Ultrafast charge transfer dynamics in 2D covalent organic frameworks/Re-complex hybrid photocatalyst
(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.
(Less)
- author
- organization
- publishing date
- 2022
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Nature Communications
- volume
- 13
- issue
- 1
- article number
- 845
- publisher
- Nature Publishing Group
- external identifiers
-
- pmid:35149679
- scopus:85124578805
- 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
- 2024-09-19 21:39:08
@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}}, 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}}, }