Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 9, Pages 3505-3512Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b12847
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Funding
- National Natural Science Foundation of China [21601157, 21501046, 21371153, 21671175]
- Program for Science & Technology Innovation Talents in Universities of Henan Province [164100510005]
- Zhengzhou University
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Recently, research on metal organic frameworks (MOFs) serving as a new type of proton conductive material has resulted in many exciting achievements. However, direct observation of a well-established proton-transfer mechanism still remains challenging in MOFs and other crystalline compounds, let alone other conductive materials. Herein we report the solvothermal synthesis of a new proton conducting MOF, (Me2NH2)[Eu(L)] (H4L = 5-(phosphonomethyl)isophthalic acid). The compound consists of a layered anionic framework [Eu(L)](-) and interlayer-embedded counter cations (Me2NH2)(+), which interact with adjacent uncoordinated O atoms of phosphonate groups to form strongly (N H center dot center dot center dot 0) hydrogen-bonded chains aligned parallel to the c axis. Facile proton transfer along these chains endows the compound with single-crystal anhydrous conductivity of 1.25 X 10(-3) S. cm(-1) at 150 degrees C, and water-assisted proton conductivity for a compacted pellet of microcrystalline crystals attains 3.76 X 10(-3) s cm(-1) at 100 degrees C and 98% relative humidity (RH). Proton dynamics (vibrating and transfer) within N-H center dot center dot center dot O chains of the compound are directly observed using a combination of anisotropic conductivity measurements and control experiments using large single-crystals and pelletized samples, in situ variable-temperature characterization techniques including powder X-ray diffraction (PXRD), single-crystal X-ray diffraction (SCXRD), diffuse reflectance infrared Fourier transform spectrum (DRIFTS), and variable-temperature photoluminescence. In particular, a scarce single-crystal to single-crystal (SCSC) transformation accompanied by proton transfer between an anionic structure (Me2NH2)[Eu(L)] and an identical neutral framework [Eu(HL)] has been identified.
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