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Void Space versus Surface Functionalization for Proton Conduction in Metal–Organic Frameworks
Author(s) -
SarangoRamírez Marvin K.,
Park Junkil,
Kim Jihan,
Yoshida Yukihiro,
Lim DaeWoon,
Kitagawa Hiroshi
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202106181
Subject(s) - porosity , metal organic framework , electrical conductor , proton , conductivity , void (composites) , materials science , thermal conduction , surface modification , characterisation of pore space in soil , density functional theory , molecule , metal , chemical engineering , biphenyl , chemistry , composite material , adsorption , organic chemistry , computational chemistry , metallurgy , physics , quantum mechanics , engineering
Void space and functionality of the pore surface are important structural factors for proton‐conductive metal–organic frameworks (MOFs) impregnated with conducting media. However, no clear study has compared their priority factors, which need to be considered when designing proton‐conductive MOFs. Herein, we demonstrate the effects of void space and pore‐surface modification on proton conduction in MOFs through the surface‐modified isoreticular MOF‐74(Ni) series [Ni 2 (dobdc or dobpdc), dobdc=2,5‐dihydroxy‐1,4‐benzenedicarboxylate and dobpdc=4,4′‐dihydroxy‐(1,1′‐biphenyl)‐3,3′‐dicarboxylate]. The MOF with lower porosity with the same surface functionality showed higher proton conductivity than that with higher porosity despite including a smaller amount of conducting medium. Density functional theory calculations suggest that strong hydrogen bonding between molecules of the conducting medium at high porosity is inefficient in inducing high proton conductivity.