Two highly proton-conductive molecular hybrids based on ionized water clusters and poly-Keggin-anion chains

Journal Article · Wed Jun 15 04:00:00 EDT 2011 · Journal of Solid State Chemistry

OSTI ID:21580117

Pengfei, Zhuang; Qiuxiang, Miao; Yan, Wang ^[1]

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1. College of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China)

Two proton-conductive molecular hybrid complexes, {l_brace}[Zn(H{sub 2}O){sub 8}][H(H{sub 2}O){sub 2}](HINO){sub 4}(PMo{sub 12}O{sub 40}){r_brace}{sub n} (1) and {l_brace}[Mn(H{sub 2}O){sub 8}][H(H{sub 2}O){sub 2.5}](HINO){sub 4}(PMo{sub 12}O{sub 40}){r_brace}{sub n} (2), were constructed by introducing protonated water clusters, transition metal ionized water clusters and [PMo{sub 12}O{sub 40}]{sup 3-} anions in the gallery of H-bonding networks based on isonicotinic acid N-oxide (HINO). Single-crystal X-ray diffraction analyses at 293 K revealed that both complexes presented exactly the same three-dimensional (3D) hydrogen-bonded networks with large one-dimensional (1D) channels. Interestingly, [PMo{sub 12}O{sub 40}]{sup 3-} anions just filled in the 1D channels and self-assembled into poly-Keggin-anion chains. Thermogravimetric analyses both show no weight loss in the temperature range of 20-100 deg. C, indicating that all water molecules in the unit structure are not easily lost below 100 deg. C. Surprisingly, the proton conductivities of 1 and 2 in the temperature range of 85-100 deg. C under 98% RH conditions reached high proton conductivities of 10{sup -3} S cm{sup -1}. A possible mechanism of the proton conduction was proposed according to the experimental results. - Graphical abstract: Two molecular hybrids constructed by ionized water clusters and poly-Keggin-anion chains showed high proton conductivities of 10{sup -3} S cm{sup -1} in the temperature range of 85-100 deg. C under 98% relative humidity. Highlights: > Proton conductors have interested us from the point of its applications in fuel cells. > Heteropolyacids have suitable characteristics to be used as excellent proton conductors. > Two new supramolecular complexes based on [PMo{sub 12}O{sub 40}]{sup 3-} and isonicotinic acid N-oxide was constructed. > The structure was determined by using single-crystal X-ray diffraction data. > Both complexes showed good proton conductivities of 10{sup -3} S cm{sup -1} in the temperature range of 85-100 deg. C.

• OSTI ID: 21580117
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 6 Vol. 184; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANIONS
BARYONS
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL ANALYSIS
COHERENT SCATTERING
CRYSTALS
DIFFRACTION
DIRECT ENERGY CONVERTERS
ELECTRIC CONDUCTIVITY
ELECTRICAL PROPERTIES
ELECTROCHEMICAL CELLS
ELEMENTARY PARTICLES
FERMIONS
FUEL CELLS
GRAVIMETRIC ANALYSIS
HADRONS
HYBRIDIZATION
HYDROGEN COMPOUNDS
IONIC CONDUCTIVITY
IONS
MONOCRYSTALS
NUCLEONS
OXIDES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
PROTON CONDUCTIVITY
PROTONS
QUANTITATIVE CHEMICAL ANALYSIS
SCATTERING
TEMPERATURE RANGE
THERMAL ANALYSIS
THERMAL GRAVIMETRIC ANALYSIS
WATER
X-RAY DIFFRACTION