skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Structural Evolution of CO 2-Filled Pure Silica LTA Zeolite under High-Pressure High-Temperature Conditions

Abstract

The crystal structure of CO 2-filled pure-SiO 2 LTA zeolite has been studied at high pressures and temperatures using synchrotron-based X-ray powder diffraction. Its structure consists of 13 CO 2 guest molecules, 12 of them accommodated in the large α-cages and one in the β-cages, giving a SiO 2/CO 2 stoichiometric ratio smaller than 2. The structure remains stable under pressure up to 20 GPa with a slight pressure-dependent rhombohedral distortion, indicating that pressure-induced amorphization is prevented by the insertion of guest species in this open framework. The ambient-temperature lattice compressibility has been determined. In situ high-pressure resistive-heating experiments up to 750 K allow us to estimate the thermal expansivity at P ≈ 5 GPa. Our data confirm that the insertion of CO 2 reverses the negative thermal expansion of the empty zeolite structure. No evidence of any chemical reaction was observed. Finally, the possibility of synthesizing a silicon carbonate at high temperatures and higher pressures is discussed in terms of the evolution of C–O and Si–O distances between molecular and framework atoms.

Authors:
ORCiD logo [1];  [1];  [2];  [1];  [3];  [1]; ORCiD logo [1];  [4];  [4];  [5];  [5];  [5];  [6]
  1. Univ. de Valencia (Spain)
  2. Atomic Weapons Establishment, Reading (United Kingdom); Imperial College London (United Kingdom)
  3. Diamond Light Source, Didcot (United Kingdom)
  4. Univ. Politècnica de València − Consejo Superior de Investigaciones Científicas, Valencia (Spain)
  5. Univ. of California, Los Angeles, CA (United States)
  6. ALBA-CELLS, Cerdanyola (Spain)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1368292
Grant/Contract Number:  
AC02-06CH11357; EAR 11-57758; FG02-94ER14466
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 10; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical structure; physical and chemical processes; phase transitions; zeolites; molecules

Citation Formats

Santamaría-Pérez, David, Marqueño, Tomas, MacLeod, Simon, Ruiz-Fuertes, Javier, Daisenberger, Dominik, Chuliá-Jordan, Raquel, Errandonea, Daniel, Jordá, Jose Luis, Rey, Fernando, McGuire, Chris, Mahkluf, Adam, Kavner, Abby, and Popescu, Catalin. Structural Evolution of CO2-Filled Pure Silica LTA Zeolite under High-Pressure High-Temperature Conditions. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b01158.
Santamaría-Pérez, David, Marqueño, Tomas, MacLeod, Simon, Ruiz-Fuertes, Javier, Daisenberger, Dominik, Chuliá-Jordan, Raquel, Errandonea, Daniel, Jordá, Jose Luis, Rey, Fernando, McGuire, Chris, Mahkluf, Adam, Kavner, Abby, & Popescu, Catalin. Structural Evolution of CO2-Filled Pure Silica LTA Zeolite under High-Pressure High-Temperature Conditions. United States. doi:10.1021/acs.chemmater.7b01158.
Santamaría-Pérez, David, Marqueño, Tomas, MacLeod, Simon, Ruiz-Fuertes, Javier, Daisenberger, Dominik, Chuliá-Jordan, Raquel, Errandonea, Daniel, Jordá, Jose Luis, Rey, Fernando, McGuire, Chris, Mahkluf, Adam, Kavner, Abby, and Popescu, Catalin. Mon . "Structural Evolution of CO2-Filled Pure Silica LTA Zeolite under High-Pressure High-Temperature Conditions". United States. doi:10.1021/acs.chemmater.7b01158. https://www.osti.gov/servlets/purl/1368292.
@article{osti_1368292,
title = {Structural Evolution of CO2-Filled Pure Silica LTA Zeolite under High-Pressure High-Temperature Conditions},
author = {Santamaría-Pérez, David and Marqueño, Tomas and MacLeod, Simon and Ruiz-Fuertes, Javier and Daisenberger, Dominik and Chuliá-Jordan, Raquel and Errandonea, Daniel and Jordá, Jose Luis and Rey, Fernando and McGuire, Chris and Mahkluf, Adam and Kavner, Abby and Popescu, Catalin},
abstractNote = {The crystal structure of CO2-filled pure-SiO2 LTA zeolite has been studied at high pressures and temperatures using synchrotron-based X-ray powder diffraction. Its structure consists of 13 CO2 guest molecules, 12 of them accommodated in the large α-cages and one in the β-cages, giving a SiO2/CO2 stoichiometric ratio smaller than 2. The structure remains stable under pressure up to 20 GPa with a slight pressure-dependent rhombohedral distortion, indicating that pressure-induced amorphization is prevented by the insertion of guest species in this open framework. The ambient-temperature lattice compressibility has been determined. In situ high-pressure resistive-heating experiments up to 750 K allow us to estimate the thermal expansivity at P ≈ 5 GPa. Our data confirm that the insertion of CO2 reverses the negative thermal expansion of the empty zeolite structure. No evidence of any chemical reaction was observed. Finally, the possibility of synthesizing a silicon carbonate at high temperatures and higher pressures is discussed in terms of the evolution of C–O and Si–O distances between molecular and framework atoms.},
doi = {10.1021/acs.chemmater.7b01158},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 10,
volume = 29,
place = {United States},
year = {2017},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share: