Authors
Qingping Ke, Meiying Niu, Xixi Liu, Jun Tang, Yuhao Zheng, Xiaohui Liu, Zhipeng Chen, Chao Wan, Liang Huang, Xiantai Zhou, Can Xue, Zehui Zhang
Published in
Angewandte Chemie (International ed. in English). Pages e5879363. Sep 27, 2026. Epub Sep 27, 2026.
Abstract
The development of noble-metal-free heterogeneous catalysts for room-temperature aerobic ammoxidation of alcohols to nitriles represents an enduring challenge, primarily hampered by unselective lattice-oxygen over-oxidation via the classical Mars-van Krevelen (MvK) pathway and strong site-blocking effects. Herein, we report a dual-anion (C/N) doped MnOx (C/N-MnOx) synthesized via a green, solvent-free crystallization strategy, which exhibits excellent catalytic performance (95.3% benzyl alcohol conversion, >99% benzonitrile selectivity) and broad substrate versatility (35 diverse alcohol substrates) under ambient conditions (25°C, 1 atm O2) without external energy inputs. Structural analyses and theoretical calculations demonstrate that N-doping introduces medium-strong Lewis acidic Mn-N sites to capture NH3, while C-doping generates localized oxygen vacancies for O2 activation. Crucially, kinetic isotope effect experiments and density functional theory (DFT) calculations prove that this anion dopant-programmed relay catalysis successfully bypasses the MvK pathway, fundamentally shifting the rate-determining step from initial alcohol dehydrogenation to the homolytic α-C-H bond scission of the aldimine intermediate. This work presents a paradigm shift in designing multifunctional non-precious catalysts for ambient-condition green organic transformations.
PMID:
42801502
Bibliographic data and abstract were imported from PubMed on 28 Sep 2026.
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