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

Abstract

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. With this being said, our results show that precise control of reactions within nano-porous materials ismore » possible, opening the way for advances in fields ranging from catalysis to electrochemistry and sensors.« less

Authors:
 [1];  [2];  [1];  [2];  [3];  [3];  [4];  [1]
  1. Univ. of Texas at Dallas, Richardson, TX (United States)
  2. Wake Forest Univ., Winston-Salem, NC (United States)
  3. Rutgers Univ., Piscataway, NJ (United States)
  4. Wake Forest Univ., Winston-Salem, NC (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Univ. of Texas at Dallas, Richardson, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1501835
Grant/Contract Number:  
FG02-08ER46491
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Applied Sciences
Additional Journal Information:
Journal Volume: 8; Journal Issue: 2; Journal ID: ISSN 2076-3417
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal organic framework; reaction mechanism; confined environment

Citation Formats

Fuentes-Fernandez, Erika, Jensen, Stephanie, Tan, Kui, Zuluaga, Sebastian, Wang, Hao, Li, Jing, Thonhauser, Timo, and Chabal, Yves. Controlling Chemical Reactions in Confined Environments: Water Dissociation in MOF-74. United States: N. p., 2018. Web. doi:10.3390/app8020270.
Fuentes-Fernandez, Erika, Jensen, Stephanie, Tan, Kui, Zuluaga, Sebastian, Wang, Hao, Li, Jing, Thonhauser, Timo, & Chabal, Yves. Controlling Chemical Reactions in Confined Environments: Water Dissociation in MOF-74. United States. doi:10.3390/app8020270.
Fuentes-Fernandez, Erika, Jensen, Stephanie, Tan, Kui, Zuluaga, Sebastian, Wang, Hao, Li, Jing, Thonhauser, Timo, and Chabal, Yves. Mon . "Controlling Chemical Reactions in Confined Environments: Water Dissociation in MOF-74". United States. doi:10.3390/app8020270. https://www.osti.gov/servlets/purl/1501835.
@article{osti_1501835,
title = {Controlling Chemical Reactions in Confined Environments: Water Dissociation in MOF-74},
author = {Fuentes-Fernandez, Erika and Jensen, Stephanie and Tan, Kui and Zuluaga, Sebastian and Wang, Hao and Li, Jing and Thonhauser, Timo and Chabal, Yves},
abstractNote = {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. With this being said, 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.},
doi = {10.3390/app8020270},
journal = {Applied Sciences},
issn = {2076-3417},
number = 2,
volume = 8,
place = {United States},
year = {2018},
month = {2}
}

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