Predicted Efficient Visible-Light Driven Water Splitting and Carbon Dioxide Reduction Using Photoredox-Active UiO-NDI Metal Organic Framework

Saied Md Pratik, Chris Cramer

Research output: Contribution to journalArticle

Abstract

The structural and electronic properties of metal-organic frameworks (MOFs) constructed from stable Zr(IV) oxide-based nodes and naphthalenediimide-based linkers (UiO(Zr)-NDI) can be tuned to make them useful for specific photoredox processes. The NDI linker presents outside, inside, and core positions where functionalization can influence its optical properties, and such substitution in combination with suitable optical band gaps and band edge positions in UiO(Zr)-NDI offers a platform for the design of efficient MOF-based photocatalysts for water splitting and CO2 reduction. The band gaps and edge positions remain similar for UiO nodes when Zr is substituted with Ti, Th, or Ce. However, in contrast to the case for Zr-, Ti-, and Th-based UiO-NDIs, where photoexcitation remains localized on the NDI linkers owing to the very high energies of unoccupied node-based bands, for UiO(Ce)-NDI, the availability of low-lying empty f orbitals in the metal node offers the potential for energy transfer and exciton migration, which could further boost photocatalytic performance by extending exciton lifetimes.

Original languageEnglish (US)
Pages (from-to)19778-19785
Number of pages8
JournalJournal of Physical Chemistry C
Volume123
Issue number32
DOIs
StatePublished - Aug 15 2019

Fingerprint

water splitting
dioxides
Carbon Dioxide
carbon dioxide
Carbon dioxide
Metals
Excitons
Water
metals
Photoexcitation
Optical band gaps
excitons
Photocatalysts
Electronic properties
Energy transfer
Oxides
Structural properties
Energy gap
Substitution reactions
Optical properties

Cite this

@article{5e91bf6de0a044728d753a76dfa29207,
title = "Predicted Efficient Visible-Light Driven Water Splitting and Carbon Dioxide Reduction Using Photoredox-Active UiO-NDI Metal Organic Framework",
abstract = "The structural and electronic properties of metal-organic frameworks (MOFs) constructed from stable Zr(IV) oxide-based nodes and naphthalenediimide-based linkers (UiO(Zr)-NDI) can be tuned to make them useful for specific photoredox processes. The NDI linker presents outside, inside, and core positions where functionalization can influence its optical properties, and such substitution in combination with suitable optical band gaps and band edge positions in UiO(Zr)-NDI offers a platform for the design of efficient MOF-based photocatalysts for water splitting and CO2 reduction. The band gaps and edge positions remain similar for UiO nodes when Zr is substituted with Ti, Th, or Ce. However, in contrast to the case for Zr-, Ti-, and Th-based UiO-NDIs, where photoexcitation remains localized on the NDI linkers owing to the very high energies of unoccupied node-based bands, for UiO(Ce)-NDI, the availability of low-lying empty f orbitals in the metal node offers the potential for energy transfer and exciton migration, which could further boost photocatalytic performance by extending exciton lifetimes.",
author = "Pratik, {Saied Md} and Chris Cramer",
year = "2019",
month = "8",
day = "15",
doi = "10.1021/acs.jpcc.9b05693",
language = "English (US)",
volume = "123",
pages = "19778--19785",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "32",

}

TY - JOUR

T1 - Predicted Efficient Visible-Light Driven Water Splitting and Carbon Dioxide Reduction Using Photoredox-Active UiO-NDI Metal Organic Framework

AU - Pratik, Saied Md

AU - Cramer, Chris

PY - 2019/8/15

Y1 - 2019/8/15

N2 - The structural and electronic properties of metal-organic frameworks (MOFs) constructed from stable Zr(IV) oxide-based nodes and naphthalenediimide-based linkers (UiO(Zr)-NDI) can be tuned to make them useful for specific photoredox processes. The NDI linker presents outside, inside, and core positions where functionalization can influence its optical properties, and such substitution in combination with suitable optical band gaps and band edge positions in UiO(Zr)-NDI offers a platform for the design of efficient MOF-based photocatalysts for water splitting and CO2 reduction. The band gaps and edge positions remain similar for UiO nodes when Zr is substituted with Ti, Th, or Ce. However, in contrast to the case for Zr-, Ti-, and Th-based UiO-NDIs, where photoexcitation remains localized on the NDI linkers owing to the very high energies of unoccupied node-based bands, for UiO(Ce)-NDI, the availability of low-lying empty f orbitals in the metal node offers the potential for energy transfer and exciton migration, which could further boost photocatalytic performance by extending exciton lifetimes.

AB - The structural and electronic properties of metal-organic frameworks (MOFs) constructed from stable Zr(IV) oxide-based nodes and naphthalenediimide-based linkers (UiO(Zr)-NDI) can be tuned to make them useful for specific photoredox processes. The NDI linker presents outside, inside, and core positions where functionalization can influence its optical properties, and such substitution in combination with suitable optical band gaps and band edge positions in UiO(Zr)-NDI offers a platform for the design of efficient MOF-based photocatalysts for water splitting and CO2 reduction. The band gaps and edge positions remain similar for UiO nodes when Zr is substituted with Ti, Th, or Ce. However, in contrast to the case for Zr-, Ti-, and Th-based UiO-NDIs, where photoexcitation remains localized on the NDI linkers owing to the very high energies of unoccupied node-based bands, for UiO(Ce)-NDI, the availability of low-lying empty f orbitals in the metal node offers the potential for energy transfer and exciton migration, which could further boost photocatalytic performance by extending exciton lifetimes.

UR - http://www.scopus.com/inward/record.url?scp=85070904913&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85070904913&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.9b05693

DO - 10.1021/acs.jpcc.9b05693

M3 - Article

VL - 123

SP - 19778

EP - 19785

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 32

ER -