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Title: Topological analysis of void spaces in tungstate frameworks: Assessing storage properties for the environmentally important guest molecules and ions: CO 2, UO 2, PuO 2, U, Pu, Sr 2+, Cs +, CH 4, and H 2

Abstract

The identification of inorganic materials, which are able to encapsulate environmentally important small molecules or ions via host-guest interactions, is crucial for the design and development of next-generation energy sources and for storing environmental waste. Especially sought after are molecular sponges with the ability to incorporate CO 2, gas pollutants, or nuclear waste materials such as UO 2 and PuO 2 oxides or U, Pu, Sr 2+ or Cs + ions. Porous framework structures promise very attractive prospects for applications in environmental technologies, if they are able to incorporate CH 4 for biogas energy applications, or to store H 2, which is important for fuel cells e.g. in the automotive industry. All of these applications should benefit from the host being resistant to extreme conditions such as heat, nuclear radiation, rapid gas expansion, or wear and tear from heavy gas cycling. As inorganic tungstates are well known for their thermal stability, and their rigid open-framework networks, the potential of Na 2O-Al 2O 3-WO 3 and Na 2O-WO 3 phases for such applications was evaluated. To this end, all known experimentally-determined crystal structures with the stoichiometric formula M aM’ bW cO d (M = any element) are surveyed together with allmore » corresponding theoretically calculated Na aAl bW cO d and Na xW yO z structures that are statistically likely to form. Network descriptors that categorize these host structures are used to reveal topological patterns in the hosts, including the nature of porous cages which are able to accommodate a certain type of guest; this leads to the classification of preferential structure types for a given environmental storage application. Crystal structures of two new tungstates NaAlW 2O 8 (1) and NaAlW 3O 11 (2) and one updated structure determination of Na 2W 2O 7 (3) are also presented from in-house X-ray diffraction studies, and their potential merits for environmental applications are assessed against those of this larger data-sourced survey. Altogether, results show that tungstate structures with three-nodal topologies are most frequently able to accommodate CH 4 or H 2, while CO 2 appears to be captured by a wide range of nodal structure types. The computationally generated host structures appear systematically smaller than the experimentally determined structures. For the structures of 1 and 2, potential applications in nuclear waste storage seem feasible.« less

Authors:
 [1];  [2];  [2]
  1. Univ. of Cambridge, Cambridge (United Kingdom); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Cambridge, Cambridge (United Kingdom)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1339566
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 3; Journal Issue: 9; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 emissions; framework structure; host-guest; nergy fuel storage; nuclear waste storage; tungstate

Citation Formats

Cole, Jacqueline M., Cramer, Alisha J., and Zeidler, Anita. Topological analysis of void spaces in tungstate frameworks: Assessing storage properties for the environmentally important guest molecules and ions: CO2, UO2, PuO2, U, Pu, Sr2+, Cs+, CH4, and H2. United States: N. p., 2015. Web. doi:10.1021/acssuschemeng.5b00369.
Cole, Jacqueline M., Cramer, Alisha J., & Zeidler, Anita. Topological analysis of void spaces in tungstate frameworks: Assessing storage properties for the environmentally important guest molecules and ions: CO2, UO2, PuO2, U, Pu, Sr2+, Cs+, CH4, and H2. United States. doi:10.1021/acssuschemeng.5b00369.
Cole, Jacqueline M., Cramer, Alisha J., and Zeidler, Anita. Wed . "Topological analysis of void spaces in tungstate frameworks: Assessing storage properties for the environmentally important guest molecules and ions: CO2, UO2, PuO2, U, Pu, Sr2+, Cs+, CH4, and H2". United States. doi:10.1021/acssuschemeng.5b00369. https://www.osti.gov/servlets/purl/1339566.
@article{osti_1339566,
title = {Topological analysis of void spaces in tungstate frameworks: Assessing storage properties for the environmentally important guest molecules and ions: CO2, UO2, PuO2, U, Pu, Sr2+, Cs+, CH4, and H2},
author = {Cole, Jacqueline M. and Cramer, Alisha J. and Zeidler, Anita},
abstractNote = {The identification of inorganic materials, which are able to encapsulate environmentally important small molecules or ions via host-guest interactions, is crucial for the design and development of next-generation energy sources and for storing environmental waste. Especially sought after are molecular sponges with the ability to incorporate CO2, gas pollutants, or nuclear waste materials such as UO2 and PuO2 oxides or U, Pu, Sr2+ or Cs+ ions. Porous framework structures promise very attractive prospects for applications in environmental technologies, if they are able to incorporate CH4 for biogas energy applications, or to store H2, which is important for fuel cells e.g. in the automotive industry. All of these applications should benefit from the host being resistant to extreme conditions such as heat, nuclear radiation, rapid gas expansion, or wear and tear from heavy gas cycling. As inorganic tungstates are well known for their thermal stability, and their rigid open-framework networks, the potential of Na2O-Al2O3-WO3 and Na2O-WO3 phases for such applications was evaluated. To this end, all known experimentally-determined crystal structures with the stoichiometric formula MaM’bWcOd (M = any element) are surveyed together with all corresponding theoretically calculated NaaAlbWcOd and NaxWyOz structures that are statistically likely to form. Network descriptors that categorize these host structures are used to reveal topological patterns in the hosts, including the nature of porous cages which are able to accommodate a certain type of guest; this leads to the classification of preferential structure types for a given environmental storage application. Crystal structures of two new tungstates NaAlW2O8 (1) and NaAlW3O11 (2) and one updated structure determination of Na2W2O7 (3) are also presented from in-house X-ray diffraction studies, and their potential merits for environmental applications are assessed against those of this larger data-sourced survey. Altogether, results show that tungstate structures with three-nodal topologies are most frequently able to accommodate CH4 or H2, while CO2 appears to be captured by a wide range of nodal structure types. The computationally generated host structures appear systematically smaller than the experimentally determined structures. For the structures of 1 and 2, potential applications in nuclear waste storage seem feasible.},
doi = {10.1021/acssuschemeng.5b00369},
journal = {ACS Sustainable Chemistry & Engineering},
number = 9,
volume = 3,
place = {United States},
year = {2015},
month = {7}
}

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