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<p>Direct oxidation of methane to methanol is valuable, but reactive oxygen species over oxidize methane and lower selectivity. Here we report a Rh-Cu heteronuclear dual atom catalyst on nitrogen doped graphite that separates sites and restrains oxygen intermediates, enabling methanol through oxygen insertion into C-H bonds. An encapsulated pyrolysis strategy yields an Rh-Cu-N<sub>6</sub> motif with a Rh-Cu distance of 2.42 Å. Electronic coupling between Rh and Cu induces charge polarization and improves reactant activation. Cu captures active oxygen species, suppressing excessive oxygen insertion and deep oxidation. The catalyst achieves up to 81% methanol selectivity and about threefold higher activity than a single atom Rh catalyst. In situ Fourier transform infrared spectroscopy (FTIR) and density functional theory (DFT) calculations reveal stable oxygen bridged intermediates, Rh-O-O-Cu and Rh-O-Cu. Rh stabilizes methyl intermediates, while Cu restrains nearby oxygen reactivity and directs oxygen insertion into C-H bonds to form methanol.</p>

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Coordination restraint of Rh-Cu diatomic catalyst and C-H bond oxygen insertion for methanol synthesis

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年2月28日

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  • Haobo Zhao,
  • Yanling Gao,
  • Yi Wang,
  • Zhongqing Yang,
  • Nianbing Li,
  • Jingyu Ran,
  • Haojie Geng

摘要

Direct oxidation of methane to methanol is valuable, but reactive oxygen species over oxidize methane and lower selectivity. Here we report a Rh-Cu heteronuclear dual atom catalyst on nitrogen doped graphite that separates sites and restrains oxygen intermediates, enabling methanol through oxygen insertion into C-H bonds. An encapsulated pyrolysis strategy yields an Rh-Cu-N6 motif with a Rh-Cu distance of 2.42 Å. Electronic coupling between Rh and Cu induces charge polarization and improves reactant activation. Cu captures active oxygen species, suppressing excessive oxygen insertion and deep oxidation. The catalyst achieves up to 81% methanol selectivity and about threefold higher activity than a single atom Rh catalyst. In situ Fourier transform infrared spectroscopy (FTIR) and density functional theory (DFT) calculations reveal stable oxygen bridged intermediates, Rh-O-O-Cu and Rh-O-Cu. Rh stabilizes methyl intermediates, while Cu restrains nearby oxygen reactivity and directs oxygen insertion into C-H bonds to form methanol.