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Fe─S Bond-Mediated Efficient Electron Transfer in Quantum Dots/Metal-Organic Frameworks for Boosting Photoelectrocatalytic Nitrogen Fixation

Jiang, Yuman LU ; Zhang, Fengying LU ; Mei, Yanglin ; Li, Tingsong ; Li, Yixuan ; Zheng, Kaibo LU ; Guo, Heng ; Yang, Guidong and Zhou, Ying (2024) In Small 20(48).
Abstract

Effective electron supply to produce ammonia in photoelectrochemical nitrogen reduction reaction (PEC NRR) remains challenging due to the sluggish multiple proton-coupled electron transfer and unfavorable carrier recombination. Herein, InP quantum dots decorated with sulfur ligands (InP QDs-S2−) bound to MIL-100(Fe) as a benchmark catalyst for PEC NRR is reported. It is found that MIL-100(Fe) can combined with InP QDs-S2− via Fe─S bonds as bridge to facilitate the electron transfer by experimental results. The formation of Fe─S bonds can facilitate electron transfer from inorganic S2− ligands of InP QDs to the Fe metal sites of MIL-100(Fe) within 52 ps, ensuring a more efficient electron transfer and... (More)

Effective electron supply to produce ammonia in photoelectrochemical nitrogen reduction reaction (PEC NRR) remains challenging due to the sluggish multiple proton-coupled electron transfer and unfavorable carrier recombination. Herein, InP quantum dots decorated with sulfur ligands (InP QDs-S2−) bound to MIL-100(Fe) as a benchmark catalyst for PEC NRR is reported. It is found that MIL-100(Fe) can combined with InP QDs-S2− via Fe─S bonds as bridge to facilitate the electron transfer by experimental results. The formation of Fe─S bonds can facilitate electron transfer from inorganic S2− ligands of InP QDs to the Fe metal sites of MIL-100(Fe) within 52 ps, ensuring a more efficient electron transfer and electron-hole separation confirmed by the time-resolved spectroscopy. More importantly, the process of photo-induced carrier transfer can be traced by in situ attenuated total reflection surface-enhanced infrared tests, certifying that the effective electron transfer can promote N≡N dissociation and N2 hydrogenation. As a result, InP QDs-S2−/MIL-100(Fe) exhibits prominent performance with an outstanding NH3 yield of 0.58 µmol cm−2 h−1 (3.09 times higher than that of MIL-100(Fe)). This work reveals an important ultrafast dynamic mechanism for PEC NRR in QDs modified metal-organic frameworks, providing a new guideline for the rational design of efficient MOFs photocathodes.

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author
; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
carrier dynamics, metal-organic frameworks, photoelectrochemical nitrogen reduction, quantum dots, transient absorption spectroscopy
in
Small
volume
20
issue
48
article number
2405512
publisher
John Wiley & Sons Inc.
external identifiers
  • pmid:39233536
  • scopus:85203086983
ISSN
1613-6810
DOI
10.1002/smll.202405512
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2024 Wiley-VCH GmbH.
id
f467844f-a6c2-4254-bd64-d99b02a8c70b
date added to LUP
2024-12-03 16:01:11
date last changed
2025-07-02 09:27:59
@article{f467844f-a6c2-4254-bd64-d99b02a8c70b,
  abstract     = {{<p>Effective electron supply to produce ammonia in photoelectrochemical nitrogen reduction reaction (PEC NRR) remains challenging due to the sluggish multiple proton-coupled electron transfer and unfavorable carrier recombination. Herein, InP quantum dots decorated with sulfur ligands (InP QDs-S<sup>2−</sup>) bound to MIL-100(Fe) as a benchmark catalyst for PEC NRR is reported. It is found that MIL-100(Fe) can combined with InP QDs-S<sup>2−</sup> via Fe─S bonds as bridge to facilitate the electron transfer by experimental results. The formation of Fe─S bonds can facilitate electron transfer from inorganic S<sup>2−</sup> ligands of InP QDs to the Fe metal sites of MIL-100(Fe) within 52 ps, ensuring a more efficient electron transfer and electron-hole separation confirmed by the time-resolved spectroscopy. More importantly, the process of photo-induced carrier transfer can be traced by in situ attenuated total reflection surface-enhanced infrared tests, certifying that the effective electron transfer can promote N≡N dissociation and N<sub>2</sub> hydrogenation. As a result, InP QDs-S<sup>2−</sup>/MIL-100(Fe) exhibits prominent performance with an outstanding NH<sub>3</sub> yield of 0.58 µmol cm<sup>−2</sup> h<sup>−1</sup> (3.09 times higher than that of MIL-100(Fe)). This work reveals an important ultrafast dynamic mechanism for PEC NRR in QDs modified metal-organic frameworks, providing a new guideline for the rational design of efficient MOFs photocathodes.</p>}},
  author       = {{Jiang, Yuman and Zhang, Fengying and Mei, Yanglin and Li, Tingsong and Li, Yixuan and Zheng, Kaibo and Guo, Heng and Yang, Guidong and Zhou, Ying}},
  issn         = {{1613-6810}},
  keywords     = {{carrier dynamics; metal-organic frameworks; photoelectrochemical nitrogen reduction; quantum dots; transient absorption spectroscopy}},
  language     = {{eng}},
  number       = {{48}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{Small}},
  title        = {{Fe─S Bond-Mediated Efficient Electron Transfer in Quantum Dots/Metal-Organic Frameworks for Boosting Photoelectrocatalytic Nitrogen Fixation}},
  url          = {{http://dx.doi.org/10.1002/smll.202405512}},
  doi          = {{10.1002/smll.202405512}},
  volume       = {{20}},
  year         = {{2024}},
}