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Title: Phase Transition of H 2 in Subnanometer Pores Observed at 75 K

Abstract

In this paper, we report a phase transition in H 2 adsorbed in a locally graphitic Saran carbon with subnanometer pores 0.5–0.65 nm in width, in which two layers of hydrogen can just barely squeeze, provided they pack tightly. The phase transition is observed at 75 K, temperatures far higher than other systems in which an adsorbent is known to increase phase transition temperatures: for instance, H 2 melts at 14 K in the bulk, but at 20 K on graphite because the solid H 2 is stabilized by the surface structure. Here we observe a transition at 75 K and 77–200 bar: from a low-temperature, low-density phase to a high-temperature, higher density phase. We model the low-density phase as a monolayer commensurate solid composed mostly of para-H 2 (the ground nuclear spin state, S = 0) and the high-density phase as an orientationally ordered bilayer commensurate solid composed mostly of ortho-H 2 (S = 1). We attribute the increase in density with temperature to the fact that the oblong ortho-H 2 can pack more densely. The transition is observed using two experiments. The high-density phase is associated with an increase in neutron backscatter by a factor of 7.0 ±more » 0.1. Normally, hydrogen produces no backscatter (scattering angle >90°). This backscatter appears along with a discontinuous increase in the excitation mass from 1.2 amu to 21.0 ± 2.3 amu, which we associate with collective nuclear spin excitations in the orientationally ordered phase. Film densities were measured using hydrogen adsorption. Finally, no phase transition was observed in H 2 adsorbed in control activated carbon materials.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [3];  [2];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  2. Univ. of Missouri, Columbia, MO (United States). Dept. of Physics and Astronomy
  3. Science and Technology Facilities Council (STFC), Didcot (United Kingdom). Rutherford Appleton Lab. ISIS Spallation Neutron Source
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Missouri, Columbia, MO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1439944
Alternate Identifier(s):
OSTI ID: 1422614
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 11; Journal Issue: 11; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; adsorption; carbon; hydrogen storage; neutron scattering; nuclear magnetism

Citation Formats

Olsen, Raina J., Gillespie, Andrew K., Contescu, Cristian I., Taylor, Jonathan W., Pfeifer, Peter, and Morris, James R. Phase Transition of H2 in Subnanometer Pores Observed at 75 K. United States: N. p., 2017. Web. doi:10.1021/acsnano.7b06640.
Olsen, Raina J., Gillespie, Andrew K., Contescu, Cristian I., Taylor, Jonathan W., Pfeifer, Peter, & Morris, James R. Phase Transition of H2 in Subnanometer Pores Observed at 75 K. United States. doi:10.1021/acsnano.7b06640.
Olsen, Raina J., Gillespie, Andrew K., Contescu, Cristian I., Taylor, Jonathan W., Pfeifer, Peter, and Morris, James R. Mon . "Phase Transition of H2 in Subnanometer Pores Observed at 75 K". United States. doi:10.1021/acsnano.7b06640.
@article{osti_1439944,
title = {Phase Transition of H2 in Subnanometer Pores Observed at 75 K},
author = {Olsen, Raina J. and Gillespie, Andrew K. and Contescu, Cristian I. and Taylor, Jonathan W. and Pfeifer, Peter and Morris, James R.},
abstractNote = {In this paper, we report a phase transition in H2 adsorbed in a locally graphitic Saran carbon with subnanometer pores 0.5–0.65 nm in width, in which two layers of hydrogen can just barely squeeze, provided they pack tightly. The phase transition is observed at 75 K, temperatures far higher than other systems in which an adsorbent is known to increase phase transition temperatures: for instance, H2 melts at 14 K in the bulk, but at 20 K on graphite because the solid H2 is stabilized by the surface structure. Here we observe a transition at 75 K and 77–200 bar: from a low-temperature, low-density phase to a high-temperature, higher density phase. We model the low-density phase as a monolayer commensurate solid composed mostly of para-H2 (the ground nuclear spin state, S = 0) and the high-density phase as an orientationally ordered bilayer commensurate solid composed mostly of ortho-H2 (S = 1). We attribute the increase in density with temperature to the fact that the oblong ortho-H2 can pack more densely. The transition is observed using two experiments. The high-density phase is associated with an increase in neutron backscatter by a factor of 7.0 ± 0.1. Normally, hydrogen produces no backscatter (scattering angle >90°). This backscatter appears along with a discontinuous increase in the excitation mass from 1.2 amu to 21.0 ± 2.3 amu, which we associate with collective nuclear spin excitations in the orientationally ordered phase. Film densities were measured using hydrogen adsorption. Finally, no phase transition was observed in H2 adsorbed in control activated carbon materials.},
doi = {10.1021/acsnano.7b06640},
journal = {ACS Nano},
number = 11,
volume = 11,
place = {United States},
year = {Mon Oct 30 00:00:00 EDT 2017},
month = {Mon Oct 30 00:00:00 EDT 2017}
}

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