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Controlling Chemical Reactions in Confined Environments: Water Dissociation in MOF-74

Department of Materials Science and Engineering, University of Texas at Dallas, Richardson, TX 75080, USA
Department of Physics and Center for Functional Materials, Wake Forest University, Winston-Salem, NC 27109, USA
Department of Chemistry and Chemical Biology, Rutgers University, Piscataway, NJ 08854, USA
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
Author to whom correspondence should be addressed.
These authors contributed equally to this work.
Appl. Sci. 2018, 8(2), 270;
Received: 5 January 2018 / Revised: 31 January 2018 / Accepted: 1 February 2018 / Published: 12 February 2018
(This article belongs to the Special Issue Nanoporous Materials and Their Applications)
PDF [1396 KB, uploaded 12 February 2018]


The confined porous environment of metal organic frameworks (MOFs) is an attractive system for studying reaction mechanisms. Compared to flat oxide surfaces, MOFs have the key advantage that they exhibit a well-defined structure and present significantly fewer challenges in experimental characterization. As an example of an important reaction, we study here the dissociation of water—which plays a critical role in biology, chemistry, and materials science—in MOFs and show how the knowledge of the structure in this confined environment allows for an unprecedented level of understanding and control. In particular, combining in-situ infrared spectroscopy and first-principles calculations, we show that the water dissociation reaction can be selectively controlled inside Zn-MOF-74 by alcohol, through both chemical and physical interactions. Methanol is observed to speed up water dissociation by 25% to 100%, depending on the alcohol partial pressure. On the other hand, co-adsorption of isopropanol reduces the speed of the water reaction, due mostly to steric interactions. In addition, we also investigate the stability of the product state after the water dissociation has occurred and find that the presence of additional water significantly stabilizes the dissociated state. Our results show that precise control of reactions within nano-porous materials is possible, opening the way for advances in fields ranging from catalysis to electrochemistry and sensors. View Full-Text
Keywords: metal organic framework; reaction mechanism; confined environment metal organic framework; reaction mechanism; confined environment

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Fuentes-Fernandez, E.M.A.; Jensen, S.; Tan, K.; Zuluaga, S.; Wang, H.; Li, J.; Thonhauser, T.; Chabal, Y.J. Controlling Chemical Reactions in Confined Environments: Water Dissociation in MOF-74. Appl. Sci. 2018, 8, 270.

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