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Study of Stability and Proton Conductivity of Zn-based Metal–Organic Framework
Son Younghu,Rao Purna Chandra,Kim Jiyun,Park Gyungse,Yoon Minyoung 대한화학회 2021 Bulletin of the Korean Chemical Society Vol.42 No.5
Among the various types of solid-state proton conductors (SSPCs), metal–organic frameworks (MOFs) have emerged as significant importance in the field of proton-exchange membrane fuel-cell (PEMFCs) applications. Herein, we have synthesized a three-dimensional trinuclear zinc-based metal–organic framework, denoted as Zn-SDC-MOF by modification of reported synthetic conditions, where stilbenedicarboxylic acid (H2SDC) and 4,40-bipyridine (bpy) are employed as an organic linker unit. With motivation of air stable trinuclear Zn-SDC MOFs, we have analyzed the water stability behavior of this compound. It resulted in exceptional water stability performance over 3 weeks as confirmed by powder X-ray diffraction (PXRD) analysis. Moreover, this MOF compounds have shown modest proton conductive performance of 0.8 × 10−3 S cm−1, at 95% relative humidity (RH) and 298 K.
Uncoordinated tetrazole ligands in metal–organic frameworks for proton‐conductivity studies
Lee Daeyeon,Lee Sangho,Son Younghu,Kim Jun Yeong,Cha Seungheon,Kwak Dongmin,Lee Jooyeon,Kwak Jaesung,Yoon Minyoung,Kim Min 대한화학회 2022 Bulletin of the Korean Chemical Society Vol.43 No.7
Zr-based metal–organic frameworks (MOFs) were modified with pendant tetrazole ligands for proton conductivity studies. Although tetrazolate ligands coordinated to metal cations have been widely utilized to construct MOFs or porous coordination polymers, to date, the use of uncoordinated tetrazole groups in MOFs has been limited. In this study, a benzene-1,4-dicarboxylic acid with pendant tetrazole groups (BDC-N4) was synthesized and used to prepare a Zr-based UiO-66 MOF using a mixed-ligand strategy. The tetrazolefunctionalized UiO-66-N4 was compared to MOFs containing other acidic functional groups (hydroxyl, carboxylic acid, and sulfonic acid) with respect to their proton conductivities and acidities (calculated pKa). Interestingly, UiO-66-N4 showed a significant decrease in the activation energy with increase in the amount of added tetrazole groups, suggesting the Grotthuss proton conduction mechanism for uncoordinated tetrazole-containing MOFs.