Controlling chemical reactions in confined environments: Water dissociation in MOF-74

Erika M.A. Fuentes-Fernandez, Stephanie Jensen, Kui Tan, Sebastian Zuluaga, Hao Wang, Jing Li, Timo Thonhauser, Yves J. Chabal

Research output: Contribution to journalArticle

1 Citation (Scopus)

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. 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.

Original languageEnglish
Article number270
JournalApplied Sciences (Switzerland)
Volume8
Issue number2
DOIs
Publication statusPublished - Feb 12 2018

Fingerprint

Chemical reactions
chemical reactions
Metals
dissociation
Water
metals
water
alcohols
Alcohols
2-Propanol
Electrochemistry
porous materials
Materials science
electrochemistry
materials science
biology
Partial pressure
Oxides
Catalysis
catalysis

Keywords

  • Confined environment
  • Metal organic framework
  • Reaction mechanism

ASJC Scopus subject areas

  • Materials Science(all)
  • Instrumentation
  • Engineering(all)
  • Process Chemistry and Technology
  • Computer Science Applications
  • Fluid Flow and Transfer Processes

Cite this

Fuentes-Fernandez, E. M. A., Jensen, S., Tan, K., Zuluaga, S., Wang, H., Li, J., ... Chabal, Y. J. (2018). Controlling chemical reactions in confined environments: Water dissociation in MOF-74. Applied Sciences (Switzerland), 8(2), [270]. https://doi.org/10.3390/app8020270

Controlling chemical reactions in confined environments : Water dissociation in MOF-74. / Fuentes-Fernandez, Erika M.A.; Jensen, Stephanie; Tan, Kui; Zuluaga, Sebastian; Wang, Hao; Li, Jing; Thonhauser, Timo; Chabal, Yves J.

In: Applied Sciences (Switzerland), Vol. 8, No. 2, 270, 12.02.2018.

Research output: Contribution to journalArticle

Fuentes-Fernandez, EMA, Jensen, S, Tan, K, Zuluaga, S, Wang, H, Li, J, Thonhauser, T & Chabal, YJ 2018, 'Controlling chemical reactions in confined environments: Water dissociation in MOF-74', Applied Sciences (Switzerland), vol. 8, no. 2, 270. https://doi.org/10.3390/app8020270
Fuentes-Fernandez, Erika M.A. ; Jensen, Stephanie ; Tan, Kui ; Zuluaga, Sebastian ; Wang, Hao ; Li, Jing ; Thonhauser, Timo ; Chabal, Yves J. / Controlling chemical reactions in confined environments : Water dissociation in MOF-74. In: Applied Sciences (Switzerland). 2018 ; Vol. 8, No. 2.
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