Bu Fanle, Xue Yurui, Sun Mingzi, Huang Bolong, Yan Jiayu, Qi Lu, Zhao Shuya, Li Yuliang
Shandong Provincial Key Laboratory for Science of Material Creation and Energy Conversion, Science Center for Material Creation and Energy Conversion, School of Chemistry and Chemical Engineering, Shandong University, Jinan, China.
Department of Chemistry, City University of Hong Kong, Kowloon, Hong Kong SAR, China.
Nat Commun. 2025 Aug 12;16(1):7466. doi: 10.1038/s41467-025-62785-9.
The efficient conversion of methane to valuable C liquid oxygenates still remains silent. Here we show a new catalytic system of C-C coupling towards the C liquid oxygenates with high selectivity and productivity by the selective anchoring zero-valent ruthenium atoms from individual ones to two and three atoms in the electron-rich 18-carbon cavity of graphdiyne. Theoretical calculations demonstrate that Ru-GDY supplies neighboring robust active sites to promote efficient C-C coupling to C liquid oxygenates, due to the p-d coupling resonance that guarantees the distributed charge among Ru sites resulting in active region to accelerate the methane oxidation. Our results show Ru atoms in GDY enable the highly efficient and selective activation of CH to the key ·CH and ·CHOH intermediates, which allows the selective C-C coupling to gain C liquid oxygenates and shows the high selectivity (67%) and yields (7.25 mmol g h) towards C liquid oxygenates.
甲烷向有价值的含碳液态氧化合物的高效转化仍然没有进展。在此，我们展示了一种用于碳-碳偶联生成含碳液态氧化合物的新型催化体系，该体系通过在富电子的石墨炔18碳空腔中，将零价钌原子从单个选择性锚定到两个和三个原子，从而具有高选择性和高生产率。理论计算表明，由于p-d耦合共振保证了钌位点之间的电荷分布，从而产生活性区域以加速甲烷氧化，Ru-GDY提供相邻的强大活性位点以促进碳-碳高效偶联生成含碳液态氧化合物。我们的结果表明，石墨炔中的钌原子能够高效且选择性地将CH活化成关键的·CH和·CHOH中间体，这使得能够通过选择性碳-碳偶联获得含碳液态氧化合物，并显示出对含碳液态氧化合物的高选择性（67%）和产率（7.25 mmol g⁻¹ h⁻¹）。
