Xu Lin, Dang Mengyu, Yang Fengfan, Lang Feifan, Li Beibei, Liang Linfeng, Pang Jiandong, Bu Xian-He
School of Materials Science and Engineering, Smart Sensing Interdisciplinary Science Centre, Nankai University, Tianjin 300350, China.
Henan Key Laboratory of Polyoxometalate, College of Chemistry and Molecular Science, Henan University, Kaifeng, Henan 475004, China.
Inorg Chem. 2024 Sep 23;63(38):17747-17754. doi: 10.1021/acs.inorgchem.4c02575. Epub 2024 Aug 29.
In the development of proton conductors, it is crucial to regulate proton conduction pathways and enhance structural stability. In this study, we designed and constructed three hydrogen-bonded organic frameworks (HOFs), namely, NKM-HOF-9, NKM-HOF-10, and NKM-HOF-11, with different dimensional hydrogen-bonding pathways using 4,4'-sulfonyldibenzoic acid and various bases. They are cost-effective and easy to synthesize, allowing for their large-scale production at room temperature. By purposefully altering the ammonium ions, we achieved enhancements in the conductivity and stability of these HOFs. Proton conductivity studies at different humidities and temperatures revealed that at 85 °C and 98% relative humidity, the proton conductivity of NKM-HOF-10 reached 1.7 × 10 S cm, surpassing that of NKM-HOF-9 by 1 order of magnitude. This improvement was accomplished by increasing the number of proton donors from the base, which resulted in a transition of the hydrogen bond network from discontinuous to continuous, thereby enhancing the proton conduction performance. Moreover, stability tests showed that raising the base's p could improve the stability of these frameworks. NKM-HOF-11, which features the highest p, demonstrated superior stability by maintaining its structural integrity even at 450 °C.
在质子导体的开发中，调节质子传导途径并增强结构稳定性至关重要。在本研究中，我们使用4,4'-磺酰二苯甲酸和各种碱设计并构建了三种具有不同维度氢键途径的氢键有机框架（HOFs），即NKM-HOF-9、NKM-HOF-10和NKM-HOF-11。它们具有成本效益且易于合成，能够在室温下大规模生产。通过有目的地改变铵离子，我们提高了这些HOFs的导电性和稳定性。在不同湿度和温度下的质子传导率研究表明，在85°C和98%相对湿度下，NKM-HOF-10的质子传导率达到1.7×10 S cm，比NKM-HOF-9高出1个数量级。这种改进是通过增加来自碱的质子供体数量实现的，这导致氢键网络从不连续转变为连续，从而提高了质子传导性能。此外，稳定性测试表明，提高碱的p值可以提高这些框架的稳定性。具有最高p值的NKM-HOF-11即使在450°C时仍能保持其结构完整性，表现出卓越的稳定性。
