Song Yong-Jie, Ren Si-Yuan, Zuo Shuaiwu, Shi Zhi-Qiang, Li Zifeng, Li Gang
College of Chemistry and Green Catalysis Centre, Zhengzhou University, Zhengzhou 450001, Henan, P. R. China.
School of Chemistry and Chemical Engineering, Suzhou University, Suzhou 234000, P. R. China.
Inorg Chem. 2024 May 6;63(18):8194-8205. doi: 10.1021/acs.inorgchem.4c00444. Epub 2024 Apr 19.
Although crystalline metal-organic frameworks (MOFs) have gained a great deal of interest in the field of proton conduction in recent years, the low stability and poor proton conductivity (σ) of some MOFs have hindered their future applications. As a result, resolving the issues listed above must be prioritized. Due to their exceptional structural stability, MOFs with ferrocene groups that exhibit particular physical and chemical properties have drawn a lot of attention. This study describes the effective preparation of a set of three-dimensional ferrocene-based MOFs, and , containing both main group metals and 1,1'-ferrocene dicarboxylic acid (HFcDC). Multiple measurements, including powder X-ray diffraction (PXRD), infrared (IR), and scanning electron microscopy (SEM), confirmed that the addition of ferrocene groups enhanced the thermal, water, and acid-base stabilities of the three MOFs. Consequently, their proton-conductive behaviors were meticulously measured utilizing the AC impedance approach, and their best proton conductivities are 5.20 × 10, 2.31 × 10, and 1.72 × 10 S/cm at 100 °C/98% relative humidity (RH), respectively. Excitingly, demonstrated an extraordinarily ultrahigh σ of above 10 S·cm under 30 °C/98% RH. Using data from structural analysis, PXRD, SEM, thermogravimetry (TG), and activation energy, their proton transport mechanisms were thoroughly examined. The fact that these MOFs are notably easy to assemble, inexpensive, toxin-free, and stable will increase the range of practical uses for them.
尽管近年来晶态金属有机框架材料(MOFs)在质子传导领域引起了广泛关注,但一些MOFs的低稳定性和较差的质子传导率(σ)阻碍了它们未来的应用。因此,必须优先解决上述问题。由于具有特殊结构稳定性且表现出特定物理和化学性质的含二茂铁基团的MOFs受到了广泛关注。本研究描述了一组含主族金属和1,1'-二茂铁二甲酸(HFcDC)的三维二茂铁基MOFs 、 和 的有效制备方法。包括粉末X射线衍射(PXRD)、红外(IR)和扫描电子显微镜(SEM)在内的多项测量证实,二茂铁基团的加入增强了这三种MOFs的热稳定性、水稳定性和酸碱稳定性。因此,利用交流阻抗法对它们的质子传导行为进行了细致测量,在100℃/98%相对湿度(RH)下,它们的最佳质子传导率分别为5.20×10、2.31×10和1.7×10 S/cm。令人兴奋的是, 在30℃/98%RH下表现出超过10 S·cm的超高σ。利用结构分析、PXRD、SEM、热重分析(TG)和活化能的数据,对它们的质子传输机制进行了深入研究。这些MOFs显著易于组装、价格低廉且无毒稳定,这将增加它们的实际应用范围。