Proton dynamics in the room-temperature phase of Cs3(HSO4)2(H2PO4) studied by 1H MAS NMR

Omi, Hironori; Suzuki, K.; Hayashi, Shigenobu

doi:10.1016/j.ssi.2007.10.004

Cited by 4 publications

(6 citation statements)

References 19 publications

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“…The small −5.5 ppm signal is ascribed to CsH 2 PO 4 , being supported by the spectrum of CsH 2 PO 4 having an isotropic signal at −5.5 ppm shown in Figure B. Another small signal at −1.5 ppm is ascribed to Cs 3 (HSO 4 ) 2 (H 2 PO 4 ) . Those small signals at −1.5 and −5.5 ppm are considered to be an impurity phase, and the Cs 2 (HSO 4 )(H 2 PO 4 ) sample is confirmed to be rather pure.…”

Section: Resultsmentioning

confidence: 54%

Section: Resultsmentioning

confidence: 99%

“…In the room-temperature phase of Cs 3 (HSO 4 ) 2 (HPO 4 ) there are five crystallographically inequivalent proton sites, and proton exchange starts to take place between protons with weaker hydrogen bonds. 14 In Cs 2 (HSO 4 )(H 2 PO 4 ), the hydrogen bond strength is not correlated with the onset of the proton motion, although there are several kinds of hydrogen bonds. The phase transition starts proton exchange between the roughly two kinds of hydrogen bonds.…”

Section: (8 Khz)mentioning

confidence: 99%

“…The presence of the superprotonic phase was demonstrated in Cs 3 (HSO 4 ) 2 (H 2 PO 4 ), , β-Cs 3 (HSO 4 ) 2 (H x (P,S)O 4 ), and Cs 2 (HSO 4 )(H 2 PO 4 ). , In those compounds, tetrahedral PO 4 and SO 4 anions form hydrogen bond networks. In the previous works, we studied proton dynamics in Cs 2 (HSO 4 )(H 2 PO 4 ) , and Cs 3 (HSO 4 ) 2 (HPO 4 ) , by means of 1 H solid-state NMR. NMR is suitable to study the dynamics at the atomic level.…”

Section: Introductionmentioning

confidence: 99%

“…9,10 In those compounds, tetrahedral PO 4 and SO 4 anions form hydrogen bond networks. In the previous works, we studied proton dynamics in Cs 2 (HSO 4 )(H 2 PO 4 ) 1 1 , 1 2 and Cs 3 (HSO 4 ) 2 (HPO 4 ) 13,14 by means of 1 H solid-state NMR. NMR is suitable to study the dynamics at the atomic level.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen Bond Networks in Cs₂(HSO₄)(H₂PO₄) As Studied by Solid-State NMR

Hayashi

Jimura

2017

J. Phys. Chem. C

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The inorganic solid acid salt Cs 2 (HSO 4 )(H 2 PO 4 ) showed high proton conductivity in the superprotonic phase above 370 K, and the phase was retained on cooling even at room temperature for a long period. These characteristic properties should correlate to the hydrogen bond network connecting the SO 4 and PO 4 groups. In the present work, the structures of the hydrogen bond network were studied by solid-state NMR. We present 31 P, 1 H, and 133 Cs magic-angle-spinning (MAS) NMR spectra, 31 P static NMR spectra to derive chemical shift anisotropy, a 31 P{ 1 H} dipolar dephasing experiment, and 1 H{ 31 P} rotational-echo double resonance (REDOR) experiments. The 31 P NMR spectra indicate that all the P sites are crystallographically equivalent, and the negative value of the chemical shift anisotropy suggests that four hydrogen bonds are formed around the PO 4 tetrahedron. The 31 P{ 1 H} dipolar dephasing experiment strongly supports that the number of hydrogen bonds around the PO 4 tetrahedron is four. The 1 H and 133 Cs MAS NMR spectra show that a part of the hydrogen bond network is disordered and that the disordered structure relaxes slowly with time. On the basis of those NMR results, we propose a model structure of the hydrogen bond network.

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Section: Resultsmentioning

confidence: 54%

Section: Resultsmentioning

confidence: 99%

Section: (8 Khz)mentioning

confidence: 99%