Cerium Metal-Organic Framework for Photocatalysis

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Ligand-to-metal charge transfer (LMCT) can bring about the separation of photogenerated charges. Here we calculate the electronic structures of metal-organic frameworks (MOFs) having the UiO-66 architecture and M 6 O 4 (OH) 4 inorganometallic nodes with M = Zr, Hf, Th, Ti, U, or Ce. We find that LMCT is favorable only in the Ce case, where it is promoted by the low-lying empty 4f orbitals of Ce 4+ . We therefore propose that incorporating Ce 4+ into the node is an effective way to facilitate LMCT in a MOF. In addition, we show that by functionalizing the linker, it should be possible to engineer the electronic structure of the Ce-MOF for a desired reaction (e.g., water splitting) while preserving favorable LMCT. We also find that linker functionalization with electron donating or withdrawing groups allows tuning of the LMCT energy, and increasing the number of functional groups on each linker enhances the tuning; these findings are encouraging for applying Ce-MOFs for visible-response photocatalytic water splitting.

Original languageEnglish (US)
Pages (from-to)7904-7912
Number of pages9
JournalJournal of the American Chemical Society
Volume140
Issue number25
DOIs
StatePublished - Jun 27 2018

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Cerium
Photocatalysis
Metals
Charge transfer
Ligands
Electronic structure
Tuning
Water
Energy Transfer
Functional groups
Electrons
Engineers

PubMed: MeSH publication types

  • Journal Article
  • Research Support, U.S. Gov't, Non-P.H.S.

Cite this

Cerium Metal-Organic Framework for Photocatalysis. / Wu, Xinping; Gagliardi, Laura; Truhlar, Donald G.

In: Journal of the American Chemical Society, Vol. 140, No. 25, 27.06.2018, p. 7904-7912.

Research output: Contribution to journalArticle

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N2 - Ligand-to-metal charge transfer (LMCT) can bring about the separation of photogenerated charges. Here we calculate the electronic structures of metal-organic frameworks (MOFs) having the UiO-66 architecture and M 6 O 4 (OH) 4 inorganometallic nodes with M = Zr, Hf, Th, Ti, U, or Ce. We find that LMCT is favorable only in the Ce case, where it is promoted by the low-lying empty 4f orbitals of Ce 4+ . We therefore propose that incorporating Ce 4+ into the node is an effective way to facilitate LMCT in a MOF. In addition, we show that by functionalizing the linker, it should be possible to engineer the electronic structure of the Ce-MOF for a desired reaction (e.g., water splitting) while preserving favorable LMCT. We also find that linker functionalization with electron donating or withdrawing groups allows tuning of the LMCT energy, and increasing the number of functional groups on each linker enhances the tuning; these findings are encouraging for applying Ce-MOFs for visible-response photocatalytic water splitting.

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