核磁共振（NMR）、傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）、BET表面积（约200 m²/g）和热重分析（TGA）对两种杂化材料Zr-POP-QA和Fe-POP-QA进行了全面表征。所得电极表现出高电化学活性表面积和对氧还原反应（ORR）的高效率，氧还原反应是能量存储和转换技术中的一个关键过程。该性能的特征在于4电子还原途径、高起始电位（相对于可逆氢电极约为0.9 V）和低塔菲尔斜率（约0.06 V）。我们将这种效率归因于高活性表面积，这是由催化过渡金属离子（锆或铁）和离子传导基团同时存在所导致的。
