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

Zuluaga, S.; Fuentes-Fernandez, E. M.  A.; Tan, K.; Arter, C. A.; Li, J.; Chabal, Y. J.; Thonhauser, T.

doi:10.1039/c6ta04388g

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

Journal Article · Fri Jan 01 00:00:00 EST 2016 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/c6ta04388g· OSTI ID:1565463

Zuluaga, S. ^[1]; Fuentes-Fernandez, E. M. A. ^[2]; Tan, K. ^[2]; Arter, C. A. ^[1]; Li, J. ^[3]; Chabal, Y. J. ^[2]; Thonhauser, T. ^[1]

Department of Physics; Wake Forest University; Winston-Salem; USA
Department of Materials Science and Engineering; University of Texas at Dallas; Richardson; USA
Department of Chemistry and Chemical Biology; Rutgers University; Piscataway; USA

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.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: AC05-00OR22725; FG02-08ER46491

OSTI ID:: 1565463

Journal Information:: Journal of Materials Chemistry. A, Vol. 4, Issue 34; ISSN 2050-7488

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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