Fe─S Bond-Mediated Efficient Electron Transfer in Quantum Dots/Metal-Organic Frameworks for Boosting Photoelectrocatalytic Nitrogen Fixation
(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
- Jiang, Yuman LU ; Zhang, Fengying LU ; Mei, Yanglin ; Li, Tingsong ; Li, Yixuan ; Zheng, Kaibo LU ; Guo, Heng ; Yang, Guidong and Zhou, Ying
- organization
- publishing date
- 2024-11
- 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}}, }