In situgenerating Cu₂O/Cu heterointerfaces on the Cu₂O cube surface to enhance interface charge transfer for the Rochow reaction

TY - JOUR

T1 - In situgenerating Cu2O/Cu heterointerfaces on the Cu2O cube surface to enhance interface charge transfer for the Rochow reaction

AU - Tang, Fei

AU - Li, Jing

AU - Zhu, Yongxia

AU - Ji, Yongjun

AU - Li, Huifang

AU - Liu, Hezhi

AU - Wang, Xueguang

AU - Zhong, Ziyi

AU - Su, Fabing

N1 - Publisher Copyright: © The Royal Society of Chemistry 2021.

PY - 2021/3/21

Y1 - 2021/3/21

N2 - In heterogeneous catalysis, successful design and construction of the desired oxide-metal interface are critical to catalytic function due to the significant interfacial effects. However, there are still challenges and obscurities in constructing and understanding the structure of various interfacial sites and their oxide-metal interactions. In the present work, a series of cubic Cu/Cu2O hetero-nanoparticles were synthesized byin situsurface restructuring cubic Cu2O nanoparticlesviaa simple reduction treatment. These nanoparticles were further used as the model catalyst for the Rochow reaction, an important industrial process for synthesizing organosilicon polymers. It is found that cubic Cu/Cu2O with appropriate heterointerfaces exhibited improved dimethyldichlorosilane (M2) selectivity, Si conversion, and stability because of a strong interaction between the Cu/Cu2O interface. The latter originates from the formation of Schottky junctions that enhance the charge transfer efficiency and the subsequent reduction of Cu+into Cu* (the active Cu atoms). Moreover, the easier cleavage of the Si-Si bond along the {110} crystal plane effectively generates Si* (the free Si atoms), which leads to inclined grooves on the surface of Si particles. The established transport and diffusion channels of Cu* and Si* greatly promoted the formation of the Cu3Si active phase and the subsequent methyl chlorosilane. This work provides a new fundamental understanding of Cu-based catalysts for the Rochow reaction and reveals a clear relationship between the Cu2O/metal heterointerface and the catalytic performance.

AB - In heterogeneous catalysis, successful design and construction of the desired oxide-metal interface are critical to catalytic function due to the significant interfacial effects. However, there are still challenges and obscurities in constructing and understanding the structure of various interfacial sites and their oxide-metal interactions. In the present work, a series of cubic Cu/Cu2O hetero-nanoparticles were synthesized byin situsurface restructuring cubic Cu2O nanoparticlesviaa simple reduction treatment. These nanoparticles were further used as the model catalyst for the Rochow reaction, an important industrial process for synthesizing organosilicon polymers. It is found that cubic Cu/Cu2O with appropriate heterointerfaces exhibited improved dimethyldichlorosilane (M2) selectivity, Si conversion, and stability because of a strong interaction between the Cu/Cu2O interface. The latter originates from the formation of Schottky junctions that enhance the charge transfer efficiency and the subsequent reduction of Cu+into Cu* (the active Cu atoms). Moreover, the easier cleavage of the Si-Si bond along the {110} crystal plane effectively generates Si* (the free Si atoms), which leads to inclined grooves on the surface of Si particles. The established transport and diffusion channels of Cu* and Si* greatly promoted the formation of the Cu3Si active phase and the subsequent methyl chlorosilane. This work provides a new fundamental understanding of Cu-based catalysts for the Rochow reaction and reveals a clear relationship between the Cu2O/metal heterointerface and the catalytic performance.

UR - http://www.scopus.com/inward/record.url?scp=85103687419&partnerID=8YFLogxK

U2 - 10.1039/d0cy02015j

DO - 10.1039/d0cy02015j

M3 - 文章

AN - SCOPUS:85103687419

SN - 2044-4753

VL - 11

SP - 2202

EP - 2213

JO - Catalysis Science and Technology

JF - Catalysis Science and Technology

IS - 6

ER -