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Title: Catechol-Ligated Transition Metals: A Quantum Chemical Study on a Promising System for Gas Separation

Abstract

We report that metal-organic frameworks (MOFs) have received a great deal of attention for their potential in atmospheric filtering, and recent work has shown that catecholate linkers can bind metals, creating MOFs with monocatecholate metal centers and abundant open coordination sites. In this study, M-catecholate systems (with M = Mg 2+, Sc 2+, Ti 2+, V 2+, Cr 2+, Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+, and Zn 2+) were used as computational models of metalated catecholate linkers in MOFs. Nitric oxide (NO) is a radical molecule that is considered an environmental pollutant and is toxic if inhaled in large quantities. Binding NO is of interest in creating atmospheric filters, both at the industrial and personal scale. The binding energies of NO to the metal-catecholate systems were calculated using density functional theory (DFT) and complete active space self-consistent field (CASSCF) followed by second order perturbation (CASPT2). Selectivity was studied by calculating the binding energies of additional guests (CO, NH 3, H 2O, N 2, and CO 2). The toxic guests have stronger binding than the benign guests for all metals studied, and NO has significantly stronger binding than other guests for most of the metals studied, suggestingmore » that metal-catecholates are worthy of further study for NO filtration. Finally, certain metal-catecholates also showed potential for separation of N 2 and CO 2 via N 2 activation, which could be relevant for carbon capture or ammonia synthesis.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Department of Chemistry, Minnesota Supercomputing Institute, and Chemical Theory Center
  2. The Dow Chemical Company, Midland, MI (United States). Core Research and Development
  3. Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry
  4. Northwestern Univ., Evanston, IL (United States). Department of Chemical & Biological Engineering
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) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Contributing Org.:
Minnesota Supercomputing Institute (MSI) at the University of Minnesota
OSTI Identifier:
1477217
Grant/Contract Number:  
FG02-12ER16362; SC0008688
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 19; 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., Livermore, Vanessa, McGreal, Meghan E., Yu, Decai, Vogiatzis, Konstantinos D., Snurr, Randall Q., and Gagliardi, Laura. Catechol-Ligated Transition Metals: A Quantum Chemical Study on a Promising System for Gas Separation. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b02685.
Stoneburner, Samuel J., Livermore, Vanessa, McGreal, Meghan E., Yu, Decai, Vogiatzis, Konstantinos D., Snurr, Randall Q., & Gagliardi, Laura. Catechol-Ligated Transition Metals: A Quantum Chemical Study on a Promising System for Gas Separation. United States. doi:10.1021/acs.jpcc.7b02685.
Stoneburner, Samuel J., Livermore, Vanessa, McGreal, Meghan E., Yu, Decai, Vogiatzis, Konstantinos D., Snurr, Randall Q., and Gagliardi, Laura. Fri . "Catechol-Ligated Transition Metals: A Quantum Chemical Study on a Promising System for Gas Separation". United States. doi:10.1021/acs.jpcc.7b02685. https://www.osti.gov/servlets/purl/1477217.
@article{osti_1477217,
title = {Catechol-Ligated Transition Metals: A Quantum Chemical Study on a Promising System for Gas Separation},
author = {Stoneburner, Samuel J. and Livermore, Vanessa and McGreal, Meghan E. and Yu, Decai and Vogiatzis, Konstantinos D. and Snurr, Randall Q. and Gagliardi, Laura},
abstractNote = {We report that metal-organic frameworks (MOFs) have received a great deal of attention for their potential in atmospheric filtering, and recent work has shown that catecholate linkers can bind metals, creating MOFs with monocatecholate metal centers and abundant open coordination sites. In this study, M-catecholate systems (with M = Mg2+, Sc2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+) were used as computational models of metalated catecholate linkers in MOFs. Nitric oxide (NO) is a radical molecule that is considered an environmental pollutant and is toxic if inhaled in large quantities. Binding NO is of interest in creating atmospheric filters, both at the industrial and personal scale. The binding energies of NO to the metal-catecholate systems were calculated using density functional theory (DFT) and complete active space self-consistent field (CASSCF) followed by second order perturbation (CASPT2). Selectivity was studied by calculating the binding energies of additional guests (CO, NH3, H2O, N2, and CO2). The toxic guests have stronger binding than the benign guests for all metals studied, and NO has significantly stronger binding than other guests for most of the metals studied, suggesting that metal-catecholates are worthy of further study for NO filtration. Finally, certain metal-catecholates also showed potential for separation of N2 and CO2 via N2 activation, which could be relevant for carbon capture or ammonia synthesis.},
doi = {10.1021/acs.jpcc.7b02685},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 19,
volume = 121,
place = {United States},
year = {2017},
month = {4}
}

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