Design of a Metal–Organic Framework with Enhanced Back Bonding for Separation of N2 and CH4
Abstract
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:
-
- Univ. of California, Berkeley, CA (United States); Univ. of Minnesota, Minneapolis, MN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of Minnesota, Minneapolis, MN (United States)
- Univ. of California, Berkeley, CA (United States); Univ. of Minnesota, Minneapolis, MN (United States)
- Univ. of Minnesota, Minneapolis, MN (United States); Univ. of California, Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States)
- National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
- National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Delaware, Newark, DE (United States)
- Univ. of Minnesota, Minneapolis, MN (United States); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of Minnesota, Minneapolis, MN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1458979
- Grant/Contract Number:
- FG02-12ER16362; SC0008688
- Resource 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)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
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., 2013.
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. https://doi.org/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. Sat .
"Design of a Metal–Organic Framework with Enhanced Back Bonding for Separation of N2 and CH4". United States. https://doi.org/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 = {Sat Dec 07 00:00:00 EST 2013},
month = {Sat Dec 07 00:00:00 EST 2013}
}
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