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Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
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Cerium Metal-Organic Framework for Photocatalysis
Xin-Ping Wu1, Laura Gagliardi1, Donald G Truhlar1
1Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute , University of Minnesota , Minneapolis , Minnesota 55455-0431 , United States.
Journal of the American Chemical Society
|May 30, 2018
Summary
Incorporating cerium (Ce) into metal-organic frameworks (MOFs) facilitates ligand-to-metal charge transfer (LMCT), enhancing photogenerated charge separation. Functionalizing linkers further tunes electronic structures for applications like photocatalytic water splitting.
Area of Science:
- Materials Science
- Photochemistry
- Inorganic Chemistry
Background:
- Ligand-to-metal charge transfer (LMCT) is crucial for separating photogenerated charges in materials.
- Metal-organic frameworks (MOFs) offer tunable structures for various applications.
Purpose of the Study:
- To investigate the electronic structures of UiO-66 MOFs with different metal nodes (M = Zr, Hf, Th, Ti, U, Ce).
- To determine the feasibility of LMCT in these MOFs and identify strategies for promoting it.
- To explore the potential of cerium (Ce)-based MOFs for photocatalytic applications, such as water splitting.
Main Methods:
- Computational electronic structure calculations were performed for various MOFs.
- The electronic structures of MOFs with M6O4(OH)4 inorganic nodes were analyzed.
- The effect of linker functionalization on LMCT energy was investigated.
Main Results:
- LMCT was found to be favorable only in cerium (Ce)-based MOFs.
- The low-lying empty 4f orbitals of Ce4+ promote LMCT in these structures.
- Linker functionalization with electron-donating or withdrawing groups allows tuning of LMCT energy.
- Increasing the number of functional groups on linkers enhances LMCT energy tuning.
Conclusions:
- Incorporating Ce4+ into MOF nodes is an effective strategy to facilitate LMCT.
- Ce-MOFs can be engineered via linker functionalization for specific reactions like water splitting.
- These findings support the application of Ce-MOFs in visible-light-driven photocatalysis.
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