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Title: Air Separation by Catechol-Ligated Transition Metals: A Quantum Chemical Screening

Abstract

In this study, the separation of O2 and N2 from air is of great importance in a variety of industrial contexts, but the primary means of accomplishing the separation is cryogenic distillation, an energy-intensive process. A material that could enable air separation to occur at conventional temperatures would be of great economic and environmental benefit. Metalated catecholates within metal-organic frameworks have been considered for other gas separations and are shown here to have significant potential for air separation. Calculations of interaction energies between catecholates with first-row transition metals and guests O2 and N2 were performed using density functional theory and multireference complete active space self- consistent field followed by second order perturbation theory. A general recipe is offered for active space selection for metalated-catecholate systems. The multireference results are used to rationalize O2 binding in terms of redox activity with the metalated catecholate. O2 is predicted to bind more strongly than N2 for all cases except Cu2+ , with general agreement in the binding trends among all methods.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1488859
Grant/Contract Number:  
SC0008688
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 39; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Stoneburner, Samuel J., and Gagliardi, Laura. Air Separation by Catechol-Ligated Transition Metals: A Quantum Chemical Screening. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.jpcc.8b03599.
Stoneburner, Samuel J., & Gagliardi, Laura. Air Separation by Catechol-Ligated Transition Metals: A Quantum Chemical Screening. United States. https://doi.org/10.1021/acs.jpcc.8b03599
Stoneburner, Samuel J., and Gagliardi, Laura. Thu . "Air Separation by Catechol-Ligated Transition Metals: A Quantum Chemical Screening". United States. https://doi.org/10.1021/acs.jpcc.8b03599. https://www.osti.gov/servlets/purl/1488859.
@article{osti_1488859,
title = {Air Separation by Catechol-Ligated Transition Metals: A Quantum Chemical Screening},
author = {Stoneburner, Samuel J. and Gagliardi, Laura},
abstractNote = {In this study, the separation of O2 and N2 from air is of great importance in a variety of industrial contexts, but the primary means of accomplishing the separation is cryogenic distillation, an energy-intensive process. A material that could enable air separation to occur at conventional temperatures would be of great economic and environmental benefit. Metalated catecholates within metal-organic frameworks have been considered for other gas separations and are shown here to have significant potential for air separation. Calculations of interaction energies between catecholates with first-row transition metals and guests O2 and N2 were performed using density functional theory and multireference complete active space self- consistent field followed by second order perturbation theory. A general recipe is offered for active space selection for metalated-catecholate systems. The multireference results are used to rationalize O2 binding in terms of redox activity with the metalated catecholate. O2 is predicted to bind more strongly than N2 for all cases except Cu2+ , with general agreement in the binding trends among all methods.},
doi = {10.1021/acs.jpcc.8b03599},
journal = {Journal of Physical Chemistry. C},
number = 39,
volume = 122,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
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Cited by: 2 works
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Figures / Tables:

Figure 1 Figure 1: DFT and PT2 electronic bonding energies (ΔEb, kcal/mol) of O2 and N2 to cat-M2+ systems. DFT N2 results are from previous work.23 M06-L results are absent for Mn-N2, V, and Cr due to convergence failures.

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