Metal doping in cerium metal-organic frameworks for visible-response water splitting photocatalysts

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Abstract

Cerium metal-organic frameworks (Ce-MOFs) show great promise for photocatalytic water splitting as they have low-lying unoccupied 4f orbitals with energies lower than the unoccupied linker orbitals to drive the ligand-to-metal charge transfer (LMCT) of the photo-generated electron at the linker to separate the photo-excited charges. Nevertheless, the large and negative LMCT energies of Ce-MOFs are often accompanied by high photon-absorption energies, which then limit the application of Ce-MOFs as visible-light-driven water splitting photocatalysts. In this work, we propose that metal (Zr or Ti) doping can raise the very negative LMCT energies of Ce-MOFs, consequently leading to the decrease of the absorption energy and promoting the response of Ce-MOFs to visible light. By functionalizing the linker of the mixed-metal MOFs, we found two possible visible-response photocatalysts for water splitting using a single photocatalyst.

Original languageEnglish (US)
Article number041701
JournalJournal of Chemical Physics
Volume150
Issue number4
DOIs
StatePublished - Jan 28 2019

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Cerium
water splitting
Photocatalysts
cerium
Metals
Doping (additives)
Water
metals
Charge transfer
charge transfer
energy absorption
Ligands
ligands
orbitals
energy
Photons

Cite this

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title = "Metal doping in cerium metal-organic frameworks for visible-response water splitting photocatalysts",
abstract = "Cerium metal-organic frameworks (Ce-MOFs) show great promise for photocatalytic water splitting as they have low-lying unoccupied 4f orbitals with energies lower than the unoccupied linker orbitals to drive the ligand-to-metal charge transfer (LMCT) of the photo-generated electron at the linker to separate the photo-excited charges. Nevertheless, the large and negative LMCT energies of Ce-MOFs are often accompanied by high photon-absorption energies, which then limit the application of Ce-MOFs as visible-light-driven water splitting photocatalysts. In this work, we propose that metal (Zr or Ti) doping can raise the very negative LMCT energies of Ce-MOFs, consequently leading to the decrease of the absorption energy and promoting the response of Ce-MOFs to visible light. By functionalizing the linker of the mixed-metal MOFs, we found two possible visible-response photocatalysts for water splitting using a single photocatalyst.",
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AU - Wu, Xin Ping

AU - Gagliardi, Laura

AU - Truhlar, Donald G.

PY - 2019/1/28

Y1 - 2019/1/28

N2 - Cerium metal-organic frameworks (Ce-MOFs) show great promise for photocatalytic water splitting as they have low-lying unoccupied 4f orbitals with energies lower than the unoccupied linker orbitals to drive the ligand-to-metal charge transfer (LMCT) of the photo-generated electron at the linker to separate the photo-excited charges. Nevertheless, the large and negative LMCT energies of Ce-MOFs are often accompanied by high photon-absorption energies, which then limit the application of Ce-MOFs as visible-light-driven water splitting photocatalysts. In this work, we propose that metal (Zr or Ti) doping can raise the very negative LMCT energies of Ce-MOFs, consequently leading to the decrease of the absorption energy and promoting the response of Ce-MOFs to visible light. By functionalizing the linker of the mixed-metal MOFs, we found two possible visible-response photocatalysts for water splitting using a single photocatalyst.

AB - Cerium metal-organic frameworks (Ce-MOFs) show great promise for photocatalytic water splitting as they have low-lying unoccupied 4f orbitals with energies lower than the unoccupied linker orbitals to drive the ligand-to-metal charge transfer (LMCT) of the photo-generated electron at the linker to separate the photo-excited charges. Nevertheless, the large and negative LMCT energies of Ce-MOFs are often accompanied by high photon-absorption energies, which then limit the application of Ce-MOFs as visible-light-driven water splitting photocatalysts. In this work, we propose that metal (Zr or Ti) doping can raise the very negative LMCT energies of Ce-MOFs, consequently leading to the decrease of the absorption energy and promoting the response of Ce-MOFs to visible light. By functionalizing the linker of the mixed-metal MOFs, we found two possible visible-response photocatalysts for water splitting using a single photocatalyst.

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