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Title: Selective, High-Temperature O2 Adsorption in Chemically Reduced, Redox-Active Iron-Pyrazolate Metal–Organic Frameworks

Abstract

Developing O2-selective adsorbents that can produce high-purity oxygen from air remains a significant challenge. Here, we show that chemically reduced metal–organic framework materials of the type AxFe2(bdp)3 (A = Na+, K+; bdp2- = 1,4-benzenedipyrazolate; 0 < x ≤ 2), which feature coordinatively saturated iron centers, are capable of strong and selective adsorption of O2 over N2 at ambient (25 °C) or even elevated (200 °C) temperature. A combination of gas adsorption analysis, single-crystal X-ray diffraction, magnetic susceptibility measurements, and a range of spectroscopic methods, including 23Na solid-state NMR, Mössbauer, and X-ray photoelectron spectroscopies, are employed as probes of O2 uptake. Significantly, the results support a selective adsorption mechanism involving outer-sphere electron transfer from the framework to form superoxide species, which are subsequently stabilized by intercalated alkali metal cations that reside in the one-dimensional triangular pores of the structure. We further demonstrate similar O2 uptake behavior to that of AxFe2(bdp)3 in an expanded-pore framework analogue and thereby gain additional insight into the O2 adsorption mechanism. The chemical reduction of a robust metal–organic framework to render it capable of binding O2 through such an outer-sphere electron transfer mechanism represents a promising and underexplored strategy for the design of next-generation O2 adsorbents.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); 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)
OSTI Identifier:
1644174
Alternate Identifier(s):
OSTI ID: 1644171; OSTI ID: 1644172
Grant/Contract Number:  
SC0019992; AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 34; 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; 36 MATERIALS SCIENCE; Metal–organic frameworks; air separation; gas adsorption; redox activity; oxygen purification; crystallography

Citation Formats

Jaffe, Adam, Ziebel, Michael E., Halat, David M., Biggins, Naomi, Murphy, Ryan A., Chakarawet, Khetpakorn, Reimer, Jeffrey A., and Long, Jeffrey R. Selective, High-Temperature O2 Adsorption in Chemically Reduced, Redox-Active Iron-Pyrazolate Metal–Organic Frameworks. United States: N. p., 2020. Web. https://doi.org/10.1021/jacs.0c06570.
Jaffe, Adam, Ziebel, Michael E., Halat, David M., Biggins, Naomi, Murphy, Ryan A., Chakarawet, Khetpakorn, Reimer, Jeffrey A., & Long, Jeffrey R. Selective, High-Temperature O2 Adsorption in Chemically Reduced, Redox-Active Iron-Pyrazolate Metal–Organic Frameworks. United States. https://doi.org/10.1021/jacs.0c06570
Jaffe, Adam, Ziebel, Michael E., Halat, David M., Biggins, Naomi, Murphy, Ryan A., Chakarawet, Khetpakorn, Reimer, Jeffrey A., and Long, Jeffrey R. Wed . "Selective, High-Temperature O2 Adsorption in Chemically Reduced, Redox-Active Iron-Pyrazolate Metal–Organic Frameworks". United States. https://doi.org/10.1021/jacs.0c06570. https://www.osti.gov/servlets/purl/1644174.
@article{osti_1644174,
title = {Selective, High-Temperature O2 Adsorption in Chemically Reduced, Redox-Active Iron-Pyrazolate Metal–Organic Frameworks},
author = {Jaffe, Adam and Ziebel, Michael E. and Halat, David M. and Biggins, Naomi and Murphy, Ryan A. and Chakarawet, Khetpakorn and Reimer, Jeffrey A. and Long, Jeffrey R.},
abstractNote = {Developing O2-selective adsorbents that can produce high-purity oxygen from air remains a significant challenge. Here, we show that chemically reduced metal–organic framework materials of the type AxFe2(bdp)3 (A = Na+, K+; bdp2- = 1,4-benzenedipyrazolate; 0 < x ≤ 2), which feature coordinatively saturated iron centers, are capable of strong and selective adsorption of O2 over N2 at ambient (25 °C) or even elevated (200 °C) temperature. A combination of gas adsorption analysis, single-crystal X-ray diffraction, magnetic susceptibility measurements, and a range of spectroscopic methods, including 23Na solid-state NMR, Mössbauer, and X-ray photoelectron spectroscopies, are employed as probes of O2 uptake. Significantly, the results support a selective adsorption mechanism involving outer-sphere electron transfer from the framework to form superoxide species, which are subsequently stabilized by intercalated alkali metal cations that reside in the one-dimensional triangular pores of the structure. We further demonstrate similar O2 uptake behavior to that of AxFe2(bdp)3 in an expanded-pore framework analogue and thereby gain additional insight into the O2 adsorption mechanism. The chemical reduction of a robust metal–organic framework to render it capable of binding O2 through such an outer-sphere electron transfer mechanism represents a promising and underexplored strategy for the design of next-generation O2 adsorbents.},
doi = {10.1021/jacs.0c06570},
journal = {Journal of the American Chemical Society},
number = 34,
volume = 142,
place = {United States},
year = {2020},
month = {7}
}

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