双核铁肟硼酸基多孔金属有机聚合物的合成、结构及其电催化析氧性能

采用氯化亚铁、2，6-二甲酰基-4-甲基苯酚二肟（H₃DFMP）和四（4-硼酸基苯基）甲烷（TBPM），通过一步配位作用和硼酸酯化脱水聚合反应，合成了一例含金属的三维多孔有机聚合物（Fe₂-POP）。Fe₂-POP是以双核亚铁配位H₃DFMP的直线单元与TBPM的四面体单元连接而成的具有三维金刚石结构的多孔有机聚合物。对模型化合物的X射线单晶衍射分析验证了双核亚铁配合物单元的结构特征。红外光谱和固体核磁表征证明了Fe₂-POP中C=N和B-O键的形成。Fe₂-POP具有较高的比表面积（510 m²·g^-1）和均一的孔径（0.6~0.8 nm）。X射线光电子能谱表明了Fe₂-POP中二价铁的存在。扫描电子显微镜和透射电子显微镜显示该聚合物是由50~100 nm的球形颗粒组成。电化学测试表明，Fe₂-POP展现出了优异的电催化析氧性能，在10 mA·cm^-2电流密度下所需析氧反应过电位仅为258 mV，Tafel斜率为71.0 mV·dec^-1。

Binuclear Iron Oxime Boric Acid Based Metal-Containing Porous Organic Polymer: Synthesis, Structure and Electrocatalytic Oxygen Evolution Properties

A three-dimensional metal-containing porous organic polymer (Fe₂-POP) was synthesized using ferrous chloride, 2, 6-diformyl-4-methylphenol dioxime (H₃DFMP) and tetra(4-(dihydroxy)borylphenyl)methane (TBPM) through one-step coordination and boric acid esterification dehydration polymerization reaction. Binuclear iron as the linear unit was formed by coordination between iron ion and H₃DFMP, while TBPM was used as the tetrahedral linking unit, so that the three-dimensional porous organic polymer Fe₂-POP with dia topology was produced. X-ray single crystal diffraction analysis of the model compound (MC-1) verified the structural characteristics of the dinuclear ferrous unit. Infrared spectroscopy and solid-state nuclear magnetism characterizations proved the formation of C=N and B-O in Fe₂-POP. Fe₂-POP had a high specific surface area of 510 m²·g^-1 and uniform pore size (0.6-0.8 nm). X-ray photoelectron spectroscopy indicated the presence of divalent iron in Fe₂-POP. Scanning electron microscopy and transmission electron microscopy showed that Fe₂-POP was composed of 50-100 nm sphere-shaped particles. Electrochemical tests showed that Fe₂-POP exhibited excellent electrochemical properties towards oxygen evolution reaction, and it only needed a small overpotential of 258 mV to deliver a current density of 10 mA·cm^-2, and the Tafel slope was 71.0 mV·dec^-1.