One-dimensional Cu-based catalysts with layered Cu–Cu₂O–CuO walls for the Rochow reaction

A series of copper catalysts with a core–shell or tubular structure containing various contents of Cu, Cu₂O, and CuO were prepared via controlled oxidation of Cu nanowires (NWs) and used in the synthesis of dimethyldichlorosilane (M2) via the Rochow reaction. The Cu NWs were prepared from copper (Ⅱ) nitrate using a solution-based reduction method. The samples were characterized by X-ray diffraction, thermogravimetric analysis, temperature-programmed reduction, X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy. It was found that the morphology and composition of the catalysts could be tailored by varying the oxidation temperature and time. During the gradual oxidation of Cu NWs, the oxidation reaction initiated on the outer surface and gradually developed into the bulk of the NWs, leading to the formation of catalysts with various structures and layered compositions, e.g., Cu NWs with surface Cu₂O, ternary Cu–Cu₂O–CuO core–shell NWs, binary Cu₂O–CuO nanotubes (NTs), and single CuO NTs. Among these catalysts, ternary Cu–Cu₂O–CuO core–shell NWs exhibited superior M2 selectivity and Si conversion in the Rochow reaction. The enhanced catalytic performance was mainly attributed to improved mass and heat transfer resulting from the peculiar heterostructure and the synergistic effect among layered components. Our work indicated that the catalytic property of Cu-based nanoparticles can be improved by carefully controlling their structures and compositions.