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

Abstract

Cerium metal-organic frameworks (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 limits 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst., Chemical Theory Center, Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1507012
Grant/Contract Number:  
SC0008688; FG02-17ER16362
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wu, Xin-Ping, Gagliardi, Laura, and Truhlar, Donald G. Metal doping in cerium metal-organic frameworks for visible-response water splitting photocatalysts. United States: N. p., 2019. Web. doi:10.1063/1.5043538.
Wu, Xin-Ping, Gagliardi, Laura, & Truhlar, Donald G. Metal doping in cerium metal-organic frameworks for visible-response water splitting photocatalysts. United States. doi:10.1063/1.5043538.
Wu, Xin-Ping, Gagliardi, Laura, and Truhlar, Donald G. Mon . "Metal doping in cerium metal-organic frameworks for visible-response water splitting photocatalysts". United States. doi:10.1063/1.5043538.
@article{osti_1507012,
title = {Metal doping in cerium metal-organic frameworks for visible-response water splitting photocatalysts},
author = {Wu, Xin-Ping and Gagliardi, Laura and Truhlar, Donald G.},
abstractNote = {Cerium metal-organic frameworks (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 limits 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.},
doi = {10.1063/1.5043538},
journal = {Journal of Chemical Physics},
number = 4,
volume = 150,
place = {United States},
year = {2019},
month = {1}
}

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