Boosting hydrogen transfer catalysis by symmetry breaking of iron site
(2025) In Applied Catalysis B: Environmental 385.- Abstract
Hydrogen transfer reactions hold pivotal importance in organic synthesis by enabling selective bond formation, achieving redox-neutral transformations, and advancing sustainable methodologies. However, designing efficient catalytic systems for such reactions under mild conditions persists as a fundamental challenge in green chemistry. In this study, we present a controllable synthesis of defective graphene-anchored iron single-atom catalysts (Fe1-DG SACs) through a hydrothermal-etching strategy. Findings reveal that micron-sized metallic Fe precursors spontaneously evolve into Fe nanoparticles and anchored on DG (FeNPs-DG), whereas Fe(II) and Fe(III) precursors yield larger Fe2O3... (More)
Hydrogen transfer reactions hold pivotal importance in organic synthesis by enabling selective bond formation, achieving redox-neutral transformations, and advancing sustainable methodologies. However, designing efficient catalytic systems for such reactions under mild conditions persists as a fundamental challenge in green chemistry. In this study, we present a controllable synthesis of defective graphene-anchored iron single-atom catalysts (Fe1-DG SACs) through a hydrothermal-etching strategy. Findings reveal that micron-sized metallic Fe precursors spontaneously evolve into Fe nanoparticles and anchored on DG (FeNPs-DG), whereas Fe(II) and Fe(III) precursors yield larger Fe2O3 nanoparticles, exhibiting an intrinsic oxidation resistance of metallic iron in the hydrothermal system. Subsequent HCl etching of FeNPs-DG generates well dispersed single Fe atoms with symmetry-broken Fe-N4 coordination structure. Remarkably, the single-atom catalyst displays an identical catalytic efficiency to its nanosized counterpart (FeNPs-DG) in hydrazine-mediated hydrogen transfer reduction of nitroaromatics under ambient conditions, attaining a turnover frequency of 6095.1 h−1 for p-nitrophenol reduction while maximizing metal utilization. Multidisciplinary characterizations and theoretical calculations demonstrate that the asymmetric Fe-N4 configuration enables dual-function catalysis: simultaneously activating hydrazine dehydrogenation and steering selective hydrogen transfer to nitroaromatics. This work advances atomic-scale understanding of symmetry engineering in single-atom catalysts and establishes a green paradigm for hydrogen transfer reactions under mild condition.
(Less)
- author
- Xiong, Miao ; Li, Shuo ; Bi, Zhuoyuan ; Liu, Pei LU ; Xue, Wenxuan ; Dai, Jianhong and Xi, Jiangbo
- organization
- publishing date
- 2025-12-15
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Catalytic Mechanism, Coordination structure, Hydrogen transfer reaction, Maximum atomic utilization, Single-atom catalyst
- in
- Applied Catalysis B: Environmental
- volume
- 385
- article number
- 126320
- publisher
- Elsevier
- external identifiers
-
- scopus:105024896024
- ISSN
- 0926-3373
- DOI
- 10.1016/j.apcatb.2025.126320
- language
- English
- LU publication?
- yes
- additional info
- Publisher Copyright: © 2025 Elsevier B.V.
- id
- 6a349d4a-1898-48c2-8ef5-518ae97a563d
- date added to LUP
- 2026-03-10 15:11:18
- date last changed
- 2026-03-10 15:12:23
@article{6a349d4a-1898-48c2-8ef5-518ae97a563d,
abstract = {{<p>Hydrogen transfer reactions hold pivotal importance in organic synthesis by enabling selective bond formation, achieving redox-neutral transformations, and advancing sustainable methodologies. However, designing efficient catalytic systems for such reactions under mild conditions persists as a fundamental challenge in green chemistry. In this study, we present a controllable synthesis of defective graphene-anchored iron single-atom catalysts (Fe<sub>1</sub>-DG SACs) through a hydrothermal-etching strategy. Findings reveal that micron-sized metallic Fe precursors spontaneously evolve into Fe nanoparticles and anchored on DG (Fe<sub>NPs</sub>-DG), whereas Fe(II) and Fe(III) precursors yield larger Fe<sub>2</sub>O<sub>3</sub> nanoparticles, exhibiting an intrinsic oxidation resistance of metallic iron in the hydrothermal system. Subsequent HCl etching of Fe<sub>NPs</sub>-DG generates well dispersed single Fe atoms with symmetry-broken Fe-N<sub>4</sub> coordination structure. Remarkably, the single-atom catalyst displays an identical catalytic efficiency to its nanosized counterpart (Fe<sub>NPs</sub>-DG) in hydrazine-mediated hydrogen transfer reduction of nitroaromatics under ambient conditions, attaining a turnover frequency of 6095.1 h<sup>−1</sup> for p-nitrophenol reduction while maximizing metal utilization. Multidisciplinary characterizations and theoretical calculations demonstrate that the asymmetric Fe-N<sub>4</sub> configuration enables dual-function catalysis: simultaneously activating hydrazine dehydrogenation and steering selective hydrogen transfer to nitroaromatics. This work advances atomic-scale understanding of symmetry engineering in single-atom catalysts and establishes a green paradigm for hydrogen transfer reactions under mild condition.</p>}},
author = {{Xiong, Miao and Li, Shuo and Bi, Zhuoyuan and Liu, Pei and Xue, Wenxuan and Dai, Jianhong and Xi, Jiangbo}},
issn = {{0926-3373}},
keywords = {{Catalytic Mechanism; Coordination structure; Hydrogen transfer reaction; Maximum atomic utilization; Single-atom catalyst}},
language = {{eng}},
month = {{12}},
publisher = {{Elsevier}},
series = {{Applied Catalysis B: Environmental}},
title = {{Boosting hydrogen transfer catalysis by symmetry breaking of iron site}},
url = {{http://dx.doi.org/10.1016/j.apcatb.2025.126320}},
doi = {{10.1016/j.apcatb.2025.126320}},
volume = {{385}},
year = {{2025}},
}