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Title: Chemistry in confined spaces: reactivity of the Zn-MOF-74 channels

Abstract

Using infrared spectroscopy combined with ab initio methods we study reactions of H2O and CO inside the confined spaces of Zn-MOF-74 channels. Our results show that, once the water dissociation reaction H2O → OH + H takes place at the metal centers, the addition of 40 Torr of CO at 200 °C starts the production of formic acid via OH + H + CO → HCO2H. Our detailed analysis shows that the overall reaction H2O + CO → HCO2H takes place in the confinement of MOF-74 without an external catalyst, unlike the same reaction on flat surfaces. This discovery has several important consequences: it opens the door to a new set of catalytic reactions inside the channels of the MOF-74 system, it suggests that a recovery of the MOF's adsorption capacity is possible after it has been exposed to water (which in turn stabilizes its crystal structure), and it produces the important industrial feedstock formic acid.

Authors:
 [1];  [2];  [2];  [1];  [3];  [2];  [1]
  1. Department of Physics; Wake Forest University; Winston-Salem; USA
  2. Department of Materials Science and Engineering; University of Texas at Dallas; Richardson; USA
  3. Department of Chemistry and Chemical Biology; Rutgers University; Piscataway; USA
Publication Date:
Research Org.:
Oak Ridge National Laboratory, Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1565463
DOE Contract Number:  
AC05-00OR22725; FG02-08ER46491
Resource Type:
Journal Article
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 4; Journal Issue: 34; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Energy & Fuels; Materials Science

Citation Formats

Zuluaga, S., Fuentes-Fernandez, E. M. A., Tan, K., Arter, C. A., Li, J., Chabal, Y. J., and Thonhauser, T. Chemistry in confined spaces: reactivity of the Zn-MOF-74 channels. United States: N. p., 2016. Web. doi:10.1039/c6ta04388g.
Zuluaga, S., Fuentes-Fernandez, E. M. A., Tan, K., Arter, C. A., Li, J., Chabal, Y. J., & Thonhauser, T. Chemistry in confined spaces: reactivity of the Zn-MOF-74 channels. United States. doi:10.1039/c6ta04388g.
Zuluaga, S., Fuentes-Fernandez, E. M. A., Tan, K., Arter, C. A., Li, J., Chabal, Y. J., and Thonhauser, T. Fri . "Chemistry in confined spaces: reactivity of the Zn-MOF-74 channels". United States. doi:10.1039/c6ta04388g.
@article{osti_1565463,
title = {Chemistry in confined spaces: reactivity of the Zn-MOF-74 channels},
author = {Zuluaga, S. and Fuentes-Fernandez, E. M. A. and Tan, K. and Arter, C. A. and Li, J. and Chabal, Y. J. and Thonhauser, T.},
abstractNote = {Using infrared spectroscopy combined with ab initio methods we study reactions of H2O and CO inside the confined spaces of Zn-MOF-74 channels. Our results show that, once the water dissociation reaction H2O → OH + H takes place at the metal centers, the addition of 40 Torr of CO at 200 °C starts the production of formic acid via OH + H + CO → HCO2H. Our detailed analysis shows that the overall reaction H2O + CO → HCO2H takes place in the confinement of MOF-74 without an external catalyst, unlike the same reaction on flat surfaces. This discovery has several important consequences: it opens the door to a new set of catalytic reactions inside the channels of the MOF-74 system, it suggests that a recovery of the MOF's adsorption capacity is possible after it has been exposed to water (which in turn stabilizes its crystal structure), and it produces the important industrial feedstock formic acid.},
doi = {10.1039/c6ta04388g},
journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 34,
volume = 4,
place = {United States},
year = {2016},
month = {1}
}

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