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Ultrafast charge transfer dynamics in 2D covalent organic frameworks/Re-complex hybrid photocatalyst

Pan, Qinying ; Abdellah, Mohamed LU ; Cao, Yuehan ; Lin, Weihua LU ; Liu, Yang ; Meng, Jie ; Zhou, Quan ; Zhao, Qian ; Yan, Xiaomei and Li, Zonglong , et al. (2022) In Nature Communications 13(1).
Abstract

Rhenium(I)-carbonyl-diimine complexes have emerged as promising photocatalysts for carbon dioxide reduction with covalent organic frameworks recognized as perfect sensitizers and scaffold support. Such Re complexes/covalent organic frameworks hybrid catalysts have demonstrated high carbon dioxide reduction activities but with strong excitation energy-dependence. In this paper, we rationalize this behavior by the excitation energy-dependent pathways of internal photo-induced charge transfer studied via transient optical spectroscopies and time-dependent density-functional theory calculation. Under band-edge excitation, the excited electrons are quickly injected from covalent organic frameworks moiety into catalytic RheniumI... (More)

Rhenium(I)-carbonyl-diimine complexes have emerged as promising photocatalysts for carbon dioxide reduction with covalent organic frameworks recognized as perfect sensitizers and scaffold support. Such Re complexes/covalent organic frameworks hybrid catalysts have demonstrated high carbon dioxide reduction activities but with strong excitation energy-dependence. In this paper, we rationalize this behavior by the excitation energy-dependent pathways of internal photo-induced charge transfer studied via transient optical spectroscopies and time-dependent density-functional theory calculation. Under band-edge excitation, the excited electrons are quickly injected from covalent organic frameworks moiety into catalytic RheniumI center within picosecond but followed by fast backward geminate recombination. While under excitation with high-energy photon, the injected electrons are located at high-energy levels in RheniumI centers with longer lifetime. Besides those injected electrons to RheniumI center, there still remain some long-lived electrons in covalent organic frameworks moiety which is transferred back from RheniumI. This facilitates the two-electron reaction of carbon dioxide conversion to carbon monoxide.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Nature Communications
volume
13
issue
1
article number
845
publisher
Nature Publishing Group
external identifiers
  • scopus:85124578805
  • pmid:35149679
ISSN
2041-1723
DOI
10.1038/s41467-022-28409-2
language
English
LU publication?
yes
id
fb8b99ea-cff1-4264-bd55-3fdf7cd8d083
date added to LUP
2022-05-18 14:58:36
date last changed
2022-08-05 00:15:33
@article{fb8b99ea-cff1-4264-bd55-3fdf7cd8d083,
  abstract     = {{<p>Rhenium(I)-carbonyl-diimine complexes have emerged as promising photocatalysts for carbon dioxide reduction with covalent organic frameworks recognized as perfect sensitizers and scaffold support. Such Re complexes/covalent organic frameworks hybrid catalysts have demonstrated high carbon dioxide reduction activities but with strong excitation energy-dependence. In this paper, we rationalize this behavior by the excitation energy-dependent pathways of internal photo-induced charge transfer studied via transient optical spectroscopies and time-dependent density-functional theory calculation. Under band-edge excitation, the excited electrons are quickly injected from covalent organic frameworks moiety into catalytic Rhenium<sup>I</sup> center within picosecond but followed by fast backward geminate recombination. While under excitation with high-energy photon, the injected electrons are located at high-energy levels in Rhenium<sup>I</sup> centers with longer lifetime. Besides those injected electrons to Rhenium<sup>I</sup> center, there still remain some long-lived electrons in covalent organic frameworks moiety which is transferred back from Rhenium<sup>I</sup>. This facilitates the two-electron reaction of carbon dioxide conversion to carbon monoxide.</p>}},
  author       = {{Pan, Qinying and Abdellah, Mohamed and Cao, Yuehan and Lin, Weihua and Liu, Yang and Meng, Jie and Zhou, Quan and Zhao, Qian and Yan, Xiaomei and Li, Zonglong and Cui, Hao and Cao, Huili and Fang, Wenting and Tanner, David Ackland and Abdel-Hafiez, Mahmoud and Zhou, Ying and Pullerits, Tonu and Canton, Sophie E. and Xu, Hong and Zheng, Kaibo}},
  issn         = {{2041-1723}},
  language     = {{eng}},
  month        = {{12}},
  number       = {{1}},
  publisher    = {{Nature Publishing Group}},
  series       = {{Nature Communications}},
  title        = {{Ultrafast charge transfer dynamics in 2D covalent organic frameworks/Re-complex hybrid photocatalyst}},
  url          = {{http://dx.doi.org/10.1038/s41467-022-28409-2}},
  doi          = {{10.1038/s41467-022-28409-2}},
  volume       = {{13}},
  year         = {{2022}},
}