Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

Boosting Photocatalytic N2 Reduction via Ligand-Engineered MOFs : Regulated Hole Utilization and Interfacial Water Coordination for Efficient Proton Supply

Jiang, Yuman LU ; Zhang, Fengying LU ; Mei, Yanglin ; Li, Yong LU ; Zheng, Kaibo LU ; Xu, Hong ; Guo, Heng ; Pullerits, Tonu LU and Zhou, Ying (2026) In ACS Nano 20(22). p.16305-16315
Abstract

Photocatalytic nitrogen reduction requires the concerted transfer of six electrons and six protons, where inefficient electron utilization and proton supply represent the critical limiting factors for proton-coupled electron transfer in this process. A key challenge lies in hole accumulation within photocatalysts, as hole transfer typically proceeds 2 to 3 orders of magnitude more slowly than electron transfer. This imbalance leads to charge recombination and sluggish water oxidation, limiting proton availability. In this work, we address these issues by engineering the ligands of metal–organic frameworks (MOFs) to serve as oxidation sites, enabling the simultaneous enhancement of hole extraction and water activation. In... (More)

Photocatalytic nitrogen reduction requires the concerted transfer of six electrons and six protons, where inefficient electron utilization and proton supply represent the critical limiting factors for proton-coupled electron transfer in this process. A key challenge lies in hole accumulation within photocatalysts, as hole transfer typically proceeds 2 to 3 orders of magnitude more slowly than electron transfer. This imbalance leads to charge recombination and sluggish water oxidation, limiting proton availability. In this work, we address these issues by engineering the ligands of metal–organic frameworks (MOFs) to serve as oxidation sites, enabling the simultaneous enhancement of hole extraction and water activation. In sulfonic-acid-functionalized MIL-101(Fe) (MIL-101(Fe)-SO3H), transient absorption spectroscopy (TAS) elucidates that photoinduced electrons are either efficiently injected to the metal center (∼986 ps) or trapped at defect states (∼9 ps), while the holes remain on organic ligands to drive water oxidation. Crucially, −SO3H groups restructure the interfacial water coordination to asymmetric configurations, facilitating the water dissociation and enhancing proton generation. Hence, MIL-101(Fe)-SO3H achieves an impressive NH3 selectivity (98.8%), surpassing that of pristine MIL-101(Fe). This work provides a rational strategy for boosting nitrogen reduction by engineering oxidation sites to promote the proton supply via coordinated control of charge transfer and water activation.

(Less)
Please use this url to cite or link to this publication:
author
; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
asymmetric hydrogen-bond networks, hole utilization, ligand engineering, metal−organic frameworks, photocatalytic nitrogen reduction
in
ACS Nano
volume
20
issue
22
pages
11 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:42190163
  • scopus:105041299507
ISSN
1936-0851
DOI
10.1021/acsnano.6c03885
language
English
LU publication?
yes
id
52c3d8c1-eec1-4fbc-9cfd-03130bcbb8aa
date added to LUP
2026-09-10 15:13:35
date last changed
2026-09-10 15:14:22
@article{52c3d8c1-eec1-4fbc-9cfd-03130bcbb8aa,
  abstract     = {{<p>Photocatalytic nitrogen reduction requires the concerted transfer of six electrons and six protons, where inefficient electron utilization and proton supply represent the critical limiting factors for proton-coupled electron transfer in this process. A key challenge lies in hole accumulation within photocatalysts, as hole transfer typically proceeds 2 to 3 orders of magnitude more slowly than electron transfer. This imbalance leads to charge recombination and sluggish water oxidation, limiting proton availability. In this work, we address these issues by engineering the ligands of metal–organic frameworks (MOFs) to serve as oxidation sites, enabling the simultaneous enhancement of hole extraction and water activation. In sulfonic-acid-functionalized MIL-101(Fe) (MIL-101(Fe)-SO<sub>3</sub>H), transient absorption spectroscopy (TAS) elucidates that photoinduced electrons are either efficiently injected to the metal center (∼986 ps) or trapped at defect states (∼9 ps), while the holes remain on organic ligands to drive water oxidation. Crucially, −SO<sub>3</sub>H groups restructure the interfacial water coordination to asymmetric configurations, facilitating the water dissociation and enhancing proton generation. Hence, MIL-101(Fe)-SO<sub>3</sub>H achieves an impressive NH<sub>3</sub> selectivity (98.8%), surpassing that of pristine MIL-101(Fe). This work provides a rational strategy for boosting nitrogen reduction by engineering oxidation sites to promote the proton supply via coordinated control of charge transfer and water activation.</p>}},
  author       = {{Jiang, Yuman and Zhang, Fengying and Mei, Yanglin and Li, Yong and Zheng, Kaibo and Xu, Hong and Guo, Heng and Pullerits, Tonu and Zhou, Ying}},
  issn         = {{1936-0851}},
  keywords     = {{asymmetric hydrogen-bond networks; hole utilization; ligand engineering; metal−organic frameworks; photocatalytic nitrogen reduction}},
  language     = {{eng}},
  number       = {{22}},
  pages        = {{16305--16315}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{ACS Nano}},
  title        = {{Boosting Photocatalytic N<sub>2</sub> Reduction via Ligand-Engineered MOFs : Regulated Hole Utilization and Interfacial Water Coordination for Efficient Proton Supply}},
  url          = {{http://dx.doi.org/10.1021/acsnano.6c03885}},
  doi          = {{10.1021/acsnano.6c03885}},
  volume       = {{20}},
  year         = {{2026}},
}