A sandwich-type POM containing mixed cations: synthesis, thermal performance and proton-conducting properties

A new sandwich-type polyoxometalate, Na 5 H[N(CH 3 ) 4 ] 2 [Co(C 3 N 2 H 4 ) 2 (H 2 O) 4 ][Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·21H 2 O (1), has been synthesized. 1 is composed of a Weakley-type polyanion, [Co 4( H 2 O) 2 (PW 9 O 34 ) 2 ] 10− , four kinds of cations (five Na + , two [N(CH 3 ) 4 ] + , one...

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Published inJournal of coordination chemistry Vol. 69; no. 3; pp. 425 - 432
Main Authors Li, Shujun, Zhang, Fanyu, Peng, Qingpo, Chen, Xuenian, Wang, Ruoya, Wang, Zhifang, Ma, Fengji, Zhao, Qianyi, Wei, Meilin
Format Journal Article
LanguageEnglish
Published Abingdon Taylor & Francis 01.02.2016
Taylor & Francis Ltd
Subjects
Alternating current
Cations
Cluster compounds
Crystal structure
Networks
polyoxometalates
Polyoxometallates
proton conduction
Relative humidity
sandwich-type
thermal behavior
Thermal decomposition
Three dimensional
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Abstract A new sandwich-type polyoxometalate, Na 5 H[N(CH 3 ) 4 ] 2 [Co(C 3 N 2 H 4 ) 2 (H 2 O) 4 ][Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·21H 2 O (1), has been synthesized. 1 is composed of a Weakley-type polyanion, [Co 4( H 2 O) 2 (PW 9 O 34 ) 2 ] 10− , four kinds of cations (five Na + , two [N(CH 3 ) 4 ] + , one [Co(C 3 N 2 H 4 ) 2 (H 2 O) 4 ] 2+ , and one H + ), and 21 crystalline H 2 O molecules. The surface oxygen of the polyanion in 1, the crystalline water, and coordinated water molecules make an extended 3-D hydrogen-bonding network. Alternating current (AC) impedance experiments of 1 reveal good proton conductivity for 1 of 5.03 × 10 − 4 S cm −1 at 25 °C under 98% relative humidity (RH). Activation energy of 1 calculated from Arrhenius plots is 0.358 eV, indicating Grotthuss mechanism is dominant in the proton transfer. Thermal decomposition behavior of 1 was examined by thermogravimetry/mass spectrometry (TG/MS) measurements.
AbstractList A new sandwich-type polyoxometalate, Na5H[N(CH3)4]2[Co(C3N2H4)2(H2O)4][Co4(H2O)2(PW9O34)2]·21H2O (1), has been synthesized. 1 is composed of a Weakley-type polyanion, [Co4(H2O)2(PW9O34)2]10-, four kinds of cations (five Na+, two [N(CH3)4]+, one [Co(C3N2H4)2(H2O)4]2+, and one H+), and 21 crystalline H2O molecules. The surface oxygen of the polyanion in 1, the crystalline water, and coordinated water molecules make an extended 3-D hydrogen-bonding network. Alternating current (AC) impedance experiments of 1 reveal good proton conductivity for 1 of 5.03 × 10- 4 S cm-1 at 25 °C under 98% relative humidity (RH). Activation energy of 1 calculated from Arrhenius plots is 0.358 eV, indicating Grotthuss mechanism is dominant in the proton transfer. Thermal decomposition behavior of 1 was examined by thermogravimetry/mass spectrometry (TG/MS) measurements.
A new sandwich-type polyoxometalate, Na 5 H[N(CH 3 ) 4 ] 2 [Co(C 3 N 2 H 4 ) 2 (H 2 O) 4 ][Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·21H 2 O (1), has been synthesized. 1 is composed of a Weakley-type polyanion, [Co 4( H 2 O) 2 (PW 9 O 34 ) 2 ] 10− , four kinds of cations (five Na + , two [N(CH 3 ) 4 ] + , one [Co(C 3 N 2 H 4 ) 2 (H 2 O) 4 ] 2+ , and one H + ), and 21 crystalline H 2 O molecules. The surface oxygen of the polyanion in 1, the crystalline water, and coordinated water molecules make an extended 3-D hydrogen-bonding network. Alternating current (AC) impedance experiments of 1 reveal good proton conductivity for 1 of 5.03 × 10 − 4 S cm −1 at 25 °C under 98% relative humidity (RH). Activation energy of 1 calculated from Arrhenius plots is 0.358 eV, indicating Grotthuss mechanism is dominant in the proton transfer. Thermal decomposition behavior of 1 was examined by thermogravimetry/mass spectrometry (TG/MS) measurements.
A new sandwich-type polyoxometalate, Na sub(5)H[N(CH sub(3)) sub(4)] sub(2)[Co(C sub(3) N sub(2)H sub(4)) sub(2)(H sub(2)O) sub(4)][Co sub(4)(H sub(2)O) sub(2)(PW sub(9)O sub( 34)) sub( 2)].21H sub(2)O (1), has been synthesized. 1 is composed of a Weakley-type polyanion, [Co sub(4()H sub(2)O) sub(2 )(PW sub(9)O sub(34)) sub(2)] super(10-), four kinds of cations (five Na super(+), two [N(CH sub(3)) sub(4)] super(+), one [Co(C sub(3)N sub(2)H sub(4 )) sub(2)(H sub(2)O) sub(4)] super(2+), and one H super(+)), and 21 crystalline H sub(2)O molecules. The surface oxygen of the polyanion in 1, the crystalline water, and coordinated water molecules make an extended 3-D hydrogen-bonding network. Alternating current (AC) impedance experiments of 1 reveal good proton conductivity for 1 of 5.03 10 super(- 4) S cm super(-1) at 25 degree C under 98% relative humidity (RH). Activation energy of 1 calculated from Arrhenius plots is 0.358 eV, indicating Grotthuss mechanism is dominant in the proton transfer. Thermal decomposition behavior of 1 was examined by thermogravimetry/mass spectrometry (TG/MS) measurements.
Author Zhao, Qianyi
Peng, Qingpo
Li, Shujun
Wang, Ruoya
Zhang, Fanyu
Wang, Zhifang
Ma, Fengji
Chen, Xuenian
Wei, Meilin
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Snippet A new sandwich-type polyoxometalate, Na 5 H[N(CH 3 ) 4 ] 2 [Co(C 3 N 2 H 4 ) 2 (H 2 O) 4 ][Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·21H 2 O (1), has been synthesized....
A new sandwich-type polyoxometalate, Na5H[N(CH3)4]2[Co(C3N2H4)2(H2O)4][Co4(H2O)2(PW9O34)2]·21H2O (1), has been synthesized. 1 is composed of a Weakley-type...
A new sandwich-type polyoxometalate, Na sub(5)H[N(CH sub(3)) sub(4)] sub(2)[Co(C sub(3) N sub(2)H sub(4)) sub(2)(H sub(2)O) sub(4)][Co sub(4)(H sub(2)O)...
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SubjectTerms Alternating current
Cations
Cluster compounds
Crystal structure
Networks
polyoxometalates
Polyoxometallates
proton conduction
Relative humidity
sandwich-type
thermal behavior
Thermal decomposition
Three dimensional
Title A sandwich-type POM containing mixed cations: synthesis, thermal performance and proton-conducting properties
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