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Title: Accurate Characterization of the Pore Volume in Microporous Crystalline Materials

Abstract

Pore volume is one of the main properties for the characterization of microporous crystals. It is experimentally measurable, and it can also be obtained from the refined unit cell by a number of computational techniques. In this work, we assess the accuracy and the discrepancies between the different computational methods which are commonly used for this purpose, i.e, geometric, helium, and probe center pore volumes, by studying a database of more than 5000 frameworks. We developed a new technique to fully characterize the internal void of a microporous material and to compute the probe-accessible and -occupiable pore volume. Lasty, we show that, unlike the other definitions of pore volume, the occupiable pore volume can be directly related to the experimentally measured pore volumes from nitrogen isotherms.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [1]
  1. Ecole Polytechnique Federale de Lausanne (EPFL), Valais (Switzerland)
  2. Univ. of California, Berkeley, CA (United States)
  3. IMDEA Materials Institute, Madrid (Spain); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1368597
Alternate Identifier(s):
OSTI ID: 1415446
Grant/Contract Number:
AC02-05CH11231; SC0001015
Resource Type:
Journal Article: Published Article
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 33; Journal Issue: 51; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Ongari, Daniele, Boyd, Peter G., Barthel, Senja, Witman, Matthew, Haranczyk, Maciej, and Smit, Berend. Accurate Characterization of the Pore Volume in Microporous Crystalline Materials. United States: N. p., 2017. Web. doi:10.1021/acs.langmuir.7b01682.
Ongari, Daniele, Boyd, Peter G., Barthel, Senja, Witman, Matthew, Haranczyk, Maciej, & Smit, Berend. Accurate Characterization of the Pore Volume in Microporous Crystalline Materials. United States. doi:10.1021/acs.langmuir.7b01682.
Ongari, Daniele, Boyd, Peter G., Barthel, Senja, Witman, Matthew, Haranczyk, Maciej, and Smit, Berend. Wed . "Accurate Characterization of the Pore Volume in Microporous Crystalline Materials". United States. doi:10.1021/acs.langmuir.7b01682.
@article{osti_1368597,
title = {Accurate Characterization of the Pore Volume in Microporous Crystalline Materials},
author = {Ongari, Daniele and Boyd, Peter G. and Barthel, Senja and Witman, Matthew and Haranczyk, Maciej and Smit, Berend},
abstractNote = {Pore volume is one of the main properties for the characterization of microporous crystals. It is experimentally measurable, and it can also be obtained from the refined unit cell by a number of computational techniques. In this work, we assess the accuracy and the discrepancies between the different computational methods which are commonly used for this purpose, i.e, geometric, helium, and probe center pore volumes, by studying a database of more than 5000 frameworks. We developed a new technique to fully characterize the internal void of a microporous material and to compute the probe-accessible and -occupiable pore volume. Lasty, we show that, unlike the other definitions of pore volume, the occupiable pore volume can be directly related to the experimentally measured pore volumes from nitrogen isotherms.},
doi = {10.1021/acs.langmuir.7b01682},
journal = {Langmuir},
number = 51,
volume = 33,
place = {United States},
year = {Wed Jun 21 00:00:00 EDT 2017},
month = {Wed Jun 21 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acs.langmuir.7b01682

Citation Metrics:
Cited by: 1work
Citation information provided by
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  • Pore volume is one of the main properties for the characterization of microporous crystals. It is experimentally measurable, and it can also be obtained from the refined unit cell by a number of computational techniques. In this work, we assess the accuracy and the discrepancies between the different computational methods which are commonly used for this purpose, i.e, geometric, helium, and probe center pore volumes, by studying a database of more than 5000 frameworks. We developed a new technique to fully characterize the internal void of a microporous material and to compute the probe-accessible and -occupiable pore volume. Lasty, wemore » show that, unlike the other definitions of pore volume, the occupiable pore volume can be directly related to the experimentally measured pore volumes from nitrogen isotherms.« less
  • The authors present a unified approach to pore size characterization of microporous carbonaceous materials such as activated carbon and carbon fibers by nitrogen, argon, and carbon dioxide adsorption at standard temperatures, 77 K for N{sub 2} and Ar and 273 K for CO{sub 2}. Reference isotherms of N{sub 2}, Ar, and CO{sub 2} in a series of model slit-shaped carbon pores in the range from 0.3 to 36 nm have been calculated from the nonlocal density functional theory (NLDFT) using validated parameters of intermolecular interactions. Carbon dioxide isotherms have also been generated by the grand canonical Monte Carlo (GCMC) methodmore » based on the 3-center model of Harris and Yung. The authors demonstrate the consistency of their approach on examples of pore structure characterization of activated carbons from adsorption isotherms of different gases and from different models (NLDFT and GCMC). Since the CO{sub 2} isotherms measured up to 1 atm are not sensitive to pores wider then 1 nm, the NLDFT method for CO{sub 2} has been extended to high-pressure CO{sub 2} adsorption up to 34 atm. The methods developed are suggested as a practical alternative to traditional phenomenological approaches such as DR, HK, and BJH methods.« less
  • The advantages of establishing the structure of new microporous, crystalline solids such as zeolites, porosils, and aluminum phosphates by using high-resolution electron microscopy are assessed and illustrated with reference to ZSM-5. In particular, it is shown that the structure and symmetry elements of this member of the pentasil family may, by comparison of computed and observed (at 200 and 1000 keV) images, be read off directly in real space. The technique is likely to be of special value in characterizing many new structures, including those that, at the sub-unit-cell level, are composed of recurrent intergrowths of other structures.