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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b07612· OSTI ID:1406619
; ; ; ;  [1]; ; ;  [1]
  1. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
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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.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Organization:
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 Inst. of Health (NIH); Philomathia Foundation
DOE Contract Number:
AC02-05CH11231; SC0001015; AC02-06CH11357
OSTI ID:
1406619
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 38 Vol. 139; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH

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