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Title: High-Pressure Effects on Hofmann-Type Clathrates: Promoted Release and Restricted Insertion of Guest Molecules

Authors:
; ; ; ORCiD logo; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1368298
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry Letters; Journal Volume: 8; Journal Issue: 12
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Li, Qian, Sha, Xiaojing, Li, Shourui, Wang, Kai, Quan, Zewei, Meng, Yue, and Zou, Bo. High-Pressure Effects on Hofmann-Type Clathrates: Promoted Release and Restricted Insertion of Guest Molecules. United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b01057.
Li, Qian, Sha, Xiaojing, Li, Shourui, Wang, Kai, Quan, Zewei, Meng, Yue, & Zou, Bo. High-Pressure Effects on Hofmann-Type Clathrates: Promoted Release and Restricted Insertion of Guest Molecules. United States. doi:10.1021/acs.jpclett.7b01057.
Li, Qian, Sha, Xiaojing, Li, Shourui, Wang, Kai, Quan, Zewei, Meng, Yue, and Zou, Bo. Mon . "High-Pressure Effects on Hofmann-Type Clathrates: Promoted Release and Restricted Insertion of Guest Molecules". United States. doi:10.1021/acs.jpclett.7b01057.
@article{osti_1368298,
title = {High-Pressure Effects on Hofmann-Type Clathrates: Promoted Release and Restricted Insertion of Guest Molecules},
author = {Li, Qian and Sha, Xiaojing and Li, Shourui and Wang, Kai and Quan, Zewei and Meng, Yue and Zou, Bo},
abstractNote = {},
doi = {10.1021/acs.jpclett.7b01057},
journal = {Journal of Physical Chemistry Letters},
number = 12,
volume = 8,
place = {United States},
year = {Mon Jun 05 00:00:00 EDT 2017},
month = {Mon Jun 05 00:00:00 EDT 2017}
}
  • The precipitation of Na{sup +} and K{sup +} mixed salts of Anderson type [SbW{sub 6}O{sub 24}]{sup 7-} by addition of excess of NaNO{sub 3} and NaCl yielded polycrystalline powders of Na{sub 2.5}K{sub 5.3}[SbW{sub 6}O{sub 24}](NO{sub 3}){sub 0.8}.12H{sub 2}O (1) and Na{sub 2}K{sub 5.35}[SbW{sub 6}O{sub 24}]Cl{sub 0.35}.12H{sub 2}O (2), respectively. The two compounds are isomorphous and exhibit a layer-like Anderson (LLA) type structure, which consists of [SbW{sub 6}O{sub 24}]{sup 7-}-containing layers and interstitial Na{sup +}, K{sup +}, NO{sub 3}{sup -} or Cl{sup -}, and water O atoms. Recrystallization of 1 and 2 from hot water yielded Na{sub 2}K{sub 5.4}[SbW{sub 6}O{sub 24}](NO{submore » 3}){sub 0.4}.12H{sub 2}O (1-recry) and Na{sub 2}K{sub 5.25}[SbW{sub 6}O{sub 24}]Cl{sub 0.25}.12H{sub 2}O (2-recry) as a result of partial release of NO{sub 3}{sup -} and Cl{sup -} (and Na{sup +} and K{sup +} for charge compensation). Dehydration of 1 and 2 at 400 and 500 {sup o}C (1-dehyd400 and 2-dehyd500) caused a shrinkage of lattice, but their the LLA structures retained. Simulation of X-ray diffraction (XRD) patterns for the dehydrated forms allowed to presume that the each [SbW{sub 6}O{sub 24}]{sup 7-} anion had been 30{sup o}-rotated within its molecular plane in order to avoid intermolecular repulsion. A compressed powder of 1-dehyd400 exhibited fast alkaline-ion conduction with a bulk conductivity of 1.2x10{sup -2} {Omega}{sup -1} cm{sup -1} at 400 {sup o}C. The hosting of a sufficient amount of NO{sub 3}{sup -} together with Na{sup +} for charge compensation into the lattice is crucial for high conduction. -- Graphical abstract: Two compounds Na{sub 2.5}K{sub 5.3}[SbW{sub 6}O{sub 24}](NO{sub 3}){sub 0.8}.12H{sub 2}O (1) and Na{sub 2}K{sub 5.35}[SbW{sub 6}O{sub 24}]Cl{sub 0.35}.12H{sub 2}O (2) possessing a layer-like Anderson (LLA) structure exhibited pseudo intercalation-deintercalation behavior. The dehydrated form of 1 is a high alkaline cation conductor with a conductivity of 1.2x10{sup -2} {Omega}{sup -1} cm{sup -1} at 400 {sup o}C. Display Omitted Research highlights: {yields} Layer-like Anderson-type POM solid accommodates and releases NO{sub 3}{sup -} and Cl{sup -}. {yields} The POM exhibits reversible dehydration by heat treatment. {yields} The dehydration involves rotation of POM molecule retaining layer structure. {yields} The dehydrated POM shows good Na{sup +} and K{sup +} conduction.« less
  • This paper reports a study of complex formation between two amphiphilic ketones and carboxymethylamylose and the photoreactiviy of the ketones in their respective inclusion complexes. The binding constants are found to increase as the chain length of the linear ketone (n in PhCO(CH/sub 2/)/sub n/COOH equals 3 and 10) increases. The CMA-included ketone is found to exhibit relatively low quantum efficiencies for the type II photoelimination process, the only reaction observed in each case. The results suggest that the ketone environment in the amylose cavities is relatively hydrophobic and conformationally restrictive; the photochemical reactivity observed is similar to that occurringmore » for related ketones incorporated into bilayer vesicles below the phase transition temperature.« less
  • It has been possible to localize the benzene guest molecule in a pentasil type zeolite by combining full profile X-ray powder diffraction structure refinements with conventional difference-Fourier synthesis, after extraction of the integrated intensities from the powder pattern. The investigations have been performed on the calcined H/sub 4.83/Al/sub 4.80/B/sub 0.03/Si/sub 91.17/O/sub 192/ phase (H-ZSM-5 form) which has been saturated with benzene vapor at low pressure. The same data-collection has been processed in two different ways: 1) a trial-and-error procedure described elsewhere shows that the benzene molecule appears to be present at the channel - intersection with two simultaneous orientations, andmore » 2) direct characterization by the interpretation of a difference-Fourier map reveals the presence of two peaks situated on the mirror plane. Combining the results yielded by both methods shows that the benzene molecule rotates freely about an axis situated on the mirror plane.« less