Shape-controlled synthesis of Cu2O microparticles and their catalytic performances in the Rochow reaction

We report the preparation of Cu2O microparticles with different shapes, by simple hydrolyzation and reduction of copper acetate with glucose in a mixture of water–ethanol solvent. The effect of the synthesis conditions on the shape of the Cu2O microparticles and their catalytic properties in the Rochow reaction were investigated. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, temperature-programmed reduction, and thermogravimetric analysis. Cu2O microparticles with different shapes, such as hexahedron, ananas-like, sphere-like, and star-like shapes, with particle sizes of 2–4 μm, were obtained by tuning the volume ratio of water : ethanol. The hexahedron Cu2O microparticles were found to exhibit the best catalytic performance for the synthesis of dimethyldichlorosilane via the Rochow reaction. This work should be helpful in the design and development of novel copper catalysts for organosilane synthesis and understanding their catalytic roles.

[1]  Alexander D. Gordon,et al.  Effects of Multiple Promotion of the Direct Synthesis Contact Mass with P, Zn, and Sn on the Synthesis of Methylchlorosilanes , 2009 .

[2]  S. De,et al.  Template-free synthesis of mesoporous CuO dandelion structures for optoelectronic applications. , 2010, ACS applied materials & interfaces.

[3]  H. Kwon,et al.  Gram‐Scale Synthesis of Cu2O Nanocubes and Subsequent Oxidation to CuO Hollow Nanostructures for Lithium‐Ion Battery Anode Materials , 2009 .

[4]  Jinfu Wang,et al.  Effect of CuCl particle size on the reduction reaction by silicon in preparation of contact mass used for methylchlorosilane synthesis , 2006 .

[5]  J. C. Vlugter,et al.  Mechanism and kinetics of the metal-catalyzed synthesis of methylchlorosilanes: II. The kinetics of the copper-catalyzed reaction of methyl chloride and silicon , 1965 .

[6]  Qing Peng,et al.  Nearly Monodisperse Cu2O and CuO Nanospheres: Preparation and Applications for Sensitive Gas Sensors , 2006 .

[7]  Jiajian Gao,et al.  Facile Synthesis of Mesoporous Cu2O Microspheres with Improved Catalytic Property for Dimethyldichlorosilane Synthesis , 2012 .

[8]  David Chadwick,et al.  The influence of point defects on the resistance of ceria to carbon deposition in hydrocarbon catalysis , 2000 .

[9]  Timothy C. Frank,et al.  Catalytic formation of silanes on copper-silicon alloys , 1985 .

[10]  H. Zeng,et al.  Controlled Synthesis and Self-Assembly of Single-Crystalline CuO Nanorods and Nanoribbons , 2004 .

[11]  Jinghui Zeng,et al.  Hydrothermal Synthesis of Uniform Cuprous Oxide Microcrystals with Controlled Morphology , 2008 .

[12]  Wenzhong Wang,et al.  Shape evolution and size-controllable synthesis of Cu2O octahedra and their morphology-dependent photocatalytic properties. , 2006, The journal of physical chemistry. B.

[13]  L. Lewis,et al.  Mechanism of the methylchlorosilane reaction: Improved lab reactor design and kinetic data , 2003 .

[14]  Song Jin,et al.  Facile and mild solution synthesis of Cu2O nanowires and nanotubes driven by screw dislocations. , 2012, Chemical communications.

[15]  Jiajian Gao,et al.  Flower-like CuO microspheres with enhanced catalytic performance for dimethyldichlorosilane synthesis , 2012 .

[16]  Li Zhang,et al.  Interior Structural Tailoring of Cu2O Shell-in-Shell Nanostructures through Multistep Ostwald Ripening , 2011 .

[17]  Guanzhong Wang,et al.  Synthesis of sub-10 nm Cu2O Nanowires by Poly(vinyl pyrrolidone)-Assisted Electrodeposition , 2009 .

[18]  J. C. Vlugter,et al.  Mechanism and kinetics of the metal-catalyzed synthesis of methylchlorosilanes: I. The synthesis of methylchlorosilanes in a fluid bed , 1964 .

[19]  Xiaoping Song,et al.  The crystal-facet-dependent effect of polyhedral Cu2O microcrystals on photocatalytic activity , 2012 .

[20]  E. G. Rochow.  The Direct Synthesis of Organosilicon Compounds , 1945 .

[21]  Haitao Zhu,et al.  Fast Synthesis of Cu2O Hollow Microspheres and Their Application in DNA Biosensor of Hepatitis B Virus , 2009 .

[22]  D. Singh,et al.  Growth of Different Nanostructures of Cu2O (Nanothreads, Nanowires, and Nanocubes) by Simple Electrolysis Based Oxidation of Copper , 2007 .

[23]  J. Acker,et al.  Thermodynamic assessment of the copper catalyzed direct synthesis of methylchlorosilanes , 2008 .

[24]  Xue-mei Wang,et al.  Rapid synthesis of flower-like Cu2O architectures in ionic liquids by the assistance of microwave irradiation with high photochemical activity. , 2011, Dalton transactions.

[25]  Xiaoping Song,et al.  Selective-etching growth of urchin-like Cu2O architectures , 2011 .

[26]  Michael H. Huang,et al.  Facile Synthesis of Cu2O Nanocrystals with Systematic Shape Evolution from Cubic to Octahedral Structures , 2008 .

[27]  Ying Zhang,et al.  Shape Effects of Cu2O Polyhedral Microcrystals on Photocatalytic Activity , 2010 .

[28]  F. d'Heurle,et al.  The formation of Cu3Si: Marker experiments , 1990 .

[29]  Enbo Wang,et al.  A controllable synthetic route to Cu, Cu2O, and CuO nanotubes and nanorods. , 2003, Chemical communications.

[30]  L. Lewis,et al.  Effect of low aluminum silicon on the direct process , 2003 .

[31]  G. Yin,et al.  Fabrication of submicron Cu2O hollow spheres in an O/W/O multiple emulsions , 2004 .

[32]  Chunhua Wang,et al.  A room-temperature chemical route to homogeneous core–shell Cu2O structures and their application in biosensors , 2011 .

[33]  G. Sberveglieri,et al.  Synthesis of Cu2O bi-pyramids by reduction of Cu(OH)2 in solution , 2010 .

[34]  H. Zeng,et al.  Formation of colloidal CuO nanocrystallites and their spherical aggregation and reductive transformation to hollow Cu2O nanospheres. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[35]  B. Bent,et al.  Chemistry of the direct synthesis of methylchlorosilanes from methyl + chlorine monolayers on a Cu3Si surface , 1997 .

[36]  Jiaguo Yu,et al.  Template-free hydrothermal synthesis of CuO/Cu2O composite hollow microspheres , 2007 .

[37]  Poonam Sharma,et al.  Synthesis of fluorescent hollow and porous Cu2O nanopolyhedras in the presence of poly(vinyl pyrrolidone) , 2009 .

[38]  Wenzhong Wang,et al.  Template synthesis of multishelled Cu2O hollow spheres with a single-crystalline shell wall. , 2007, Angewandte Chemie.

[39]  M. Carter,et al.  Production of cuprous oxide, a solar cell material, by thermal oxidation and a study of its physical and electrical properties , 1998 .

[40]  W. J. Ward,et al.  The Use of a Fixed-Bed Reactor to Evaluate the Interactions of Catalysts and Promoters in the Methyl Chlorosilane Reaction and to Determine the Effect of Cu in the Form of the Eta Phase on This Reaction , 2002 .

[41]  Yadong Li,et al.  Catalysis based on nanocrystals with well-defined facets. , 2012, Angewandte Chemie.