Chen Siao, Xue Yurui, Gao Yang, Wu Han, Zheng Xuchen, Li Yuliang
Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
Sci Adv. 2025 Aug 29;11(35):eadu9264. doi: 10.1126/sciadv.adu9264.
The highly negative reduction potential prevents the selective coupling of two aldehydes to construct C─C bonds and hinders the formation of ketyl radicals. However, this important comprehensive issue remains unsolved. Here, we report the efficient activation of aldehydes by the in situ growth of a molybdenum selenide-graphdiyne heterointerface structure, allowing an aldehyde molecule to be selectively coupled with another aldehyde at room temperature and ambient pressure. High-resolution transmission electron microscopy and scanning transmission electron microscopy (HAADF-STEM) images reveal the formation of high-density active sites at the interface structure. The synchrotron x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and electron paramagnetic resonance spectroscopy results confirmed the selective formation of ketyl radicals. The noninteger charge transfer between graphdiyne and metal atoms promotes the continuous selectivity and efficient activation of aldehydes and C─C coupling of ketyl radicals. The ultrahigh selectivity of 2-furaldehyde for hydrofurion reached 92 ± 2%, while the turnover frequency reached 57 ± 4 per second.
高度负的还原电位阻碍了两个醛的选择性偶联以构建碳-碳键，并妨碍了酮基自由基的形成。然而，这个重要的综合问题仍然没有得到解决。在此，我们报道了通过原位生长硒化钼-石墨二炔异质界面结构实现醛的有效活化，使得醛分子在室温和常压下能够与另一个醛选择性偶联。高分辨率透射电子显微镜和扫描透射电子显微镜（高角度环形暗场扫描透射电子显微镜）图像揭示了在界面结构处形成了高密度活性位点。同步辐射X射线光电子能谱、X射线吸收光谱和电子顺磁共振光谱结果证实了酮基自由基的选择性形成。石墨二炔与金属原子之间的非整数电荷转移促进了醛的持续选择性和有效活化以及酮基自由基的碳-碳偶联。2-糠醛对氢呋喃的超高选择性达到92±2%，而转化频率达到每秒57±4。
