Here we report the first work on the synthesis of a series of xIn-CuO model catalysts for the Rochow reaction with formed P–N junctions at interfaces and with different In/Cu molar ratios. These composites were prepared by a one-pot hydrothermal method using metal nitrate salts and K₂CO₃ as the precursors and precipitant, respectively. Scanning electron microscopy and transmission electron microscopy characterization revealed the formation of the P–N junctions at the hetero-interfaces between CuO and In₂O₃, and X-ray photoelectron spectroscopy and H₂ temperature-programmed reduction demonstrated a strong interaction between the CuO and In₂O₃ phases. The addition of In₂O₃ increased the electron density in the Cu nucleus, causing Cu²⁺ and In³⁺ to become less and more positively charged, respectively. When used for the Rochow reaction, the catalyst 2In–CuO (2wt.% In on CuO) exhibited a significantly higher Si conversion and dimethyldichlorosilane ((CH₃)₂SiCl₂, M2) selectivity than CuO, which is attributed to the formation of P–N junctions that can facilitate the charge transfer. In addition, the detailed characterizations of the fresh and spent contact masses indicated that the Rochow reaction occurred on the Si surface and probably in the areas between ultrathin two-dimensional Cu–Si species and Cu doping deposits. In₂O₃ species promote the outward spreading of Cu^∗ (intermediate species) and improve the Cu^∗ diffusion rate at the reactive interfaces. This work not only deepens the fundamental understanding of the Rochow reaction, but also provides a new approach for the design of more efficient Cu-based catalysts by adding promoters such as In₂O₃ and by engineering the interfaces.

中文翻译：

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Rochow反应中In2O3对CuO的促进作用：异质界面上P–N结的形成

在这里，我们报告了有关用于Rochow反应的一系列xIn-CuO模型催化剂的合成的第一项工作，该Rochow反应在界面处形成了P-N键，并且具有不同的In / Cu摩尔比。这些复合材料是通过一锅法水热法制备的，分别使用金属硝酸盐和K ₂ CO ₃作为前体和沉淀剂。扫描电子显微镜和透射电子显微镜表征表明，在CuO和In ₂ O ₃之间的异质界面上形成了P–N结，X射线光电子能谱和H _2程序升温还原表明CuO之间有很强的相互作用和In ₂ O ₃阶段。In ₂ O _3的添加增加了Cu核中的电子密度，导致Cu ²⁺和In ³⁺分别带负电和带正电。当用于Rochow反应时，催化剂2In–CuO（占CuO的2wt。％In）表现出明显更高的Si转化率和二甲基二氯硅烷（（CH ₃）₂ SiCl ₂，M2）的选择性比CuO高，这归因于可以促进电荷转移的P–N结的形成。另外，对新鲜和废接触物质的详细表征表明，Rochow反应发生在Si表面上，并且可能在超薄二维Cu-Si物种与Cu掺杂沉积物之间的区域中发生。在₂ O _3中，促进了Cu ^*（中间物种）的向外扩散，并提高了Cu ^*在反应性界面处的扩散速率。这项工作不仅加深了对Rochow反应的基本了解，而且通过添加诸如In ₂ O _3的促进剂，为设计更有效的Cu基催化剂提供了一种新方法。 并通过设计接口。