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Title: Iodine in Metal–Organic Frameworks at High Pressure

Abstract

Capture of highly volatile radioactive iodine is a promising application of metal–organic frameworks (MOFs), thanks to their high porosity with flexible chemical architecture. Specifically, strong charge-transfer binding of iodine to the framework enables efficient and selective iodine uptake as well as its long-term storage. As such, precise knowledge of the electronic structure of iodine is essential for a detailed modeling of the iodine sorption process, which will allow for rational design of iodophilic MOFs in the future. Here we probe the electronic structure of iodine in MOFs at variable iodine···framework interaction by Raman and optical absorption spectroscopy at high pressure (P). The electronic structure of iodine in the straight channels of SBMOF-1 (Ca-sdb, sdb = 4,4'-sulfonyldibenzoate) is modified irreversibly at P > 3.4 GPa by charge transfer, marking a polymerization of iodine molecules into a 1D polyiodide chain. In contrast, iodine in the sinusoidal channels of SBMOF-3 (Cd-sdb) retains its molecular (I2) character up to at least 8.4 GPa. Such divergent high-pressure behavior of iodine in the MOFs with similar port size and chemistry illustrates adaptations of the electronic structure of iodine to channel topology and strength of the iodine···framework interaction, which can be used to tailor iodine-immobilizing MOFs.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [5];  [6];  [7]; ORCiD logo [4];  [8]
  1. Stony Brook Univ., NY (United States). Dept. of Geosciences; Helmholtz Center Potsdam, (Germany). German Research Center for GeoSciences (GFZ)
  2. Stony Brook Univ., NY (United States). Dept. of Chemistry
  3. Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
  4. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  6. Stony Brook Univ., NY (United States). Joint Photon Sciences Inst.
  7. Stony Brook Univ., NY (United States). Dept. of Geosciences; Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  8. Stony Brook Univ., NY (United States). Dept. of Geosciences, Dept. of Chemistry and Joint Photon Sciences Inst.; Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1463855
Report Number(s):
BNL-207930-2018-JAAM
Journal ID: ISSN 1089-5639; TRN: US1902336
Grant/Contract Number:  
SC0012704; EAR 1763287
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 29; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Lobanov, Sergey S., Daly, John A., Goncharov, Alexander F., Chan, Xiaojun, Ghose, Sanjit K., Zhong, Hui, Ehm, Lars, Kim, Taejin, and Parise, John B. Iodine in Metal–Organic Frameworks at High Pressure. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b05443.
Lobanov, Sergey S., Daly, John A., Goncharov, Alexander F., Chan, Xiaojun, Ghose, Sanjit K., Zhong, Hui, Ehm, Lars, Kim, Taejin, & Parise, John B. Iodine in Metal–Organic Frameworks at High Pressure. United States. https://doi.org/10.1021/acs.jpca.8b05443
Lobanov, Sergey S., Daly, John A., Goncharov, Alexander F., Chan, Xiaojun, Ghose, Sanjit K., Zhong, Hui, Ehm, Lars, Kim, Taejin, and Parise, John B. Tue . "Iodine in Metal–Organic Frameworks at High Pressure". United States. https://doi.org/10.1021/acs.jpca.8b05443. https://www.osti.gov/servlets/purl/1463855.
@article{osti_1463855,
title = {Iodine in Metal–Organic Frameworks at High Pressure},
author = {Lobanov, Sergey S. and Daly, John A. and Goncharov, Alexander F. and Chan, Xiaojun and Ghose, Sanjit K. and Zhong, Hui and Ehm, Lars and Kim, Taejin and Parise, John B.},
abstractNote = {Capture of highly volatile radioactive iodine is a promising application of metal–organic frameworks (MOFs), thanks to their high porosity with flexible chemical architecture. Specifically, strong charge-transfer binding of iodine to the framework enables efficient and selective iodine uptake as well as its long-term storage. As such, precise knowledge of the electronic structure of iodine is essential for a detailed modeling of the iodine sorption process, which will allow for rational design of iodophilic MOFs in the future. Here we probe the electronic structure of iodine in MOFs at variable iodine···framework interaction by Raman and optical absorption spectroscopy at high pressure (P). The electronic structure of iodine in the straight channels of SBMOF-1 (Ca-sdb, sdb = 4,4'-sulfonyldibenzoate) is modified irreversibly at P > 3.4 GPa by charge transfer, marking a polymerization of iodine molecules into a 1D polyiodide chain. In contrast, iodine in the sinusoidal channels of SBMOF-3 (Cd-sdb) retains its molecular (I2) character up to at least 8.4 GPa. Such divergent high-pressure behavior of iodine in the MOFs with similar port size and chemistry illustrates adaptations of the electronic structure of iodine to channel topology and strength of the iodine···framework interaction, which can be used to tailor iodine-immobilizing MOFs.},
doi = {10.1021/acs.jpca.8b05443},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 29,
volume = 122,
place = {United States},
year = {2018},
month = {7}
}

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