Grain-Boundary-Free Super-Proton Conduction of a Solution-Processed Prussian-Blue Nanoparticle Film

被引:55
作者
Ono, Kenta [1 ]
Ishizaki, Manabu [1 ]
Kanaizuka, Katsuhiko [1 ]
Togashi, Takanari [1 ]
Yamada, Teppei [2 ]
Kitagawa, Hiroshi [3 ]
Kurihara, Masato [1 ]
机构
[1] Yamagata Univ, Dept Mat & Biol Chem, 1-4-12 Kojirakawa Machi, Yamagata 9908560, Japan
[2] Kyushu Univ, Grad Sch Engn, Dept Appl Chem, Nishi Ku, 744 Moto Oka, Fukuoka 8190395, Japan
[3] Kyoto Univ, Div Chem, Grad Sch Sci, Sakyo Ku, Kyoto 6068502, Japan
关键词
grain-boundary free proton conduction; metalorganic frameworks; nanoparticles; Prussian blue; super-proton conductivity; METAL-ORGANIC FRAMEWORK; SELF-ASSEMBLED MONOLAYERS; DOPED BARIUM ZIRCONATE; CHARGE-TRANSPORT; WATER-MOLECULES; COORDINATION; MECHANISM; CRYSTALLINE; SOLIDS;
D O I
10.1002/anie.201701759
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A porous crystal family has been explored as alternatives of Nafion films exhibiting super-proton conductivities of >= 10(-2) Scm(-1). Here, the proton-conduction natures of a solution-processed film of nanoparticles (NPs) have been studied and compared to those of a Nafion film. A monoparticle film of Prussian-blue NPs is spontaneously formed on a self-assembled monolayer substrate by a one-step solution process. A low-temperature heating process of the densely packed, pinhole-free mono-particle NP film enables a maximum 105-fold enhancement of proton conductivity, reaching ca. 10(-1) Scm(-1). The apparent highest conductivity, compared to previously reported data of the porous crystal family, remains constant against humidity changes by an improved water-retention ability of the film. In our proposed mechanism, the high-performing solution-processed NP film suggests that heating leads to the self-restoration of hydrogen-bonding networks throughout their innumerable grain boundaries.
引用
收藏
页码:5531 / 5535
页数:5
相关论文
共 40 条
[1]   THE GROTTHUSS MECHANISM [J].
AGMON, N .
CHEMICAL PHYSICS LETTERS, 1995, 244 (5-6) :456-462
[2]  
[Anonymous], 1982, ANGEW CHEM, V94, P224
[3]  
[Anonymous], 2004, ANGEW CHEM, V116, P2388
[4]  
[Anonymous], 2013, ANGEW CHEM, V125, P2752
[5]   Hydrophilic Sparse Ionic Monolayer-Protected Metal Nanoparticles: Highly Concentrated Nano-Au and Nano-Ag "Inks" that can be Sintered to Near-Bulk Conductivity at 150°C [J].
Anto, Bibin T. ;
Sivaramakrishnan, Sankaran ;
Chua, Lay-Lay ;
Ho, Peter K. H. .
ADVANCED FUNCTIONAL MATERIALS, 2010, 20 (02) :296-303
[6]   CRYSTAL-STRUCTURE OF PRUSSIAN BLUE - FE4[FE(CN)6]3.XH2O [J].
BUSER, HJ ;
SCHWARZENBACH, D ;
PETTER, W ;
LUDI, A .
INORGANIC CHEMISTRY, 1977, 16 (11) :2704-2710
[7]   PROTON-TRANSFER AND SUPERIONIC CONDUCTIVITY IN SOLIDS AND GELS [J].
COLOMBAN, P ;
NOVAK, A .
JOURNAL OF MOLECULAR STRUCTURE, 1988, 177 :277-308
[8]   High-contrast electrochromism and controllable dissolution of assembled Prussian blue/polymer nanocomposites [J].
DeLongchamp, DM ;
Hammond, PT .
ADVANCED FUNCTIONAL MATERIALS, 2004, 14 (03) :224-232
[9]   Electrochemistry of redox-active self-assembled monolayers [J].
Eckermann, Amanda L. ;
Feld, Daniel J. ;
Shaw, Justine A. ;
Meade, Thomas J. .
COORDINATION CHEMISTRY REVIEWS, 2010, 254 (15-16) :1769-1802
[10]   Charge transport in Prussian Blue films deposited on ITO electrodes [J].
GarciaJareno, JJ ;
NavarroLaboulais, J ;
Vicente, F .
ELECTROCHIMICA ACTA, 1996, 41 (06) :835-841