Encapsulating Mobile Proton Carriers into Structural Defects in Coordination Polymer Crystals: High Anhydrous Proton Conduction and Fuel Cell Application.
We describe the encapsulation of mobile proton carriers into defect sites in nonporous coordination polymers (CPs). The proton carriers were encapsulated with high mobility and provided high proton conductivity at 150 °C under anhydrous conditions. The high proton conductivity and nonporous nature of the CP allowed its application as an electrolyte in a fuel cell. The defects and mobile proton carriers were investigated using solid-state NMR, XAFS, XRD, and ICP-AES/EA. On the basis of these analyses, we concluded that the defect sites provide space for mobile uncoordinated H3PO4, H2PO4(-), and H2O. These mobile carriers play a key role in expanding the proton-hopping path and promoting the mobility of protons in the coordination framework, leading to high proton conductivity and fuel cell power generation.
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University , Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.|Graduate School of Science and Technology, Tokushima University , 2-1 minami-Josanjima-Cho, Tokushima 770-8506, Japan.
Munehiro
M
Inukai
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University , Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
Satoshi
S
Horike
DENSO Corporation, 1-1, Showa-cho, Kariya, Aichi 448-8661, Japan.
Tomoya
T
Itakura
DENSO Corporation, 1-1, Showa-cho, Kariya, Aichi 448-8661, Japan.
Ryota
R
Shinozaki
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University , Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
Naoki
N
Ogiwara
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University , Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
Daiki
D
Umeyama
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University , Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.
Sanjog S
SS
Nagarkar
JEOL Resonance Inc., 3-1-2 Musashino, Akishima, Tokyo 196-8558, Japan.|RIKEN CLST-JEOL Collaboration Center, Yokohama, Kanagawa 230-0045, Japan.
Yusuke
Y
Nishiyama
JEOL Resonance Inc., 3-1-2 Musashino, Akishima, Tokyo 196-8558, Japan.|RIKEN CLST-JEOL Collaboration Center, Yokohama, Kanagawa 230-0045, Japan.
Michal
M
Malon
International Research Center for Hydrogen Energy, Kyushu University , 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan.
Akari
A
Hayashi
J-PARC Center, Japan Atomic Energy Agency, Tokai, Naka-gun 319-1195, Japan.|Research Center for Neutron Science and Technology, Comprehensive Research Organization for Science and Society, Tokai, Ibaraki 319-1106, Japan.
Takashi
T
Ohhara
J-PARC Center, Japan Atomic Energy Agency, Tokai, Naka-gun 319-1195, Japan.
Ryoji
R
Kiyanagi
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University , Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.|Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University , Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
Susumu
S
Kitagawa