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Title: A Diaminopropane-Appended Metal–Organic Framework Enabling Efficient CO 2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism

Abstract

A new diamine-functionalized metal–organic framework comprised of 2,2-dimethyl-1,3-diaminopropane (dmpn) appended to the Mg 2+ sites lining the channels of Mg 2(dobpdc) (dobpdc4– = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) is characterized for the removal of CO 2 from the flue gas emissions of coal-fired power plants. Unique to members of this promising class of adsorbents, dmpn–Mg2(dobpdc) displays facile step-shaped adsorption of CO 2 from coal flue gas at 40 °C and near complete CO 2 desorption upon heating to 100 °C, enabling a high CO 2 working capacity (2.42 mmol/g, 9.1 wt %) with a modest 60 °C temperature swing. Evaluation of the thermodynamic parameters of adsorption for dmpn–Mg 2(dobpdc) suggests that the narrow temperature swing of its CO 2 adsorption steps is due to the high magnitude of its differential enthalpy of adsorption (Δhads = -73 ± 1 kJ/mol), with a larger than expected entropic penalty for CO 2 adsorption (Δsads = -204 ± 4 J/mol·K) positioning the step in the optimal range for carbon capture from coal flue gas. In addition, thermogravimetric analysis and breakthrough experiments indicate that, in contrast to many adsorbents, dmpn–Mg 2(dobpdc) captures CO 2 effectively in the presence of water and can be subjected to 1000 humid adsorption/desorption cyclesmore » with minimal degradation. Solid-state 13C NMR spectra and single-crystal X-ray diffraction structures of the Zn analogue reveal that this material adsorbs CO 2 via formation of both ammonium carbamates and carbamic acid pairs, the latter of which are crystallographically verified for the first time in a porous material. Taken together, these properties render dmpn–Mg 2(dobpdc) one of the most promising adsorbents for carbon capture applications.« less

Authors:
; ; ; ;  [1]; ; ; ORCiD logo [1]
  1. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Advanced Research Projects Agency - Energy (ARPA-E); Exxonmobil Research and Engineering Company (EMRE), Clinton, NJ (United States); National Institutes of Health (NIH); Philomathia Foundation
OSTI Identifier:
1406619
DOE Contract Number:  
AC02-05CH11231; SC0001015; F32GM120799; AC02-06CH11357; S10OD023523
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 38; 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

Milner, Phillip J., Siegelman, Rebecca L., Forse, Alexander C., Gonzalez, Miguel I., Runčevski, Tomče, Martell, Jeffrey D., Reimer, Jeffrey A., and Long, Jeffrey R. A Diaminopropane-Appended Metal–Organic Framework Enabling Efficient CO 2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism. United States: N. p., 2017. Web. doi:10.1021/jacs.7b07612.
Milner, Phillip J., Siegelman, Rebecca L., Forse, Alexander C., Gonzalez, Miguel I., Runčevski, Tomče, Martell, Jeffrey D., Reimer, Jeffrey A., & Long, Jeffrey R. A Diaminopropane-Appended Metal–Organic Framework Enabling Efficient CO 2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism. United States. doi:10.1021/jacs.7b07612.
Milner, Phillip J., Siegelman, Rebecca L., Forse, Alexander C., Gonzalez, Miguel I., Runčevski, Tomče, Martell, Jeffrey D., Reimer, Jeffrey A., and Long, Jeffrey R. Thu . "A Diaminopropane-Appended Metal–Organic Framework Enabling Efficient CO 2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism". United States. doi:10.1021/jacs.7b07612.
@article{osti_1406619,
title = {A Diaminopropane-Appended Metal–Organic Framework Enabling Efficient CO 2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism},
author = {Milner, Phillip J. and Siegelman, Rebecca L. and Forse, Alexander C. and Gonzalez, Miguel I. and Runčevski, Tomče and Martell, Jeffrey D. and Reimer, Jeffrey A. and Long, Jeffrey R.},
abstractNote = {A new diamine-functionalized metal–organic framework comprised of 2,2-dimethyl-1,3-diaminopropane (dmpn) appended to the Mg2+ sites lining the channels of Mg2(dobpdc) (dobpdc4– = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) is characterized for the removal of CO2 from the flue gas emissions of coal-fired power plants. Unique to members of this promising class of adsorbents, dmpn–Mg2(dobpdc) displays facile step-shaped adsorption of CO2 from coal flue gas at 40 °C and near complete CO2 desorption upon heating to 100 °C, enabling a high CO2 working capacity (2.42 mmol/g, 9.1 wt %) with a modest 60 °C temperature swing. Evaluation of the thermodynamic parameters of adsorption for dmpn–Mg2(dobpdc) suggests that the narrow temperature swing of its CO2 adsorption steps is due to the high magnitude of its differential enthalpy of adsorption (Δhads = -73 ± 1 kJ/mol), with a larger than expected entropic penalty for CO2 adsorption (Δsads = -204 ± 4 J/mol·K) positioning the step in the optimal range for carbon capture from coal flue gas. In addition, thermogravimetric analysis and breakthrough experiments indicate that, in contrast to many adsorbents, dmpn–Mg2(dobpdc) captures CO2 effectively in the presence of water and can be subjected to 1000 humid adsorption/desorption cycles with minimal degradation. Solid-state 13C NMR spectra and single-crystal X-ray diffraction structures of the Zn analogue reveal that this material adsorbs CO2 via formation of both ammonium carbamates and carbamic acid pairs, the latter of which are crystallographically verified for the first time in a porous material. Taken together, these properties render dmpn–Mg2(dobpdc) one of the most promising adsorbents for carbon capture applications.},
doi = {10.1021/jacs.7b07612},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 38,
volume = 139,
place = {United States},
year = {2017},
month = {9}
}