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Title: Design of a Metal–Organic Framework with Enhanced Back Bonding for Separation of N 2 and CH 4

Gas separations with porous materials are economically important and provide a unique challenge to fundamental materials design, as adsorbent properties can be altered to achieve selective gas adsorption. Metal–organic frameworks represent a rapidly expanding new class of porous adsorbents with a large range of possibilities for designing materials with desired functionalities. Given the large number of possible framework structures, quantum mechanical computations can provide useful guidance in prioritizing the synthesis of the most useful materials for a given application. Here, we show that such calculations can predict a new metal–organic framework of potential utility for separation of dinitrogen from methane, a particularly challenging separation of critical value for utilizing natural gas. In conclusion, an open V(II) site incorporated into a metal–organic framework can provide a material with a considerably higher enthalpy of adsorption for dinitrogen than for methane, based on strong selective back bonding with the former but not the latter.
Authors:
 [1] ;  [2] ;  [2] ;  [2] ;  [2] ;  [3] ;  [1] ;  [4] ;  [5] ;  [6] ;  [7] ;  [8] ;  [9] ;  [1] ;  [2] ;  [2] ;  [2]
  1. Univ. of California, Berkeley, CA (United States); Univ. of Minnesota, Minneapolis, MN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Univ. of California, Berkeley, CA (United States); Univ. of Minnesota, Minneapolis, MN (United States)
  4. Univ. of Minnesota, Minneapolis, MN (United States); Univ. of California, Berkeley, CA (United States)
  5. Univ. of California, Berkeley, CA (United States)
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  7. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Delaware, Newark, DE (United States)
  8. Univ. of Minnesota, Minneapolis, MN (United States); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  9. Univ. of Minnesota, Minneapolis, MN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
FG02-12ER16362; SC0008688
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 136; Journal Issue: 2; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1458979

Lee, Kyuho, Isley, III, William C., Dzubak, Allison L., Verma, Pragya, Stoneburner, Samuel J., Lin, Li -Chiang, Howe, Joshua D., Bloch, Eric D., Reed, Douglas A., Hudson, Matthew R., Brown, Craig M., Long, Jeffrey R., Neaton, Jeffrey B., Smit, Berend, Cramer, Christopher J., Truhlar, Donald G., and Gagliardi, Laura. Design of a Metal–Organic Framework with Enhanced Back Bonding for Separation of N2 and CH4. United States: N. p., Web. doi:10.1021/ja4102979.
Lee, Kyuho, Isley, III, William C., Dzubak, Allison L., Verma, Pragya, Stoneburner, Samuel J., Lin, Li -Chiang, Howe, Joshua D., Bloch, Eric D., Reed, Douglas A., Hudson, Matthew R., Brown, Craig M., Long, Jeffrey R., Neaton, Jeffrey B., Smit, Berend, Cramer, Christopher J., Truhlar, Donald G., & Gagliardi, Laura. Design of a Metal–Organic Framework with Enhanced Back Bonding for Separation of N2 and CH4. United States. doi:10.1021/ja4102979.
Lee, Kyuho, Isley, III, William C., Dzubak, Allison L., Verma, Pragya, Stoneburner, Samuel J., Lin, Li -Chiang, Howe, Joshua D., Bloch, Eric D., Reed, Douglas A., Hudson, Matthew R., Brown, Craig M., Long, Jeffrey R., Neaton, Jeffrey B., Smit, Berend, Cramer, Christopher J., Truhlar, Donald G., and Gagliardi, Laura. 2013. "Design of a Metal–Organic Framework with Enhanced Back Bonding for Separation of N2 and CH4". United States. doi:10.1021/ja4102979. https://www.osti.gov/servlets/purl/1458979.
@article{osti_1458979,
title = {Design of a Metal–Organic Framework with Enhanced Back Bonding for Separation of N2 and CH4},
author = {Lee, Kyuho and Isley, III, William C. and Dzubak, Allison L. and Verma, Pragya and Stoneburner, Samuel J. and Lin, Li -Chiang and Howe, Joshua D. and Bloch, Eric D. and Reed, Douglas A. and Hudson, Matthew R. and Brown, Craig M. and Long, Jeffrey R. and Neaton, Jeffrey B. and Smit, Berend and Cramer, Christopher J. and Truhlar, Donald G. and Gagliardi, Laura},
abstractNote = {Gas separations with porous materials are economically important and provide a unique challenge to fundamental materials design, as adsorbent properties can be altered to achieve selective gas adsorption. Metal–organic frameworks represent a rapidly expanding new class of porous adsorbents with a large range of possibilities for designing materials with desired functionalities. Given the large number of possible framework structures, quantum mechanical computations can provide useful guidance in prioritizing the synthesis of the most useful materials for a given application. Here, we show that such calculations can predict a new metal–organic framework of potential utility for separation of dinitrogen from methane, a particularly challenging separation of critical value for utilizing natural gas. In conclusion, an open V(II) site incorporated into a metal–organic framework can provide a material with a considerably higher enthalpy of adsorption for dinitrogen than for methane, based on strong selective back bonding with the former but not the latter.},
doi = {10.1021/ja4102979},
journal = {Journal of the American Chemical Society},
number = 2,
volume = 136,
place = {United States},
year = {2013},
month = {12}
}