@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}},
}